阅读说明：本技术 纺织品着色方法 (Textile colouring process ) 是由 本锡安.兰达 萨希.阿布拉莫维奇 于 2019-01-22 设计创作，主要内容包括：本发明公开了涂覆哺乳动物毛发或纺织纤维的方法,所述方法包括：在纺织纤维的外表面涂覆预处理水包油乳液,其包括：(i)包含水的水相；和(ii)包含可选地在额外反应物的存在下在缩合固化后形成氨基硅酮涂层的至少一种反应性可缩合固化成膜的氨基硅酮预聚物的预处理油相。所述预处理反应性油相包括至少一种预处理反应物或预处理预聚物。然后将包含亲水性聚合物材料的颗粒的水性分散体涂覆至所述氨基硅酮涂层,以便在其上形成聚合物层。形成第一涂层的水包油乳液中的至少一种和形成第二涂层的水分散体中的至少一种可进一步包含分散在其中的多种亚微米颜料颗粒。还公开了合适的组合物和包括该组合物的试剂盒,以及制备该组合物的方法。(The present invention discloses a method of coating mammalian hair or textile fibres, the method comprising: coating the outer surface of the textile fibers with a pre-treated oil-in-water emulsion comprising: (i) an aqueous phase comprising water; and (ii) a pre-treatment oil phase comprising at least one reactive condensation curable film-forming aminosilicone prepolymer which forms an aminosilicone coating upon condensation curing, optionally in the presence of additional reactants. The pretreatment reactive oil phase comprises at least one pretreatment reactant or pretreatment prepolymer. An aqueous dispersion comprising particles of a hydrophilic polymeric material is then applied to the aminosilicone coating so as to form a polymeric layer thereon. At least one of the oil-in-water emulsion forming the first coating and at least one of the aqueous dispersion forming the second coating may further comprise a plurality of sub-micron pigment particles dispersed therein. Suitable compositions and kits comprising the compositions, as well as methods of making the compositions, are also disclosed.)

1. A method of coating textile fibres, the method comprising:

(a) providing an oil phase comprising at least one reactive condensation curable film-forming aminosilicone prepolymer, the oil phase satisfying at least one of:

(i) the at least one reactive condensation curable film-forming aminosilicone prepolymer includes at least one reactive condensation curable film-forming aminosilicone monomer having a molecular weight of up to 1000 grams/mole; and

(ii) the oil phase further comprises a non-amino crosslinking agent adapted or selected to cure the at least one reactive condensation curable film-forming aminosilicone prepolymer, the non-amino crosslinking agent having a molecular weight of up to 1000 grams/mole;

wherein at least one of the reactive condensation curable film-forming aminosilicone prepolymer, the reactive condensation curable film-forming aminosilicone monomer, the non-amino crosslinker, or optionally any of a silicone oil, an aminosilicone oil, a pigment dispersant and a reactive hydrophobic inorganic filler further comprised in the oil phase is a water-rich reactant;

the water-rich reactant has a water content such that, after a length of time of pretreatment of the oil phase, the pretreated oil phase has at least 0.01 wt.%, at least 0.05 wt.%, at least 0.1 wt.%, at least 0.15 wt.%, at least 0.2 wt.%, at least 0.25 wt.%, at least 0.5 wt.%, at least 0.75 wt.%, or at least 1 wt.% water, and optionally has at most 8 wt.%, at most 7 wt.%, at most 5 wt.%, at most 2.5 wt.%, at most 2 wt.%, at most 1 wt.%, or at most 0.5 wt.% water, based on the weight of the pretreated oil phase;

(b) emulsifying the pre-treated oil phase with an aqueous phase to obtain a pre-treated oil-in-water emulsion;

(c) applying the pre-treated oil-in-water emulsion to the outer surface of the textile fibers; and

(d) after partial condensation curing of the polymer of the pre-treatment oil-in-water emulsion to form an at least partially cured aminosilicone coating on the outer surface of the textile fibers, applying an aqueous dispersion comprising a plurality of polymer particles made of a hydrophobic polymer material having neutralized acid moieties dispersed in the aqueous dispersion on the at least partially cured aminosilicone coating to produce an overlying polymer layer adhered to the outer surface of the aminosilicone coating.

2. The method of claim 1, wherein the volume ratio of oil phase and aqueous phase in the oil phase or the pre-treated oil phase, optionally without aqueous phase, is at least 9:1, at least 9.33:0.67, at least 9.5:0.5, or at least 9.75: 0.25.

3. The process of claim 1 or 2, wherein the water-rich reactant is obtained by adding an aqueous pretreatment solution to a substantially dry reactant comprising less than 1 wt.%, or less than 0.5 wt.%, or less than 0.1 wt.%, or less than 0.05 wt.%, or less than 0.01 wt.% water, by weight of dry reactant.

4. The process of any one of claims 1 to 3, wherein the water content of the water-rich reactant is obtained by adding at most 15 wt.%, at most 12.5 wt.%, at most 10 wt.%, and optionally at least 0.1 wt.%, at least 0.2 wt.%, or at least 0.3 wt.% of an aqueous pretreatment solution, based on the weight of the water-rich reactant prior to the addition.

5. The method of any of claims 1 to 4, wherein the pre-treatment oil phase is obtained by adding an aqueous pre-treatment solution to the oil phase in an amount of 8 wt.% or less, 7 wt.% or less, 5 wt.% or less, 2.5 wt.% or less, 1.0 wt.% or less, or 0.5 wt.% or less, and optionally 0.01 wt.% or more, 0.05 wt.% or more, or 0.1 wt.% or more, based on the weight of the oil phase.

6. The method of any one of claims 3 to 5, wherein the aqueous pretreatment solution consists essentially of distilled water having a pH in the range of 6.5 to 7.5.

7. The method of any one of claims 3 to 5, wherein the aqueous pretreatment solution further comprises an acid, optionally a volatile acid.

8. The method of claim 7, wherein the aqueous pretreatment solution has a pH in the range of 0.5 to 2.5, 0.5 to 2.0, 0.7 to 1.4, or 0.9 to 1.2.

9. The method of any one of claims 1 to 8, wherein the duration of the pretreatment of the oil phase is 24 hours or less, 4 hours or less, 2 hours or less, 1 hour or less, 30 minutes or less, 20 minutes or less, 10 minutes or less, or 5 minutes or less.

10. The method according to any one of claims 1 to 9, wherein a first aminosilicone prepolymer of the at least one reactive condensation curable film-forming aminosilicone prepolymer has at least 3 silanol and/or hydrolysable groups (3+ SiOH) to form a 3-dimensional network structure.

11. A method according to any one of claims 1 to 10, wherein the at least one reactive condensation curable film-forming aminosilicone prepolymer comprises reactive aminosilicone monomers having a solubility of less than 1%, less than 0.5% or less than 0.1% by weight in water at 23 ℃.

12. The method of any of claims 1-11, wherein the condensation-curable aminosilicone prepolymer comprises reactive groups selected from the group consisting of alkoxysilane reactive groups, silanol reactive groups, and combinations thereof.

13. The method of any of claims 1 to 12 wherein the oil phase or the pre-treated oil phase, free of all inorganic ingredients and any pigments, has no glass transition temperature.

14. The method of any one of claims 1 to 13, wherein the total concentration of the prepolymer, the non-amino crosslinker, the solid hydrophobic reactive inorganic filler, the aminosilicone oil, and the non-aminosilicone oil, including any pigment particles and dispersant for the pigment particles, in the oil phase or the pre-treatment oil phase is at least 90%, at least 93%, at least 95%, at least 97%, at least 98%, or at least 95% by weight.

15. The method of any one of claims 1 to 14, wherein the partial condensation curing is performed at a temperature of at most 75 ℃, at most 65 ℃, at most 55 ℃, at most 45 ℃, at most 38 ℃, at most 36 ℃, at most 34 ℃, or at most 32 ℃, and optionally, at a temperature of at least 15 ℃.

16. The method of any one of claims 1 to 15, wherein the oil-in-water emulsion or pre-treated oil-in-water emulsion has a surface electromotive force greater than zero, or is at least +1mV, at least +2mV, at least +3mV, at least +5mV, at least +7mV, at least +10mV, at least +15mV, at least +20mV, at least +30mV, at least +40mV, or at least +60 mV; and optionally at most +100mV or at most +80mV, said surface potential further optionally being measured at the natural pH of said oil-in-water emulsion.

17. The method of any one of claims 1 to 16, wherein the oil-in-water or pretreated oil-in-water emulsion has a first surface electromotive force (ζ 1) and a second electromotive force (ζ 2) at the pH of the aqueous dispersion, wherein a difference in electromotive force (Δ ζ) at the pH is defined as Δ ζ ═ ζ 1- ζ 2, and wherein Δ ζ, in millivolts (mV), satisfies at least one of:

(i) Δ ζ is at least 10, at least 15, at least 20, at least 25, at least 30, at least 40, or at least 50;

(ii) Δ ζ is in a range of 10 to 80, 10 to 70, 10 to 60, 15 to 80, 15 to 70, 15 to 60, 20 to 80, 20 to 70, 20 to 60, 25 to 80, 25 to 70, 25 to 60, 30 to 80, 30 to 70, 30 to 60, 35 to 80, 35 to 70, or 35 to 60;

(iii) the first surface electromotive force (ζ 1) is greater than zero (ζ 1>0) for the pH in a range of 4 to 11, 4 to 10.5, 4 to 10, 6 to 11, 6 to 10.5, 6 to 10, 7 to 11, 7 to 10.5, or 7 to 10.

18. The method of any one of claims 1 to 17, further comprising sufficiently converting the hydrophilic polymeric material to its conjugate acid to obtain a hydrophobic polymeric layer.

19. The method of any one of claims 1 to 18, wherein at least one of the oil phase, the pre-treated oil phase, or the polymer particles of hydrophobic polymer having neutralized acid moieties further comprises a pigment, optionally a plurality of submicron pigment particles.

20. The method of claim 19, wherein the oil phase or the pretreated oil phase comprises submicron pigment particles and further comprises a dispersant in which the submicron pigment particles are dispersed, optionally in an amount in the range of 25% to 400%, 50% to 200%, or 75% to 125% by weight of pigment.

21. The method of any one of claims 19 or 20, wherein the pre-treating oil-in-water emulsion comprises a first pigment and the aqueous dispersion comprises a second pigment.

22. The method of any one of claims 1 to 21, wherein the textile fiber is a natural keratin fiber.

23. The method of any one of claims 1 to 21, wherein the textile fiber is a natural non-keratin fiber.

24. The method of any one of claims 1 to 21, wherein the textile fibers are synthetic fibers.

25. A kit for producing a reactive composition for coating the outer surface of textile fibres, the kit comprising:

(A) a first oil phase compartment comprising a first oil phase comprising:

(i) at least one reactive condensation curable film-forming aminosilicone monomer having a molecular weight of up to 1000 g/mole; and optionally also,

(ii) a non-amino crosslinking agent; and further optionally also,

(iii) at least one of an aminosilicone oil and a non-aminosilicone oil; and further optionally also,

(iv) at least one reactive condensation curable film-forming aminosilicone prepolymer comprising at least one of a reactive condensation curable film-forming aminosilicone polymer and a reactive condensation curable film-forming aminosilicone oligomer;

(b) an aqueous dispersion compartment comprising an aqueous dispersion, the aqueous dispersion comprising:

(i) an aqueous medium; and

(ii) submicron particles comprising or made of a hydrophilic polymeric material having a neutralized acid moiety and disposed in an aqueous medium, each of at least a portion of the submicron particles optionally comprising at least one pigment particle, the at least one pigment particle optionally being at least partially encapsulated by the polymeric material; and

(c) an optional second oil phase compartment comprising a second oil phase comprising:

(i) at least one of an aminosilicone oil and a non-aminosilicone oil, and optionally,

(ii) a solid hydrophobic reactive inorganic filler; and further optionally also,

(iii) at least one reactive condensation curable film-forming aminosilicone prepolymer comprising at least one of a reactive condensation curable film-forming aminosilicone polymer and a reactive condensation curable film-forming aminosilicone oligomer; and further optionally also,

(iv) pigment particles disposed in the second oil phase;

wherein at least one of the first oil phase compartment or the optional second oil phase compartment further comprises an aqueous pretreatment solution; and is

Wherein the kit further optionally comprises at least one of a thickener, an emulsifier, a surfactant, and a dispersion.

26. A kit according to claim 25, wherein at least one of i) the aqueous dispersion compartment (b) and ii) the second oil phase compartment (c) further comprises a pigment, optionally consisting of a plurality of sub-micron pigment particles, at least one of which, if present in an aqueous dispersion, is optionally at least partially encapsulated by the polymeric material, in the respective aqueous dispersion and/or second oil phase.

Technical Field

The present invention relates to a method for coloring textiles and fibers thereof. The invention also relates to a method for preparing a suitable colouring composition and to a kit capable of implementing such a method.

Background

In textile manufacturing, coloration is one of the most important steps in providing the final appearance (including color and luster) to the cloth. There are many different coloring methods with different effects depending on the type of textile fibers constituting the yarn and cloth and when they are used in the manufacturing process.

Textile fibers may be of natural origin or may be made synthetically from synthetic polymers. Natural fibers typically exhibit large differences in the length, shape and quality of their individual constituent filaments, and may also contain impurities derived from the animal or plant from which they are derived. Man-made or synthetic fibers prepared under controlled conditions generally have more uniform properties and may generally contain less impurities that are detrimental to color.

Natural fibers include keratin fibers of animal origin, such as wool, silk, mohair or cashmere; and cellulose fibers of plant origin, such as cotton, flax, ramie or hemp. Rayon includes synthetic fibers such as nylon, polyester, acrylic, rayon, or polyolefin; and regenerated fibers such as viscose or cellulose acetate. Synthetic fibers may be manufactured according to desired specifications, e.g., having predetermined dimensions (e.g., diameter), mechanical properties, and even color shades (e.g., mixing colorants with a polymer prior to forming the strands). While natural fibers are generally prepared as follows.

Filament fibers are spun or otherwise combined together to form a filament, which in turn can be assembled to form a yarn, which can be arranged by a variety of techniques (e.g., by weaving, knitting, crocheting, felting, sewing, etc.) to form a cloth. The cloth may then be cut and/or the various sheets assembled to form any desired article (e.g., a garment) made of a textile.

The colouring of textile fibres can be carried out at the thread or yarn stage, at the clothing stage or at the garment stage, each stage having its own advantages and disadvantages. For example, the coloring of cloth or clothing may be more economical, coloring only where needed, but may be less efficient when a high color density is desired, and the cloth alignment reduces the exposure of its constituent fibers to the colorant. In this case, the coloration of the textile fibers at an earlier stage of the thread and yarn manufacture may prove to be more advantageous.

The textile coloring composition may comprise chemical, organic, herbal or natural colorants. Regardless of their origin, colorants are generally divided into two classes, a) soluble dyes that can penetrate into the fibers, and b) water-insoluble pigments, which are generally limited to the external coloring of the fibers in view of their size.

When coloring textiles, a permanent effect is often desired, i.e., the color retains its original shade over time (e.g., exposure to light) and the color does not wash off (e.g., exposure to chemical and/or mechanical stress during cleaning). Dyes are relatively small molecules that can more easily penetrate into and remain in textile fibers, after which an additional treatment step (e.g., using a fixing agent) is optionally applied. Thus, when considering chemical and/or mechanical resistance, dyes are the primary colorants that physically protect the resulting color from undesirable fading at their relatively internal locations within the textile fiber. However, dyes are generally less resistant to sunlight than pigments.

Although pigments should be preferred over dyes in terms of sunlight resistance, they increase the risk of discoloration at relatively external locations on the outer surface of the textile fiber due to undesirable chemical and/or mechanical exposure (e.g., exposure to detergent during washing and abrasion from contact).

Thus, there remains a need for a textile colouring process which can provide effective and, when desired, permanent colouring of textile fibres.

Disclosure of Invention

The present inventors have disclosed methods and compositions for coating or coloring keratin fibers, such as human hair, which are aqueous dispersions comprising a plurality of polymeric particles formed from a hydrophilic polymeric material having neutralized acid moieties, wherein the hydrophilic polymeric material optionally encapsulates at least one pigment core particle. An optionally pigmented aqueous dispersion is applied to mammalian hair having an aminosilicone coating to produce an overlying, optionally pigmented, polymer layer. The aminosilicone coating may be obtained by applying to the hair fibres at least one reactive condensation curable aminosilicone prepolymer disposed in the oil phase of an oil-in-water emulsion. The oil phase may further comprise the same or different pigments to enhance or modify the coloration achieved by the pigmented polymer layer. The aminosilicone coating is formed by subjecting the prepolymer to in situ condensation curing on the individual hair fibres. The two continuous coatings applied to the exterior of the hair fiber advantageously provide one or more of the following: pleasant to the touch, satisfactory coloration (e.g., in terms of optical density, depth, vividness, etc.) and color persistence (e.g., resistance to repeated laundering or other external factors). Details of related methods and compositions can be found in WO2018/187246 with respect to this technology.

The present invention relates to a method for the pretreatment of an oil phase and/or components thereof, which method provides improved properties of aminosilicone emulsions and aminosilicone coatings produced therefrom. The improved properties of the first aminosilicone coating in turn enhance the effectiveness of the second polymeric coating. Any feature or combination of features of the present invention may be combined with any feature or combination of features detailed in WO 2018/187246. Although the use disclosed and claimed in WO2018/187246 is the coating or colouring of individual keratin mammalian hair fibres, the method and possible composition of the invention also allow for coating or colouring textile fibres.

As used herein, the terms "mammalian hair (individual mammalian hair)", "individual mammalian hair fibers (individual mammalian hair fibers)", and the like are used interchangeably. As used herein, the term "textile fibers" refers to any form of natural or synthetic textile material, for example, from the form of a thread (yarn) (usually formed by a plurality of individual filaments arranged longitudinally one above the other) or a yarn (yarn) (usually formed by a plurality of individual threads arranged longitudinally one above the other) as of a fabric (fabric) produced by any known method (e.g. weaving (weaves), knitting, crocheting, felting, sewing). Unless the context clearly indicates otherwise, the term also encompasses end products made from such woven or nonwoven fabrics.

Although it is clear from the context that the term "fiber" may refer to a hair filament, a textile filament or both a hair and textile filament (filament), it is generally clear to distinguish between these two types of filaments. Mammalian hair fibers are typically arranged as individual fibers, each fiber being attached to the mammal at a different location. For example, the roots of the human hair fibers are attached at various positions on the scalp, and the human hair fibers are not physically connected to each other except for unwanted tangles. Mammalian hair fibers can be seen as a spaced array of monofilaments (mono-filament). In contrast, in order to provide the necessary mechanical properties to the cloth produced using threads (threads) or yarns (yarns) or to the final product made of textile material, textile fibers, in particular natural textile fibers, are essentially composed of a plurality of individual filaments (for example, assembled by spinning) which overlap one another along the entire length of the strand. Thus, textile fibers, with the exception of certain synthetic fibers, refer not to monofilaments, but to closely packed multifilament elongated threads.

In one aspect the present invention provides a method of coating mammalian hair or textile fibres, the method comprising:

(a) providing an oil phase comprising at least one reactive condensation curable film-forming aminosilicone prepolymer, the oil phase satisfying at least one of:

(i) the at least one reactive condensation curable film-forming aminosilicone prepolymer includes at least one reactive condensation curable film-forming aminosilicone monomer having a molecular weight of up to 1000 grams/mole;

(ii) the oil phase further comprises a non-amino crosslinking agent adapted or selected to cure the at least one reactive condensation curable film-forming aminosilicone prepolymer, the non-amino crosslinking agent having a molecular weight of up to 1000 grams/mole;

(iii) the oil phase according to (i) and/or (ii) further comprises at least one of a silicone oil, an aminosilicone oil, a pigment dispersion and a reactive hydrophobic inorganic filler; and

wherein the oil phase comprises at least 0.01 wt.% (i.e., (weight)), at least 0.05 wt.%, at least 0.1 wt.%, at least 0.15 wt.%, at least 0.2 wt.%, at least 0.25 wt.%, at least 0.5 wt.%, at least 0.75 wt.%, or at least 1 wt.% water, based on the weight of the oil phase;

(b) after pre-treating the oil phase to obtain a pre-treated oil phase, emulsifying the pre-treated oil phase with an aqueous phase to obtain a pre-treated oil-in-water emulsion;

(c) applying the pre-treated oil-in-water emulsion to the outer surface of individual hairs of mammalian hair or to the outer surface of textile fibers;

(d) after the pre-polymer of the pre-treatment oil-in-water emulsion has undergone partial condensation curing to form an at least partially cured amino silicone coating on the outer surface of the individual hairs or the textile fibers, optionally washing the hairs or the textile fibers with a rinse liquid to remove excess of the pre-treatment oil-in-water emulsion;

(e) applying an aqueous dispersion comprising a plurality of polymer particles dispersed in the aqueous dispersion and made of a hydrophilic polymeric material having neutralized acid moieties onto the at least partially cured aminosilicone film to produce an overlying polymer layer adhered to the outer surface of the aminosilicone film; and optionally

(f) Washing the hair or the textile fibres with a rinsing liquid to remove excess of the aqueous dispersion.

In some embodiments of said aspect, the pre-treatment oil-in-water emulsion is applied on the outer surface of the textile fibers and the method is for coating textile fibers. In some such embodiments, the textile fibers are natural keratin fibers. In some such alternative embodiments, the textile fibers are natural non-keratin fibers. In such other alternative embodiments, the textile fibers are synthetic fibers, in which case the textile fibers may optionally be monofilaments.

In another aspect of the present invention, there is provided a method for coating mammalian hair or textile fibres, the method comprising:

(a) providing an oil phase comprising at least one reactive condensation curable film-forming aminosilicone prepolymer, the oil phase satisfying at least one of:

(i) the at least one reactive condensation curable film-forming aminosilicone prepolymer includes at least one reactive condensation curable film-forming aminosilicone monomer having a molecular weight of up to 1000 grams/mole;

(ii) the oil phase further comprises a non-amino crosslinking agent adapted or selected to cure the at least one reactive condensation curable film-forming aminosilicone prepolymer, the non-amino crosslinking agent having a molecular weight of up to 1000 grams/mole; and is

(iii) (iii) the oil phase according to (i) and/or (ii), wherein at least one of the reactive condensation curable film-forming aminosilicone prepolymer, the reactive condensation curable film-forming aminosilicone monomer, the non-amino crosslinker, or optionally any of a silicone oil, an aminosilicone oil, a pigment dispersion and a reactive hydrophobic inorganic filler further comprised in the oil phase, is a water-rich reactant; and

(b) pre-treating the oil phase for a pre-treatment time to yield water having at least 0.01 wt.%, at least 0.05 wt.%, at least 0.1 wt.%, at least 0.15 wt.%, at least 0.2 wt.%, at least 0.25 wt.%, at least 0.5 wt.%, at least 0.75 wt.%, or at least 1 wt.% of the weight of the oil phase;

(c) emulsifying the pre-treatment oil phase with an aqueous phase comprising water to obtain a pre-treatment oil-in-water emulsion;

(d) applying the pre-treated oil-in-water emulsion on the outer surface of individual hairs of the mammalian hair or on the outer surface of the textile fibers;

(e) after the pre-polymer of the pre-treatment oil-in-water emulsion has undergone partial condensation curing to form an at least partially cured amino silicone coating on the outer surface of the individual hairs or the outer surface of the textile fibers, optionally washing the hairs or the textile fibers with a rinse liquid to remove excess of the pre-treatment oil-in-water emulsion;

(f) applying an aqueous dispersion comprising a plurality of polymer particles dispersed in the aqueous dispersion and made of a hydrophilic polymer material having neutralized acid moieties on the at least partially cured aminosilicone film to produce an overlying polymer layer adhered to the outer surface of the aminosilicone film; and optionally

(g) Washing the hair or the textile fibres with a rinsing liquid to remove excess of the aqueous dispersion.

In some embodiments of said aspect, the pre-treatment oil-in-water emulsion is applied on the outer surface of the textile fibers and the method is for coating textile fibers. In some such embodiments, the textile fibers are natural keratin fibers. In such other alternative embodiments, the textile fibers are synthetic fibers, in which case the textile fibers may optionally be monofilaments.

In one aspect the present invention provides a method of treating the external surface of mammalian hair or textile fibres, the method comprising:

(a) pre-treating an oil phase containing at least one reactive condensation curable film-forming aminosilicone prepolymer to form an aminosilicone coating after condensation curing, the oil phase satisfying at least one of:

(i) the at least one reactive condensation curable film-forming aminosilicone prepolymer comprises at least one reactive condensation curable film-forming aminosilicone monomer having a molecular weight of at most 1000 g/mole, at least one of the prepolymer and the monomer being a water-rich or pre-treated reactant;

(ii) the at least one reactive condensation curable film-forming aminosilicone prepolymer comprises at least one reactive condensation curable film-forming aminosilicone monomer having a molecular weight of up to 1000 grams/mole, the oil phase further comprising at least one water-rich or pre-treated reactant;

(iii) the oil phase further comprises a non-amino crosslinker adapted or selected to cure the prepolymer, the non-amino crosslinker having a molecular weight of at most 1000 grams/mole, at least one of the prepolymer and the crosslinker being a water-rich or pretreated reactant; and

(iv) the oil phase further comprises a non-amino crosslinker adapted or selected to cure the prepolymer, the non-amino crosslinker having a molecular weight of up to 1000 grams/mole, the oil phase further comprising at least one water-rich or pretreated reactant;

(b) incubating the oil phase for a pretreatment time to obtain a pretreated oil phase;

(c) emulsifying the pre-treatment oil phase with an aqueous phase comprising water to obtain a pre-treatment oil-in-water emulsion;

(d) applying the pre-treated oil-in-water emulsion on the outer surface of individual hairs of the mammalian hair or on the outer surface of the textile fibers;

(e) after the pre-polymer of the pre-treatment oil-in-water emulsion has undergone partial condensation curing to form an at least partially cured amino silicone coating on the outer surface of the individual hairs or the outer surface of the textile fibers, optionally washing the hairs or the textile fibers with a rinse liquid to remove excess of the pre-treatment oil-in-water emulsion;

(f) applying an aqueous dispersion comprising a plurality of polymer particles dispersed in the aqueous dispersion and made of a hydrophilic polymer material having neutralized acid moieties on the at least partially cured aminosilicone film to produce an overlying polymer layer adhered to the outer surface of the aminosilicone film; and optionally

(g) Washing the hair or the textile fibres with a rinsing liquid to remove excess of the aqueous dispersion.

In some embodiments of said aspect, the pre-treatment oil-in-water emulsion is applied on the outer surface of the textile fibers and the method is for coating textile fibers. In some such embodiments, the textile fibers are natural keratin fibers. In some such alternative embodiments, the textile fibers are natural non-keratin fibers. In such other alternative embodiments, the textile fibers are synthetic fibers, in which case the textile fibers may optionally be monofilaments.

As used herein, the term "water-rich reactant" refers to a reactant comprising an amount of water within the ranges further detailed herein, while the "pre-treated reactant" is a reactant treated with an aqueous pretreatment solution such that, after incubation with the pretreatment aqueous solution, the amount of water contained in the pretreatment reactant is in the range of the desired amount. The reactant treated with the aqueous pretreatment solution may be a substantially dry reactant or a water-rich reactant whose water content is considered insufficient. Regardless of the manner in which such reactants are obtained, as being "water-rich" or "pretreated" per se, the reactants capable of delivering water to the composition according to the present method are collectively referred to as "water-rich" reactants. The oil phase composition, which may be a water-rich reactant (whether originally water-rich or pre-treated with an aqueous pre-treatment solution), includes reactive condensation curable film-forming aminosilicone prepolymers such as reactive condensation curable film-forming aminosilicone monomers, non-amino crosslinkers, silicone oils, aminosilicone oils, dispersions and fillers (e.g., reactive hydrophobic inorganic fillers).

In one embodiment of any of the above aspects, the aqueous dispersion further comprises pigment particles, at least a portion of which are encapsulated in the hydrophilic polymeric material in at least a portion of the polymeric particles. In this case, the resulting polymer layer may be referred to as a "pigmented polymer layer" and similar variants.

In another embodiment of any of the above aspects, the pre-treatment oil-in-water emulsion further comprises pigment particles dispersed in the pre-treatment oil phase, optionally in the presence of a pigment dispersion. In this case, the resulting aminosilicone coating or covering may be referred to as a "pigmented aminosilicone coating" and similar variants.

In another embodiment of any of the above aspects, the aqueous dispersion and the pre-treated oil-in-water emulsion each independently further comprise the same or different pigment particles disposed in the dispersion and emulsion as previously described and described in more detail below.

Another aspect of the present invention is to provide a method of treating the outer surface of mammalian hair or textile fibres, wherein a film-forming masking formulation is applied to the outer surface of individual hairs or to the outer surface of textile fibres to produce a masking film on said hair or textile fibres, prior to application of an oil-in-water emulsion according to the present teachings, and optionally after a degreasing step (if carried out). In some embodiments, the film-forming masking formulation is an oil-in-water emulsion as described herein, further comprising a metallic pigment adapted or selected to mask the color of the fibers upon application to the hair or textile fibers. In some embodiments, the film-forming camouflage formulation is an aqueous dispersion as described herein, the dispersion further comprising a metallic pigment adapted or selected to camouflage the color of the fibers after being applied to the hair or textile fibers.

In some embodiments of said aspect, the pre-treatment oil-in-water emulsion is applied on the outer surface of the textile fibers and the method is for coating textile fibers. In some such embodiments, the textile fibers are natural keratin fibers. In some such alternative embodiments, the textile fibers are natural non-keratin fibers. In such other alternative embodiments, the textile fibers are synthetic fibers, in which case the textile fibers may optionally be monofilaments.

Another aspect of the invention is to provide a kit for producing a reactive composition for coating, coloring or masking the outer surface of a textile fibre, the kit comprising:

(a) a first oil phase compartment comprising a first oil phase comprising:

(i) at least one reactive condensation curable film-forming aminosilicone monomer having a molecular weight of up to 1000 g/mole; and optionally also,

(ii) a non-amino crosslinking agent; and further optionally also,

(iii) at least one of an aminosilicone oil and a non-aminosilicone oil; and further optionally also,

(iv) a reactive condensation curable film-forming aminosilicone prepolymer comprising at least one of a reactive condensation curable film-forming aminosilicone polymer and a reactive condensation curable film-forming aminosilicone oligomer;

(b) an aqueous dispersion compartment comprising an aqueous dispersion, the aqueous dispersion comprising:

(i) an aqueous medium; and

(ii) submicron particles comprising or made of a hydrophilic polymeric material having a neutralized acid moiety and disposed in an aqueous medium, each of at least a portion of the submicron particles optionally comprising at least one pigment particle, the at least one pigment particle optionally being at least partially encapsulated by the polymeric material; and

(c) an optional second oil phase compartment comprising a second oil phase comprising:

(i) at least one of an aminosilicone oil or said aminosilicone oil and a non-aminosilicone oil or said non-aminosilicone oil, and optionally,

(ii) a solid hydrophobic reactive inorganic filler; and further optionally also,

(iii) at least one amino silicone prepolymer that is reactive condensation curable to form a film comprising at least one of a reactive condensation curable film-forming amino silicone polymer and a reactive condensation curable film-forming amino silicone oligomer; and further optionally also,

(iv) pigment particles disposed in the second oil phase;

wherein at least one of the first oil phase compartment or the optional second oil phase compartment further comprises an aqueous pretreatment solution; and is

Wherein the kit further optionally comprises at least one of a thickener, an emulsifier, a surfactant, and a dispersion.

In some embodiments of said aspect, said textile fiber, the surface of which is modified in accordance with the present teachings, is of natural origin, is an animal or plant based material, which is separate from the animal body from which said textile fiber is derived or isolated from the plant from which it is derived.

In a particular embodiment, the methods and kits of the present invention are applied and applied to natural keratin fibers. In another particular embodiment, the methods and kits are applied and applied to natural non-keratin fibers.

In some embodiments of the invention, the methods and kits are applied and applied to synthetic fibers.

Drawings

Some embodiments of the invention are described herein with reference to the accompanying drawings. This description together with the drawings make apparent to those skilled in the art how certain embodiments of the invention may be practiced.

The drawings are for illustrative purposes and are not intended to show structural details of the embodiments in more detail than is necessary for a fundamental understanding of the invention. For clarity, some objects depicted in the figures are not drawn to scale.

In the figure:

fig. 1A is a schematic illustration of a single textile thread in the presence of some emulsion droplets containing a reactive amino silicone prepolymer, according to some embodiments;

FIG. 1B is a schematic diagram showing how some of the emulsion droplets of FIG. 1A can move toward and line up on a fine thread of a textile;

FIG. 1C schematically shows how the emulsion droplets may further collect on the outer surface of the textile thread;

FIG. 1D schematically shows how the emulsion droplets may further merge to form a continuous film on the outer surface of the textile thread;

FIG. 1E schematically illustrates a top view of the surface of an uncoated wool thread showing the scales of wool on an enlarged scale;

FIG. 1F schematically shows, in an enlarged scale, a side view in longitudinal section of the surface of a coated wool thread, including raised wool scales;

figure 2A schematically shows how polymer particles of a neutralized polymer with acid moieties can move towards an amino silicone film on the outer surface of the textile thread;

figure 2B schematically shows how the polymer particles may further aggregate on the outer surface of the aminosilicone membrane;

figure 2C schematically shows how the polymer particles may further merge to form a continuous layer on the outer surface of the aminosilicone membrane;

FIG. 2D schematically illustrates how a neutralizing agent may evaporate from a polymer layer to modify the properties of a polymer material;

figure 2E schematically shows how an aminosilicone film under the polymer layer can be attached to the outer surface of the underlying thread;

FIG. 3A is a graph showing the percentage of hydroxyl groups present in an exemplary pretreatment composition as a function of pretreatment duration for a reactive oil phase;

FIG. 3B is a graph showing the achievable degree of coloration of an exemplary pretreatment composition as a function of the pretreatment duration of a reactive oil phase;

FIG. 3C is a graph showing the achievable degree of color persistence of a schematic oil-in-water emulsion as a function of the duration of pretreatment of the reactive oil phase;

FIG. 3D is a schematic showing the level of tack exhibited by illustrative oil-in-water emulsions as a function of the duration of pretreatment of the reactive oil phase;

FIG. 4 is a graph similar to FIGS. 3A through 3D shown as a single graph, with the various curves representing the degree of hydrolysis, coloration, durability, and tackiness in a modified embodiment; and

figure 5 depicts a simplified schematic of a process for preparing a composition including a pretreatment composition, according to various embodiments of the present teachings.

Detailed Description

The present invention relates to a method for colouring or treating natural keratin and non-keratin textile fibres and synthetic textile fibres, in particular using an oil-in-water emulsion comprising an oily phase comprising a reactive condensation curable aminosilicone prepolymer capable of forming an aminosilicone coating on the external surface of said textile fibres. The aminosilicone coating can in turn serve as a substrate for an aqueous dispersion comprising polymer particles (including micelles of hydrophilic polymer material optionally encapsulating pigment particles) applied in a subsequent step. The invention relates more particularly to a method for pre-treating the oil phase, in order to improve, among other things, the properties of the oil-in-water emulsion thus emulsified, of the resulting aminosilicone coating and of the subsequent layers of polymeric material.

Overview of the coating Process

Before explaining the pretreatment method in detail, an innovative coating or coloring process using a reactive condensation curing aminosilicone to form a first coating is outlined with reference to fig. 1. For simplicity, the various stages of the process are shown on one side of isolated textile threads, but this may be similarly applied to other forms of textile fibres such as yarns or cloth, in which case the illustrated shape will correspond to the normal cross-sectional profile of a woven or non-woven cloth. The formation of an aminosilicone coating ("AS coating") on the outer surface of the textile thread 10 requires a driving force. Without wishing to be bound by theory, the inventors believe that in the various methods of the present invention, the initial driving force for transferring the aminosilicone containing the reaction phase droplets 12 from within the emulsion to the surface of the fine wire comprises or consists essentially of an electrostatic attractive force 14 between negatively charged functional groups (e.g., hydroxyl, carboxyl) located on the outer surface of the fine wire (above isoelectric pH) and positively charged amino functional groups in the aminosilicone containing the reaction phase droplets. This electrostatic attraction force is schematically shown in fig. 1A. This driving force can also be evaluated by the difference in surface energy of the wetting liquid and the wetting surface. Aminosilicones having a surface energy not greater than the surface energy of the substrate are considered advantageous. For example, polyester fibers typically have a surface energy of 40-45 millinewtons per meter (mN/m; also known as dyn/cm), and cotton fibers typically have a surface energy in the range of 70-75 mN/m. The aminosilicones of the present teachings have a surface energy of 24-28mN/m, thus allowing the aminosilicones to wet textile fibres.

The inventors believe that after the hydrophobic reactive phase droplet reaches the surface of the thread, the droplet displaces any water or air disposed thereon, as shown by arrows 16 in fig. 1B, and that certain positively charged amino functional groups in the aminosilicone material are drawn close enough to attach or otherwise associate with certain negatively charged functional groups located on the surface of the thread (see fig. 1B).

In a very short time (typically up to several minutes) an initial aminosilicone film is formed on the surface of the thin wire, with an exemplary thickness of about 500 nm (typically in the range of 100 nm-2000 nm). The membrane may advantageously be self-terminating. Without wishing to be bound by theory, the inventors believe that subsequent amino silicone-containing droplets, after formation of the initial amino silicone monolayer, continue to be attracted by the negative charge of the thread surface, even "through" the first (intercepting) layer 12' of amino silicone, but are repelled by the positive charge of the amino moieties therein. Initially, the resultant force of the attractive and repulsive forces is positive, so the aminosilicone-containing droplets continue to be attracted to the surface of the filament where the aminosilicone accumulates, as shown in fig. 1C. The aminosilicone on the fine wire is driven electrostatically to continue to accumulate as long as the combined force of the attractive and repulsive forces remains positive.

As the thickness of such aggregates increases, the negatively charged textile thread surface is at a distance from the positively charged droplets that are free at or near the aggregated aminosilicone, thereby reducing the attractive forces thereon. In addition, the total positive charge of the aminosilicone aggregates increases with increasing aggregate mass, so that the repulsion force continues to increase. After the resultant force approaches zero, there is substantially no net flux of the amino silicone-containing droplets to the surface of the fine line, thereby achieving self-termination. Figure 1C schematically shows self-terminating positively charged aminosilicone aggregates on the surface of a negatively charged fine wire. The membrane self-terminates once the movement of the charged species reaches a critical point where the repulsive force between the immobilized layer on the fine thread of the textile and the free droplets overcomes the previous attractive force. In other words, when self-termination is achieved, no more material is gathered on the textile threads.

The self-termination of the process advantageously prevents an endless accumulation of material once the driving gradient is no longer present, which often leads to an uncontrolled thickness of the coating. In extreme cases, an endless pile of material can accumulate unseparated clumps of fibers that cannot be practically used. In a more forgiving case, although material accumulation cannot be prevented, the coating can be interrupted and the textile threads bridged in such an undesirable process can be individualized and disentangled mechanically, which usually results in poor appearance and/or reduced adhesion of the mechanical resistance/colour coating, if any. Advantageously, the self-terminating process according to the present teachings results in a coating having a reasonable thickness, which allows the coated threads to remain separate and not stick together. The thickness of the coating can be controlled by the size of the droplets of the emulsion (e.g., as easily formed by vigorous manual shaking D_V50 are 1-2 micron droplets that will produce a coating thickness of 0.5-1 micron).

Over time, the aminosilicone aggregates encapsulated on the surface of the fine textile threads coalesce to form an AS film or AS coating (fig. 1D).

According to some embodiments, the reactive condensation curable amino functional silicone prepolymer forms an average particle size (D) when in emulsion_V50) Emulsion droplets in the range of 200 nanometers to 100 micrometers, 200 nanometers to 50 micrometers, 200 nanometers to 25 micrometers, or from 1 micrometer to 20 micrometers, or from 200 nanometers to 1 micrometer, or from 0.5 micrometers to 5 micrometers, or from 0.7 micrometers to 3 micrometers, or from 1 micrometer to 2.5 micrometers, or from 1 micrometer to 10 micrometers. The size of the droplets and/or the size uniformity of the droplet population can be adjusted by selecting any desired emulsification method, for example adjusting the energy input in the process and its duration. Low energy processes (e.g., manually shaking the mixture) may be sufficient to provide droplets in the 1-5 micron range, which may not be uniform in size. A moderate energy process (e.g., using a planetary centrifugal mill) may provide a more uniform population, the size of which may be adjusted by duration and speed (e.g., if short, providing droplets in the range of 10-20 microns). High energy processes (e.g., using an ultrasonograph) may rapidly provide droplets in the submicron range.

Advantageously, since textile fibers wetted by the positively charged coating of the amino silicone repel each other, there are no liquid bridges between adjacent fibers, thus preventing the textile fiber clusters from sticking together. When the partial condensation cure is sufficiently rapid, the outermost layer of the aminosilicone coating may be sufficiently strong (forming a crusty-like barrier) prior to drying, thereby preventing the formation of lumps.

Without being bound by theory, it is believed that prepolymers with relatively low MW (relatively low viscosity) have the prospect of better fully wetting the textile fibers than prepolymers with relatively high MW (relatively high viscosity). Thus, once the constituent components are brought sufficiently close to the textile fibres due to electrostatic bonding, for example the acid: other mechanisms of alkali hydrogen bonding, or even covalent bonding, can be used to attach the aminosilicone molecules to the surface of the textile fibres. Such a process is believed to provide, along with the ongoing condensation cure of the prepolymer molecules, (a) adhesion to the underlying fibers ("adhesion") and (b) the "bondability" of the aminosilicone film.

Although not shown in the figures, the pigment particles, optionally coated in combination with the aminosilicone composition according to the present invention, are advantageously embedded in a growing network of a prepolymer, the curing of which is done in situ on the textile fibers. This embedding is believed to improve the adhesion of the pigment particles to the textile fibers and ensure that their retention time thereon is longer than can be tolerated by mere physical deposition in the presence of the non-reactive polymer. When using pigment dispersions in a separate preliminary step to reduce the pigment size and/or disperse the pigment into particles, it is believed that the pigment particles are first partially encapsulated by the pigment dispersion, which in turn forms an interface with the surrounding amino silicone matrix. In this case, it is preferable to subject the pigment dispersion to pretreatment instead of the pigment particles. Further, it is preferable to perform the pretreatment of the pigment dispersion after dispersing the pigment.

Although not shown in the figures, it is believed that the aminosilicone membrane 20 formed according to the above-described exemplary embodiments will be positively charged (e.g., allowing protonation of the amino moieties at alkaline pH).

The inventors have surprisingly found that the use of an AS formulation (e.g. an oil-in-water emulsion) having an alkaline pH (at least 9.0, at least 9.5 or at least 9.75, and typically 9.0-11.5, 9.0-11.0, 9.5-11.5, 9.5-11.0 or 9.5-10.7) can significantly enhance the adhesion of the AS film to the surface of the textile fibers. Without wishing to be bound by theory, considering keratin textile fibers, the inventors believe that at such alkaline pH, the epidermal scales 30 (as schematically shown in top view in fig. 1E) of the fibers on the outer surface of the textile threads 10 open. This allows some aminosilicone to contact the area "under" the open epidermal hair scale 30 (fig. 1F, not drawn to scale). Subsequently, after the pH is lowered (e.g., by evaporation of volatile carriers that change the degree of protonation), the epidermal hair scales of the keratin textile fibers return to their normally closed, overlapping structure, thereby mechanically capturing or immobilizing a portion of the aminosilicone membrane 20 and enhancing the aminosilicone membrane adhesion. This mechanical entrapment of the aminosilicone membrane may be referred to as "mechanical macroscopic binding forces" or simply "macroscopic binding forces".

It is further believed that this basic pH of the oil-in-water emulsion further increases the charge difference between the coated textile fibers and the reactive aminosilicone prepolymer droplets. At alkaline pH values, the prepolymer of the composition (cationic according to its amino functionality) is positively charged, whereas at similar pH values, the surface of the textile fibres is negatively charged. It will be appreciated that, according to these principles, the anionic polymer and the nonionic polymer will not be electrostatically driven towards the textile fibres, and their expected adhesion forces (if any) will be correspondingly reduced (e.g. at most allowing physical deposition or hydrophobicity: hydrophobic interactions).

Although electrostatic attraction may be the primary method of achieving initial adhesion of the film, the inventors have discovered that there may be significant additional obstacles that must be overcome to enable the initial attraction to establish adhesion and subsequently maintain and strengthen the adhesion.

One such obstacle involves the transport of substances containing interacting moieties (e.g., amino or silanol moieties) to the interface with the outer surface of the textile fiber. The inventors have found that this transport may be strongly influenced or controlled by the degree of wetting of the textile fibres by the droplets of the amino silicone-containing reaction phase in the emulsion. More specifically, the surface tension of the reactive phase is preferably controlled such that the liquid phase substantially wets the hydrophobic surface of the textile fibers. The inventors further believe that in certain embodiments, the viscosity of the formulation, and more particularly the viscosity of the reactive phase, should preferably be sufficiently low to facilitate transport of such materials to the surface of the textile fibers.

The inventors believe that despite the various advantages of using tacky polymeric materials, such materials may be significantly less suitable for achieving a long-lasting level of textile coloration than their less tacky monomeric and/or oligomeric counterparts.

Furthermore, the inventors found that even if all these conditions are met, the interaction of the electrostatic attraction between negatively charged functional groups located on the surface of the textile fibres and positively charged amino functional groups already transported to the surface of the fibres, and any other attractive forces, may not be sufficient to overcome the various types of steric hindrance. For example, large polymer structures may not be properly dispatched to locations on the surface of textile fibers because of other such (even smaller) structures that have already been located on the surface of the fibers. Even without such interference, the large polymer structures may not be matched to the surface of the textile fibers, such that the electrostatic attraction, which decreases significantly with increasing distance, cannot draw the polymer structures closer to the fiber surface, or any significant or sufficient connection between the charged functional groups is not achieved. In some cases, even if such connections are formed, they may not be sufficient to hold the large polymer structure in place when subjected to shear and/or drag forces (e.g., during washing). The large polymer structure may have a small available surface area (located close enough to the surface of the textile fiber) relative to the surface of the textile fiber, which further reduces the ability of the connection to withstand such shear and drag forces.

According to some embodiments, the reactive condensation curable amino functional silicone prepolymer has an average molecular weight of about 100 to about 100000. Typically, the MW of one monomer is in the range of about 100 to about 1000, the average MW of the oligomer is in the range of about 200 to about 2000, and the average MW of the polymer is at least in the range of about 2000, and in some embodiments, at most 50000.

The inventors have found that the strength of the initial AS attachment to the textile fibres is generally associated with an increase in the number of amines of the one or more aminosilicone species in the reaction phase in the emulsion. However, it is clear that the accessibility of each amino group also needs to be considered (e.g. due to steric hindrance, etc.). The inventors have found that in order to have sufficient electrostatic attraction and/or bonding to the textile fibres, the amine number or average (e.g. weighted average) amine number of these one or more aminosilicone species should be at least 3 or at least 4, and more typically at least 5, at least 6, at least 8, or at least 10, and/or in the range of 3-200, 5-500, 10-1000, 10-400, 10-300 or 25-250. While the aminosilicone prepolymer is primarily considered when referring to the amine number, it should be borne in mind that aminosilicones lacking condensation curing groups may also affect the total and average amine number of the reactive oil phase.

The amine number of the aminosilicone prepolymer, aminosilicone or any other aminosilicone species is generally supplied by the manufacturer but can be independently determined by standard methods as described in, for example, astm d 2074-07. May be provided in terms of the volume (milliliters) of 0.1N HCl required to neutralize 10 grams of the target material.

According to aspects of the present invention, an aqueous dispersion comprising a polymeric material having neutralized acid moieties can be applied to an underlying AS film to produce an overlying polymeric film overlying the AS film. In some embodiments, the polymeric material has acid moieties that can be neutralized, including, for example, as non-limiting examples carboxylic acid groups, which can be present in acrylic and methacrylic acid moieties.

In many embodiments, the polymeric material may comprise, consist essentially of, consist of, or consist of: neutralized olefin-acrylic acid copolymers (e.g., ethylene-acrylic acid (EAA) copolymers), or neutralized olefin-methacrylic acid copolymers (e.g., ethylene-methacrylic acid (EMAA) copolymers), or neutralized acrylamide/acrylate (AAA) copolymers. In some embodiments, the polymeric material may comprise, consist essentially of, or consist of: an acrylic acid copolymer having a neutralized acrylic acid moiety and a neutralized methacrylic acid moiety.

Such a polymer layer, which may include pigment particles, may provide various advantageous properties to the film structure (with pigment), including abrasion resistance, resistance to insertion of chemicals (e.g., soap and shampoo), and the like.

Furthermore, the inventors have found that such copolymers can be advantageously used AS pigment dispersions, thereby avoiding or at least eliminating the need for specialized dispersions (e.g., AS is often necessary when pigments are dispersed in AS coatings). Thus, more pigment can be loaded into the overlying polymer film, thereby increasing optical density (coloration) for a given film thickness. Such specialized dispersions may also compromise the bondability of the overlying polymer film, and/or the adhesion from the overlying polymer film to the underlying AS coating, and/or water resistance. Such specialty dispersions can also (often disadvantageously) lower the softening point temperature and/or glass transition temperature of the polymer layer.

The formation of the polymer layer over and encapsulating the AS film requires a driving force. Without wishing to be bound by theory, the inventors believe that the initial driving force for delivering polymeric material having neutralized acid moieties to the external AS surface in the various methods of the present invention comprises or consists essentially of: the electrostatic attraction between the positively charged amino functional groups disposed on and within the AS membrane and the negatively charged functional groups (e.g., carboxyl moieties) in the dispersed polymer particles 22 within the aqueous dispersion. This electrostatic attraction force 24 is schematically shown in fig. 2A. This electrostatic attraction is enhanced at alkaline pH values. The inventors believe that the dispersed polymer particles driven by this electrostatic attraction force reach the AS membrane surface, wherein negatively charged functional groups near the outer surface of the particles and facing the AS membrane are linked to positively charged amino functional groups located on the outer surface of the AS membrane to encapsulate the AS membrane. The outer (with respect to the underlying AS film) polymer layer may advantageously be self-terminating. Also, without wishing to be bound by theory, the inventors believe that the dispersed negatively charged polymer particles 22 continue to be attracted to the overall positive charge of the AS membrane, such that multiple layers 22' of polymer particles may bond together with the surface of the AS membrane (see fig. 2B). However, AS the polymer particles "free" in the dispersion are repelled by the negative charge of the polymer particles (see arrow 28 in fig. 2B), the electrostatically driven accumulation of the polymer particles on the AS membrane gradually stops (essentially AS explained above for the AS membrane), so that the accumulation of the polymer layer is self-terminating. In other words, the formation of the polymer layer continues AS long AS there is an electromotive force difference between the surface of the AS coating layer and the polymer particle layer accumulated thereon.

Since, as mentioned above, the coating of the aminosilicone coating by the polymer particles during processing is believed to be driven in part by their respective charges, another method of describing the threshold conditions that are advantageous for the present method relies on the initiation of materials due to interactionsSurface electromotive force. At the pH of the applied aqueous dispersion, the textile fibers pre-coated with the aminosilicone coating have a first surface electromotive force (ζ 1), whereas the aqueous dispersion has a second electromotive force (ζ 2). The difference between the two values, also called the electromotive potential difference (Δ ζ) at the pH, is defined as Δ ζ ═ ζ as follows₁-ζ₂Each ζ₁、ζ₂And Δ ζ is provided in millivolts (mV). In some embodiments, Δ ζ is at least 10mV, at least 15mV, at least 20mV, at least 25mV, at least 30mV, at least 40mV, or at least 50 mV. In some embodiments, Δ ζ is V in a range of 10 to 80mV, 10 to 70mV, 10 to 60mV, 15 to 80mV, 15 to 70mV, 15 to 60mV, 20 to 80mV, 20 to 70mV, 20 to 60mV, 25 to 80mV, 25 to 70mV, 25 to 60mV, 30 to 80mV, 30 to 70mV, 30 to 60mV, 35 to 80mV, 35 to 70mV, or 35 to 60 m. A first surface electromotive force (ζ 1) of the aminosilicone coating having a pH of the aqueous dispersion in the range of 4 to 11, 4 to 10.5, 4 to 10, 6 to 11, 6 to 10.5, 6 to 10, 7 to 11, 7 to 10.5 or 7 to 10 is greater than zero (ζ 1)>0)。

The surface electromotive force of a material is generally measured in a liquid phase. The electromotive force of the solid coating can be measured using a flow current detector in an electromotive force analyzer adapted to force a flow of water through a tube in which the sample is placed. The results obtained by this method reflect to some extent the electromotive force of the same particles in the suspension. Vice versa, it is believed that the electromotive force of the oil-in-water aminosilicone emulsion can predict the surface electromotive force of the aminosilicone coating produced thereby.

Once the electromotive potential difference (Δ ζ) between the two surfaces is substantially zero or zero, the application of the aminosilicone coating formed by the overlying polymer layer is self-terminating.

Over time, the aggregation of the dispersed polymer particles on the AS membrane undergoes coalescence to form the polymer overcoat layer 30 schematically provided in fig. 2C. At the same time, volatile materials, including the aqueous carrier and neutralizing agent, evaporate, as indicated by arrows 26.

The waiting time after coating is at most 10 minutes or at most 5 minutes, more typically at most 3 minutes, at most 2 minutes, at most 1.5 minutes or at most 1 minute. The thickness of the polymer overcoat can be about 100-5000 nm, more typically 150-2000 nm, and even more typically 150-1000 nm or 150-600 nm.

As schematically shown, the outer surface of the outer polymer coating facing and contacting the aqueous dispersion body contains negatively charged moieties. For example, it may be advantageous to neutralize these moieties on the outer surface by a volatile base (e.g., ammonia) typically present in aqueous dispersions containing polymers having neutralized acid moieties. Such an operation may result in a conjugated acid coating (shown schematically as 32 in fig. 2D) of the polymeric material that exhibits improved water resistance and/or improved mechanical properties, particularly after the volatile base has evaporated.

In order to accelerate acid conjugation, water resistant polymer layer formation and viscosity reduction, which leads in particular to a return of the neutralized part of the hydrophilic material to the natural hydrophobic polymer, by faster evaporation, an excess of neutralizing agent is preferably avoided. In addition, excess neutralizing agents (e.g., bases) can block silanol groups of the aminosilicones of the first coating by forming hydrogen bonds therewith, limiting the accessibility of such hydroxyl groups to amine moieties of other aminosilicones, and thus delaying the condensation cure of the aminosilicone coating. In other words, an excess of base in the second coating inhibits curing of the first coating.

To avoid excess neutralizing agent, the amount of a particular base to be added (with a particular content of acid moieties) to a particular polymeric material can be estimated based on the degree of neutralization desired. In addition, the amount of base in the neutralized dispersion can be monitored. For example, pH can be monitored using a pH meter. In one embodiment, the amount of neutralizing agent in the neutralized dispersion is monitored by conductivity. The base was added or the dispersion was evaporated until the conductivity was less than 3 millisiemens.

It may be desirable to produce one or more additional coatings on top of the above-described polymeric overcoat. Another aminosilicone containing formulation (usually an emulsion) is added. In an alkaline medium, this neutralizes the acid groups on the outer surface of the polymer overcoat, forming negatively charged moieties, so that positively charged amino moieties can be electrostatically attracted and subsequently attached to these negatively charged moieties.

Over a long period of time (e.g. 12 to 36 hours, unless special pre-treatment is performed) it may be advantageous to form additional bonds between the textile fibres and the aminosilicone film. Figure 2E provides a schematic cross-sectional view of a textile filament 10 having an aminosilicone film 20 covalently bonded 15 to the textile filament 10, wherein the aminosilicone coating is further encapsulated by a polymeric overcoat layer 30.

For example, when the glass transition temperature of the polymer (or film formed from the reactive prepolymer) no longer changes over time, in other words the temperature has reached a substantially stable value, indicating that no further crosslinking has occurred, the polymer is considered to have fully cured. Alternatively and additionally, the aminosilicone polymer (or film produced therefrom) will be fully cured when the number of silicone linkages that the prepolymer can form in the curable fluid is substantially unchanged over time under applicable curing conditions. The number of siloxane bonds in the cured aminosilicone polymer can be assessed by conventional analytical methods, for example by Fourier Transform Infrared (FTIR) spectroscopy.

Amino silicone coating

Hereinafter, unless the context clearly indicates otherwise, an oil phase or reactive oil phase (and similar variants) encompasses or refers to a reactive oil phase pretreated in accordance with the present teachings. Similarly, a (reactive) oil-in-water aminosilicone emulsion comprises or relates to an emulsion whose oil phase has been pretreated in accordance with the present teachings.

Prepolymers generally refer to materials (e.g., uncured/curable monomers, oligomers, and/or polymers) that can be crosslinked to form larger macromolecules by crosslinkable groups, also referred to as reactive groups, by techniques known as curing methods. As used herein, prepolymers are considered reactive (still capable of participating in polymerization or curing) when they lack the glass transition temperature (Tg) (initially in the oil phase). There are various curing methods depending on the chemical composition of the prepolymers to be crosslinked, their reactive groups and curing co-factors (crosslinking agents, curing accelerators or catalysts, etc.).

While the reactive aminosilicone prepolymer lacks an initial Tg, once incorporated into the emulsion and coated onto textile fibres and sufficiently cured, forms a network, the at least partially cured aminosilicone film appears to lack a brittle flexible elastomer, the prepolymer preferably curing to form a 3D network with a Tg below 25 ℃, i.e. a Tg between-100 ℃ and +20 ℃, typically not more than +10 ℃, or 0 ℃, possibly below-5 ℃, below-15 ℃ or below-25 ℃; and optionally in the range of-80 ℃ to-20 ℃ or-70 ℃ to-30 ℃. However, brittleness can also be avoided by using very thin coatings (e.g., thicknesses of a few microns or less). In this case, cured polymer films with a Tg of greater than 25 ℃ may also be used. Cured films having a relatively high Tg have a higher crosslink density than cured films having a relatively low Tg. Cured films with higher Tg/crosslink density should be more resistant to abrasion, swelling, or chemical attack (e.g., alcohol).

Typically, the condensation curable aminosilicone prepolymer forms a phase that is separated from water and is substantially immiscible with water. Such different phases may also be referred to as "oil phases", reactive oil phases or similar variants. For reasons that will be explained in further detail below, in some embodiments, the reactive oil phase may further include at least one silicone oil other than the reactive aminosilicone prepolymer, an aminosilicone oil, a crosslinking agent, a 3D network former, pigment particles, and a pigment dispersant. All substances present in the oil phase may be referred to as "reactants" even if they lack the specific ability to react or interact with other molecules of the oil phase.

The invention relates to silicone prepolymers which are condensation-curable, i.e. carry crosslinkable groups which can react with one another to form a silicone bond by condensation with simultaneous release of alcohol, oxime or water molecules in the process. Although there are a variety of reactive groups that can condensation cure, they can be readily divided into silanol groups and hydrolyzable groups (e.g., alkoxy groups) that form silanol groups upon hydrolysis. Condensation curable aminosilicone prepolymers can be classified not only by the chemical nature of their reactive groups, but also by the number of reactive groups per molecule. For simplicity, a condensation-cured aminosilicone prepolymer having one reactive group per molecule may be represented as 1-SiOH, one having two reactive groups per molecule as 2-SiOH, and one having three or more reactive groups per molecule as 3+ SiOH. Condensation curable aminosilicone prepolymers having two or more groups may have different groups for each reactive moiety.

Although condensation-curable aminosilicone prepolymers having a single reactive group (1-SiOH) can participate in the polymerization (curing) via their unique condensation-curing groups, they are generally regarded as terminating such processes in terms of network development. Thus, when a three-dimensional (3D) network structure of the aminosilicone film is desired, the presence of condensation curable aminosilicone prepolymers having a single condensation reactive group per molecule in the prepolymer mixture should be kept low, and such prepolymers are preferably avoided. The same principle applies analogously to any other material present in the oil phase. Preferably, none of the reactants should function in a manner equivalent to terminating polymerization or inhibiting curing. In some embodiments, the concentration of aminosilicone prepolymer having a single condensation-reactive group per molecule and/or any reactant capable of inhibiting curing is at most 7 wt.%, at most 5 wt.%, at most 2 wt.%, or at most 1 wt.% of the weight of the oil phase. In some embodiments, the oil phase is free of the 1-SiOH prepolymer or terminating reactant.

Aminosilicone prepolymers (2-SiOH) having two condensation-curable reactive groups per molecule can be more meaningfully involved in the formation of network structures than the previously mentioned 1-SiOH counterparts. Preferably, such a network should not rely solely on linear chain-like extensions to enable the formation of a well-bonded 3D-matrix between the chains of such a prepolymer undergoing curing. By analogy, reactants capable of interacting with two different groups (typically, but not exclusively, on different molecules) may be referred to herein as "bifunctional". An example of a difunctional reactant for the non-amino silicone prepolymer may be a non-amino crosslinker. In some embodiments, the concentration of the aminosilicone prepolymer having two condensation-reactive groups and/or any difunctional reactant per molecule is at most 30 wt.%, at most 20 wt.%, at most 10 wt.%, or at most 5 wt.% of the weight of the oil phase. In some embodiments, the oil phase is free of the 2-SiOH prepolymer and/or difunctional reactant.

Reactive polymer-forming condensation-curable aminosilicone prepolymers having at least three condensation-curable reactive groups (e.g., three silanol and/or hydrolyzable groups) advantageously facilitate the formation of three-dimensional networks. Similarly, "trifunctional" reactants that accelerate or otherwise enhance the formation of 3D-networks are preferred over less functional counterparts. Examples of such "trifunctional" reactants include certain crosslinking agents and reactive fillers. In some embodiments, the polymer-forming aminosilicone first reactant comprises at least one reactant having at least three condensation-reactive groups and/or a 3D-network former.

Condensation curable amino functional silicones are also characterized by the presence of amino groups attached to the silicone prepolymer backbone via carbon atoms. These amino groups (at the terminal or pendant ends) can also be linked or interacted with other molecules through nucleophilic reactions or interactions, such as, but not limited to, on carboxylic acid, anhydride, or epoxy functional molecules or substrates. Thus, while certain silicone prepolymers disclosed herein are referred to as "reactive" or "condensation curable" amino-functional silicones, the term is not intended to limit the curing process to proceeding by condensation of condensation curable reactive groups, as amino groups can also proceed by curing by a "non-condensation" process, such as the formation of nitrogen-carbon bonds. The product of this curing process, in terms of their viscoelastic properties, is a network of cross-linked oligomers or polymers, called an elastomeric or elastic network (rubbery). Although elastomers generally refer to cured polymers having a glass transition temperature below typical environmental values, thin coatings of "elastomeric" polymers having a Tg above that environmental value and which behave as regular elastomers for all practical purposes can be tolerated. Thus, because the cured aminosilicone coatings resulting from the process of the present invention are thin, both elastomers (e.g., Tg < 30 ℃) and elastomeric networks (e.g., Tg > 30 ℃) are suitable. Because such cured network structures (preferably three-dimensional structures to enhance bonding) can form continuous films, prepolymers that participate in such formation, used alone or in combination with other film formers (e.g., crosslinkers, 3D network formers), can also be referred to as film-forming prepolymers.

The amino-functional silicone prepolymers (otherwise referred to as "aminosilicones") of the present invention may be considered to be positively charged or positively chargeable under the appropriate chemical environment (e.g., a pH above the isoelectric point of the textile fibers). The charge of a particular material can be derived from its chemical structure and type of protonation. The evaluation can be performed when the material is dispersed or dissolved in water or any aqueous environment relevant to the operating conditions of the material under study. In the present case, the aminosilicone prepolymer is used in the form of an oil-in-water emulsion (alone or in combination with other reactants).

In some embodiments, the oil-in-water emulsion has a surface electromotive force of greater than 0, or is at least +1mV, at least +2mV, at least +3mV, at least +5mV, at least +7mV, at least +10mV, at least +15mV, at least +20mV, at least +30mV, at least +40mV, or at least +60 mV; alternatively, at most +100mV or at most +80 mV.

In some embodiments, the oil-in-water emulsion has a surface electromotive force greater than 0 and less than 90mV, or in the range of 1-50mV, 1-30mV, 1-20mV, 1-15mV, 2-100mV, 2-30mV, 3-100mV, 3-50mV, 3-30mV, 3-20mV, 5-100mV, 5-50mV, 5-30mV, 5-20mV, 7-100mV, 10-80mV, 15-80mV, 20-80mV, or 20-60 mV.

In some embodiments, the surface electromotive force of the oil-in-water emulsion is measured at a pH of 9. In other embodiments, the surface electromotive force is measured at the natural pH of the oil-in-water emulsion (about pH 10). If the solids content of the oil-in-water emulsion is too high, the electromotive force can be determined with a diluted sample containing 2 wt.% or less material on solids basis.

Such materials can be characterized in part by their amine number, which indicates the number of amines per molecule (or per given weight of aminosilicone material, whether film-forming or not). In some embodiments, at least one, optionally all, of the reactive condensation curable film-forming aminosilicone prepolymers in the reactive oil phase have an amine number or a weighted average amine number in the following range: 3-1000, 3-500 or 3-200. In some embodiments, the reactive oil phase as a whole exhibits an amine number in the range of 3 to 1000, 3 to 500, or 3 to 200.

In some embodiments, the condensation curable aminosilicone prepolymer is water insoluble or substantially water insoluble, in which case the prepolymer may also be said to be hydrophobic. In some embodiments, the solubility of the prepolymer, relative to the weight of the aqueous composition in which it is located, is 5 wt.% or less, 2 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, or 0.1 wt.% or less. Solubility can be assessed visually, and the composition is typically at 23 ℃. If a clear solution is formed in water, the material is water soluble or below a threshold concentration. When the material is a macromolecule, such as a polymer, if the micelles formed therefrom cannot be detected, the polymer is water soluble and the water carrier remains transparent. In contrast, the material (or prepolymer) is insoluble if it is not soluble in water (e.g., forms a visually detectable dispersion or emulsion).

In some embodiments, the reactive condensation curable film-forming aminosilicone prepolymer has at least three condensation reactive groups per molecule and has a solubility in water of less than 1% by weight at 23 ℃. In some embodiments, a reactive condensation curable film-forming aminosilicone prepolymer having at least three condensation reactive groups per molecule includes a reactive condensation curable film-forming aminosilicone monomer having a solubility in water of less than 1% by weight at 23 ℃.

As noted above, the aminosilicone prepolymers used in the compositions and methods of the present invention are reactive and condensation curable. While the presence or absence of a glass transition temperature enables an assessment of the reaction potential of a material or mixture, viscosity may provide an alternative indication, often more readily available or assessable. Aminosilicone materials having relatively high viscosities, particularly those that are solid at temperatures associated with the performance of the process of the present invention (e.g., at ambient temperatures of about 23 ℃), are predominantly or fully crosslinked. Even if not fully crosslinked, the aminosilicones having the higher viscosities cannot participate in further crosslinking under the conditions (e.g., temperature, time frame, etc.) associated with the process of the present invention. For similar reasons, aminosilicone materials having higher Molecular Weights (MW) are also less reactive or cure more slowly than aminosilicones having lower molecular weights, which in the case of polymers generally refer to the weight average molecular weight of the material, given certain possible heterogeneities.

The molecular weight of the aminosilicone prepolymer may depend on the number of identical or different repeating units in the prepolymer. Prepolymers having a single unit are monomers. Prepolymers with several repeating units are oligomers. Larger prepolymers may be defined as polymers. In the absence of chemical information, these three main classes of prepolymers can be arbitrarily distinguished by chemical structure or by molecular weight. The molecular weight or weight average molecular weight of the material is typically provided by the manufacturer, but can be independently determined by known analytical methods, including gel permeation chromatography, High Pressure Liquid Chromatography (HPLC), or matrix assisted laser desorption ionization time of flight mass spectrometry MALDI-TOFMS.

In some embodiments, the aminosilicone prepolymer consists essentially of, or consists of, individual aminosilicone monomers, including mixtures thereof. Due to their smaller size/higher accessibility of reactive groups, aminosilicone monomers can be condensation cured faster than their oligomers or polymers. Such monomers can form three-dimensional (3D) networks with high crosslink density. In some embodiments, when the aminosilicone prepolymer is predominantly monomeric, the reactive oil phase may also include a silicone oil and/or an aminosilicone oil.

In some embodiments, the condensation curable aminosilicone monomer has an amine number of at least 200, at least 220, at least 240, at least 275, at least 325, or at least 400. In some embodiments, the amine number of the aminosilicone monomer is at most 1500, at most 1250, at most 1150, at most 1050, or at most 1000. In some embodiments, the amine number of the aminosilicone monomer is in the range of 200 to 1500, 220 to 1250, 200 to 1150, 200 to 1100, 220 to 1250, or 220 to 1150.

In some embodiments, the aminosilicone prepolymer consists essentially of or consists of individual aminosilicone oligomers, including mixtures thereof. The aminosilicone oligomer is capable of faster condensation curing than the polymer counterpart, while providing a softer coating than the single monomer. Such oligomers can form 3D networks with a degree of crosslinking lower than that of the monomers and higher than that of the polymers. In some embodiments, when the aminosilicone prepolymer is primarily an oligomer, the reactive oil phase may further include a silicone oil, an aminosilicone oil, a non-amino crosslinker, and/or a reactive filler.

In some embodiments, the condensation curable aminosilicone oligomer has an amine number of at least 20, at least 40, at least 60, at least 75, at least 85, at least 100, at least 125, at least 150, at least 200, or at least 250. In some embodiments, the amine number of the aminosilicone oligomer is at most 600, at most 500, at most 450, or at most 400. In some embodiments, the amine number of the aminosilicone oligomer is in the range of 20 to 600, 40 to 600, 60 to 500, 60 to 400, or 75 to 500.

In some embodiments, the aminosilicone prepolymer consists essentially of or consists of individual aminosilicone polymers, including mixtures thereof. Aminosilicone polymers are capable of providing flexible 3D networks with low cross-link density, suitable for use in flexible substrates such as textile fibres. In some embodiments, when the aminosilicone prepolymer is primarily a polymer, the reactive oil phase may further include a non-amino crosslinker, a silicone oil, an aminosilicone oil, and/or a reactive filler.

In some embodiments, the condensation curable aminosilicone polymer has an amine number of at least 2, at least 5, at least 10, at least 15, at least 25, at least 40, at least 75, at least 100, or at least 125. In some embodiments, the amine number of the aminosilicone polymer is at most 200, at most 180, at most 160, or at most 140. In some embodiments, the amine number of the aminosilicone polymer is in the range of 2 to 200, 5 to 200, 10 to 200, 25 to 200, 5 to 150, or 10 to 135.

The inventors have found that by mixing different types of prepolymers or at least one specific type of prepolymer with a further non-reactive silicone, the properties of the cured film that may result therefrom can be tailored to obtain the advantages of each type while reducing their respective disadvantages. For example, while the following observations may depend on the exact composition of each subtype, it is generally observed that the use of monomers alone may result in a coating that is too brittle, while the use of polymers alone may result in a coating that is too slow to fully cure or lack sufficient bonding. Therefore, to reduce brittleness, it may be desirable to reduce the degree of crosslinking between the prepolymers. This effect can be achieved, for example, by adding a larger prepolymer (typically a condensation curable aminosilicone polymer). Alternatively or additionally, aminosilicone oils and/or non-aminosilicone oils may be added. Such molecules can reduce crosslink density and reduce brittleness.

Too much larger prepolymer and silicone oil may reduce the crosslink density and may impair various mechanical properties of the film or coating. In addition, too much non-amino silicone oil may reduce the positive charge density of the amino groups, thereby reducing the electrostatic attraction mechanism, and/or weakening or destroying the self-termination mechanism of the film.

In some embodiments, the aminosilicone prepolymer is comprised of a mixture of at least two prepolymers selected from the group consisting of condensation curable aminosilicone monomers, aminosilicone oligomers, and aminosilicone polymers. For example, the mixture of prepolymers may comprise condensation-curable aminosilicone monomers (e.g., for their fast cure speed), condensation-curable aminosilicone oligomers (e.g., for their ability to control crosslinker density), and condensation-curable aminosilicone polymers (e.g., for their contribution to coating flexibility).

In some embodiments, the condensation-curable aminosilicone monomer is present in the mixture of prepolymers in an amount greater than the amount of condensation-curable aminosilicone oligomer. In some embodiments, the condensation-curable aminosilicone monomer is present in an amount greater than the amount of condensation-curable aminosilicone polymer. In some embodiments, the condensation-curable aminosilicone monomer is present in an amount greater than the total amount of condensation-curable aminosilicone oligomer and polymer.

With respect to viscosity, aminosilicone prepolymers having lower viscosity are not only expected to have higher reactivity and/or more flow than their higher viscosity counterparts, but also to better wet textile fibers after application to the textile fibers.

In certain embodiments, the oil phase, excluding all inorganic content, has no glass transition temperature.

In some embodiments, the condensation curable film-forming amino silicone prepolymer is liquid at 23 ℃.

According to some embodiments, the reactive condensation curable aminosilicone prepolymer satisfies at least one, at least two, or at least three of the following structural characteristics:

a) the prepolymer includes reactive groups selected from alkoxy-silane reactive groups, silanol reactive groups, and combinations thereof;

b) the prepolymer has no glass transition temperature;

c) the prepolymer is not a solid at 23 ℃;

D) said prepolymer having a viscosity in the range of 1-2000 millipascal-seconds (mPa · s, also known as cps), 10-2000mPa · s, 2-1000mPa · s, 2-500mPa · s, 5-100mPa · s, 10-20000mPa · s, 10-15000mPa · s, 20-15000mPa · s, 30-15000mPa · s, 40-10000mPa · s or 50-10000mPa · s, as measured in a suitable rheometer at 23 ℃;

e) the prepolymer is capable of wetting the textile fibers;

f) the prepolymer is a film-forming prepolymer;

g) the prepolymer includes a primary amine;

h) the prepolymer has an amine number in the range of 3-1000, 3-500, or 3-200;

i) the prepolymer includes a terminal amino moiety;

j) the prepolymer includes pendant amino moieties;

k) the prepolymer is miscible with a reactive oil phase comprising, in addition to the prepolymer, at least one of a different prepolymer, a non-reactive silicone oil, a non-reactive aminosilicone oil, a crosslinker and a pigment dispersant;

l) the refractive index of the prepolymer is within ± 10% of the refractive index of a reactive oil phase comprising at least one of different prepolymers, non-reactive silicone oils, non-reactive amino silicone oils, cross-linking agents, hydrophobic fumed silica (hydrophobic fumed silica), and pigment dispersants;

m) the prepolymer is hydrophobic;

n) the prepolymer has a solubility in water (e.g., about pH7) at 23 ℃ of less than 5 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, or less than 0.25 wt%;

o) the prepolymer is a linear or branched polymer;

p) the prepolymer is a linear or branched oligomer;

q) the prepolymer is a monomer; and

r) the ratio of the number of amines of the prepolymer (AN) to the viscosity in mPas (Visc.) is at least 40, at least 100, at least 200 or at least 500 after multiplying by 1000, which can be expressed mathematically as 1000 (AN/Visc.) or more than 40, and so on.

Although it has been disclosed that silicone materials which are solid at 23-25 ℃ are suitable for improving the lubricity of textiles, when coated in particulate form, it is clear that such solids are non-reactive and do not participate in the formation of the intended continuous layer, which can be formed by coalescence of droplets of silicone material at the same temperature. The solid silicone particles are believed to act as friction reducers in a manner similar to mechanical bearings.

In some embodiments, the prepolymer has no glass transition temperature and has a solubility in water at 23 ℃ (pH7) of less than 1 wt.%, less than 0.5 wt.%, or less than 0.25 wt.%, by weight of the aqueous composition.

In some embodiments, the prepolymer has no glass transition temperature and has a viscosity ranging from 1 to 2000 mPas, 10 to 2000 mPas, 2 to 1000 mPas, 2 to 500 mPas, 5 to 100 mPas, 10 to 20000 mPas, 10 to 15000 mPas, 20 to 15000 mPas, 30 to 15000 mPas, 40 to 10000 mPas, or 50 to 10000 mPas, as measured at 23 ℃.

In some embodiments, the prepolymer has no glass transition temperature and has reactive groups selected from alkoxy-silane reactive groups, silanol reactive groups, and combinations thereof.

In some embodiments, the prepolymer has an amine number in the range of 3-1000, 3-500, or 3-200 and has a viscosity in the range of 1-2000 mPas, 10-2000 mPas, 2-1000 mPas, 2-500 mPas, 5-100 mPas, 10-20000 mPas, 10-15000 mPas, 20-15000 mPas, 30-15000 mPas, 40-10000 mPas, or 50-10000 mPas when detected at 23 ℃.

In some embodiments, the prepolymer has an amine number in the range of 3-1000, 3-500, or 3-200 and has a solubility in water at 23 ℃ (pH7) of less than 1 wt.%, less than 0.5 wt.%, or less than 0.25 wt.%, by weight of the aqueous composition.

In some embodiments, the prepolymer has an amine number in the range of 3-1000, 3-500, or 3-200 and is miscible with a reactive oil phase that comprises at least one of a different prepolymer, a non-reactive silicone oil, a non-reactive aminosilicone oil, a crosslinker, and a pigment dispersant in addition to the prepolymer.

In some embodiments, the prepolymer has no glass transition temperature; having a reactive group selected from alkoxy-silane reactive groups, silanol reactive groups, and combinations thereof; has a viscosity in the range of 1-2000 mPas, 10-2000 mPas, 2-1000 mPas, 2-500 mPas, 5-100 mPas, 10-20000 mPas, 10-15000 mPas, 20-15000 mPas, 30-15000 mPas, 40-10000 mPas or 50-10000 mPas, as measured in a suitable rheometer at 23 ℃.

In some embodiments, the prepolymer has an amine number ranging from 3 to 1000, 3 to 500, or 3 to 200; has a solubility in water at 23 ℃ (pH7) of less than 1 wt.%, less than 0.5 wt.%, or less than 0.25 wt.%, by weight of the aqueous composition; and is miscible with a reactive oil phase comprising, in addition to the prepolymer, at least one of a different prepolymer, a non-reactive silicone oil, a non-reactive aminosilicone oil, a crosslinker and a pigment dispersant.

In some embodiments, the prepolymer has no glass transition temperature; having a reactive group selected from alkoxy-silane reactive groups, silanol reactive groups, and combinations thereof; has a viscosity ranging from 1 to 2000 mPas, from 10 to 2000 mPas, from 2 to 1000 mPas, from 2 to 500 mPas, from 5 to 100 mPas, from 10 to 20000 mPas, from 10 to 15000 mPas, from 20 to 15000 mPas, from 30 to 15000 mPas, from 40 to 10000 mPas or from 50 to 10000 mPas when measured at 23 ℃; and have amine numbers ranging from 3 to 1000, 3 to 500, or 3 to 200.

In some embodiments, the prepolymer has no glass transition temperature; having a reactive group selected from alkoxy-silane reactive groups, silanol reactive groups, and combinations thereof; has a viscosity ranging from 1 to 2000 mPas, from 10 to 2000 mPas, from 2 to 1000 mPas, from 2 to 500 mPas, from 5 to 100 mPas, from 10 to 20000 mPas, from 10 to 15000 mPas, from 20 to 15000 mPas, from 30 to 15000 mPas, from 40 to 10000 mPas or from 50 to 10000 mPas when measured at 23 ℃; having an amine number in the range of 3-1000, 3-500, or 3-200; and has a solubility in water at 23 ℃ (pH7) of less than 1 wt.%, less than 0.5 wt.%, or less than 0.25 wt.%, by weight of the aqueous composition.

According to some embodiments, suitable reactive condensation curable aminosilicone prepolymers may be selected from: ATM1322 bis [ methyl-diethoxysilyl-propyl ]]Amines, diethoxydimethylsilane, aminopropyltriethoxysilane, DMS-S12,KF-857、GP-145、GP-34、GP-397、GP-657、GP-846、KF-862、OFX8630、OFX8822、SIB1824.5、SF1706、SIO6629.1, SIT8187.2, TSF4703, TSF4707, TSF4708, and any commercially available equivalents of the foregoing. According to some embodiments, the oil-in-water emulsion (which may be one formulation or a combination of sub-formulations) further comprises an oil, which is miscible with the at least one prepolymer, and/or with the cross-linker, and/or with the at least one pre-polymerCondensation promoters or catalysts, including but not limited to silicone oils.

Since the coated textile fibers according to the present teachings can be used to make cloth or garments for human use, the ingredients used to prepare the compositions for use in the steps of the present method are preferably compatible with human skin without undue hypersensitivity, toxicity, instability, and the like.

In the above, and as described in further detail herein, some properties of the aminosilicone prepolymers suitable for use in the present invention are considered for a single material. However, since the reactive oil phase may comprise more than one aminosilicone prepolymer and in addition additional reactants, the recommended properties of such a mixture should also be noted. The skilled person will readily appreciate that although specific properties are allowed, or the opposite is true for the individual materials, mixing the materials in the oil phase may provide different tolerances. Since the reactants of the oil phase may include solid inorganic particles (e.g. pigment particles, 3D-network formers) that may affect specific measurements, they may be omitted for specific determinations, but the fact does not imply that such inorganic particles are not present in the entire oil phase emulsified for application to textile fibres.

In some embodiments, the reactive oil phase comprising at least one of a condensation curable aminosilicone prepolymer, a non-reactive silicone oil, a non-reactive aminosilicone oil, a liquid hydrophobic crosslinker, and a pigment dispersant does not have a glass transition temperature.

In some embodiments, the reactive oil phase comprising at least one of the condensation curable amino silicone prepolymer, the non-reactive silicone oil, the non-reactive amino silicone oil, the liquid hydrophobic cross-linker, and the pigment dispersant has a viscosity in the range of 1 to 2000 mPa-s, 2 to 1000 mPa-s, 2 to 500 mPa-s, 2 to 400 mPa-s, 2 to 300 mPa-s, 2 to 200 mPa-s, or 2 to 50 mPa-s, as measured in a suitable rheometer at 23 ℃.

In some embodiments, the solubility of the reactive oil phase comprising at least one of the condensation curable aminosilicone prepolymer, the non-reactive silicone oil, the non-reactive aminosilicone oil, the liquid hydrophobic crosslinker, and the pigment dispersant in water at 23 ℃ is less than 5% (by weight), less than 2% (by weight), less than 1% (by weight), less than 0.5% (by weight), less than 0.25% (by weight) based on the weight of the total aqueous composition.

When it is desired to assess the solubility of the oil phase but the phase is emulsified or in any other mixed form, the oil may be separated by any suitable method known to the skilled person (e.g. by centrifugation). Any desired characteristic of the oil phase so extracted can then be assessed by any appropriate standard method (e.g., solubility, glass transition temperature, chemical analysis).

Since solvents such as organic solvents can, among other things, change the solubility of the material, the use of such solvents should be avoided in order to maintain a proper separation of the oil-in-water emulsion and/or the components of the oil-in-water emulsion between the water phase and the oil phase.

As used herein in the specification and in the claims section that follows, the term "organic solvent" within or relative to the oil phase refers to an organic liquid disposed within the oil phase, containing at least one solute (e.g., prepolymer or reactant), and which does not participate positively in intra-polymer bonding, nor in bonding of the aminosilicone film to the textile fiber surface.

As used herein in the specification and in the claims section that follows, the term "co-solvent" within or relative to an aqueous phase refers to an organic liquid that is at least partially miscible within the aqueous phase. The organic liquid is further characterized in that it increases the solubility of at least one component in the oil phase in the aqueous phase. In extreme terms, a co-solvent that is miscible with water may cause the entire oil phase to "dissolve" in the water phase.

As a non-limiting example, the organic solvent may include a volatile C such as ethanol₁-C₆An alkanol; volatile C of, for example, hexane₅-C₇An alkane; liquid C₁-C₂₀Volatile C of acids and, for example, methyl acetate₁-C₈Esters of alcohols; volatile ketones such as acetone which are liquid at room temperature; volatilizeHydrocarbon-based oils, e.g. C, such as isododecane₈-C₁₆An alkane; volatile ethers such as dimethoxymethane or diethylene glycol monomethyl ether or glycol ethers; and mixtures thereof.

As used herein, "silicone compatible co-solvent" refers to an organic solvent that is miscible with water with the silicone based component (e.g., as described in detail with reference to the reactive oil phase). Thus, the presence of such silicone compatible co-solvents in the aqueous phase can result in an undesirable transition of either silicone component from the oil phase to the aqueous phase. By way of non-limiting example, the silicone compatible co-solvent may include a volatile C such as ethanol₁-C₆An alkanol; liquid C₁-C₂₀Volatile C of acids and, for example, methyl acetate₁-C₈Esters of alcohols; volatile ketones such as acetone which are liquid at room temperature; and mixtures thereof.

It is believed that if such a solvent is present in the same phase as the condensation curable aminosilicone prepolymer, condensation curing may be reduced or delayed in addition to the effect of reducing the oil phase and/or preventing emulsion formation.

In some embodiments, the total concentration of organic solvents in the oil phase of the emulsion is at most 10%, at most 5%, at most 2%, or at most 1% by weight. In some embodiments, the oil phase does not contain any organic solvent.

In some embodiments, the total concentration of silicone compatible co-solvents in the aqueous phase of the emulsion is at most 10%, at most 5%, at most 2%, or at most 1% by weight. In some embodiments, the aqueous phase does not contain any such co-solvent.

In some embodiments, the total concentration of organic solvent in the oil phase of the emulsion and silicone compatible co-solvent in the water phase is at most 10%, at most 5%, at most 2%, or at most 1% by weight of the oil-in-water emulsion. In some embodiments, the oil-in-water emulsion is substantially free of organic solvents and silicone compatible co-solvents.

The oil-in-water emulsion of the present invention is a two-phase system consisting of an oil phase in the form of droplets dispersed in a continuous second phase. The second phase may be water or an aqueous medium, or may be a carrier in which the oil phases are retained and which are immiscible with each other. Such carriers must be incompatible with the silicone to prevent any undesirable transformation of the silicone composition from the oil phase to the continuous second phase. Suitable carriers are selected from glycols (liquid or water-soluble solids), pegylated silicones or silicone polyethers. These carriers may be present as the sole component of the continuous second phase or used in combination with up to 50% by weight of water of the continuous second phase to maintain the positive surface potential of the oil-in-water emulsion.

As used herein in the specification and in the claims section that follows, the terms "solubility" with respect to a component or mixture of components ("component") and a solvent or mixture of solvents ("solvent") refer to the solubility of the component in the solvent at its natural pH, at the natural pH, obtained by merely adding the component to the solvent in the absence of other components and in the absence of any pH adjusting agent. In the case of specific water solubility, the definition assumes an initial pH of 7 for water.

In contrast to dyes, pigments are generally insoluble in water. In some embodiments, the pigment particles dispersed in the reactive oil phase of the emulsion are optionally insoluble therein.

In some embodiments, the concentration of condensation curable aminosilicone prepolymer having 3 or more silanol and/or hydrolyzable groups per molecule is at least 15%, at least 20%, at least 30%, at least 40%, at least 50%, or at least 60% by weight of the oil phase. In certain embodiments, the concentration of the 3-SiOH prepolymer is at most 95%, at most 90%, at most 85%, at most 80%, at most 75%, or at most 70%. In some embodiments, the concentration of the aminosilicone prepolymer in the oil phase is in the range of 20-95%, 20-85%, 30-95%, 30-85%, 40-95%, 40-85%, 40-75%, 45-95%, 45-85%, 50-95%, 50-85%, 55-95%, 55-85%, 55-75%, 60-95%, 60-90%, 60-85%, or 60-80%.

In some embodiments, the non-amino crosslinking agent is present in the oil phase. In such embodiments, the combined concentration of the aminosilicone prepolymer and the non-amino crosslinker in the oil phase ranges from 35-95%, 40-85%, 40-75%, 45-95%, 45-85%, 50-95%, 50-85%, 55-95%, 55-85%, 55-75%, 60-95%, 60-90%, 60-85%, or 60-80% by weight of the oil phase.

In some embodiments, the concentration of non-amino crosslinking agent within the combined concentration is limited by the following conditions: the surface electromotive force of the oil-in-water emulsion is greater than zero (>0), alternatively at least +1mV, at least +2mV, at least +3mV, at least +5mV, at least +7mV or at least +10 mV.

In some embodiments, in the oil phase, the total concentration by weight of any condensation curable amino silicone prepolymer having less than three condensation reactive groups per molecule, non-amino silicone oil, and amino silicone oil in the oil phase is in a range of 3% to 65%, 3% to 60%, 3% to 55%, 3% to 50%, 3% to 45%, 3% to 40%, 7% to 40%, 10% to 50%, 15% to 45%, 15% to 40%, 20% to 45%, 25% to 50%, 30% to 45%, 30% to 60%, 35% to 50%, or 35% to 60%. In some embodiments, the total concentration of the different components of the oil phase is such that the viscosity of the oil phase, measured at 23 ℃, is not more than 2000mPa s, not more than 500mPa s or not more than 100mPa s.

In some embodiments, the oil-in-water emulsion further comprises a solid hydrophobically reactive inorganic filler located or dispersed in the oil phase, the filler being selected or adapted to promote curing of the condensation curable film-forming amino silicone prepolymer. Such film reinforcing fillers may also be referred to as reactive fillers. Advantageously, the reactive reinforcing filler is a hydrophobic 3D network former that helps to increase the binding of the aminosilicone film.

The reinforcing filler may be generally chosen from fumed silica, precipitated silica, magnesia, alumina (for example Al)₂O₃·3H₂O), black fillers, amorphous fillers, carbon (carbon black, channel black or lamp black). The reinforcing filler may be selected to suit a particular color. For example, if relatively large amounts of reinforcing filler are required, then black filler should be avoided if within a size range that may affect the relatively light shade. Phase (C)Conversely, if a dark color is desired, a black reinforcing filler may be advantageous.

Suitable reactive fillers may be selected from hydrophobic fumed silicas, the surface of which is at least partially covered with siloxane groups or other groups having hydrophobic properties, which groups typically react with silanol functional groups on the silica. Thus, in this case, the hydrophobic fumed silica may be referred to as silanol-terminated silica, and surface treatment of the fumed silica may be achieved by one or more of HDMS, polysiloxane, cyclic polysiloxane, silazane, aminosilane, and silicone oil. The capping treatment need not be complete and some residual silanol groups are permissible, which may even be desirable to ensure or promote at least partial cure. When hydrophobic fumed silica is present, it is typically placed in the oil phase of an oil-in-water emulsion of condensation curable silicone.

In some embodiments, the reactive filler comprises, consists essentially of, or consists of hydrophobic fumed silica.

In some embodiments, the solid hydrophobically reactive inorganic filler has an average particle diameter (Dv50) in a range from 5 to 500 nanometers, 5 to 250 nanometers, 10 to 200 nanometers, 20 to 200 nanometers, 40 to 300 nanometers, 60 to 250 nanometers, or 60 to 200 nanometers.

In some embodiments, the concentration of the solid hydrophobic reactive inorganic filler as to or dispersed in the oil phase is in the range of 0.2% to 12%, 0.2 to 10%, 0.2 to 8%, 0.4 to 10%, 0.4 to 8%, 0.6 to 10%, 0.6 to 8%, 0.8 to 8%, or 0.8 to 6% by weight.

In some embodiments, the concentration of the solid hydrophobically reactive inorganic filler in the oil-in-water emulsion ranges from 0.005% to 0.5%, 0.005% to 0.3% by weight.

In some embodiments, the refractive index of the solid hydrophobic reactive inorganic filler, which may be selected as fumed silica filler, is within 10%, ± 7%, ± 5% or ± 3% of the refractive index of the oil phase excluding any pigment particles.

According to some embodiments, the pH of the oil-in-water emulsion is at least 4.0, at least 5.5, at least 7.0, at least 8.5, at least 10.0; and optionally at most 11.0. In some embodiments, the oil-in-water emulsion has a pH in the range of 4.0 to 12.0, 5.5 to 12.0, 7.0 to 11.0, or 8.5 to 11.0. A pH value above the isoelectric point of the textile fibers to be coated can negatively charge the fibers and/or positively charge the amino functional groups of the aminosilicone prepolymer. In the case of cotton fibers, the isoelectric point is reported to be about ph2.9, while wool has been reported to have an isoelectric point of about ph4.7, while synthetic fibers such as acrylic or polyester have been reported to have an isoelectric point of 3 or less than 2.5. As will be described in detail below, as a first step in the formation of the coating, a charge gradient between the surface of the textile fiber and the prepolymer of the composition is expected to allow electrostatic adhesion between the two. In particular embodiments, the oil-in-water emulsion has a basic pH of at least 7.5, at least 8.0, at least 9.0, or at least 9.5, and at most 11.0.

When using a composition with a pH above the isoelectric point of the fiber (e.g., >4, preferably >7), the surface of the textile fiber should be negatively charged. In some embodiments, the reactive condensation curable amino functional silicone prepolymer is positively charged when dispersed (e.g., emulsified) in a carrier. For example, aminosilicone prepolymers can be positively charged at a pH of 4.0 until the isoelectric point is reached (typically in the range of pH 10-12). Interestingly, protonation of amino groups above acidic pH (assuming sufficient concentration) can maintain the composition in the alkaline pH range even in the absence of a dedicated pH buffer. It is noted that for keratin textile fibers, at relatively high pH (>9), the scales of keratin fibers will be sufficiently charged to repel each other, resulting in open access to the fiber axis. The lifting of the hair flakes increases the surface area of the fibers, increasing the contact surface with the reactive aminosilicone prepolymer emulsion. As the carrier evaporates, the pH of the coating gradually decreases and the scales return to their original position, during which a portion of the aminosilicone film may become embedded, further enhancing its adhesion to the keratin textile fibers by mechanical interlocking.

According to some embodiments, the oil-in-water emulsion is applied to the textile fibers for a sufficient time to achieve a gradient that drives sufficient droplet wetting and formation of a continuous coating on the fibers. In one embodiment, the coating time is between 5 seconds and 60 minutes, or between 5 seconds and 30 minutes, or between 5 seconds and 10 minutes, or between 10 seconds and 2 minutes, or 1 minute or less. According to some embodiments, the duration of the partial curing is between 5 seconds and 30 minutes, or between 1 minute and 15 minutes. While partial curing may begin when applying the oil-in-water emulsion, it may also occur when excess emulsion is removed (e.g., before rinsing the textile fibers).

In some embodiments, the at least partially cured film self-terminates on the outer surface of the fiber.

In some embodiments, the partial curing is performed or occurs at a temperature of at most 75 ℃, at most 65 ℃, at most 55 ℃, at most 45 ℃, at most 38 ℃, at most 36 ℃, at most 34 ℃, at most 32 ℃, at most 30 ℃, or at most 28 ℃, and optionally, at a temperature of at least 15 ℃. In some embodiments, the partial cure occurs or occurs at a temperature range of 15 ℃ to 75 ℃, 15 ℃ to 65 ℃,20 ℃ to 55 ℃, or 20 ℃ to 45 ℃.

The maximum cure temperature may be determined by the heat sensitivity of the most sensitive component of the amino silicone emulsion, and thus, if the composition contains ingredients that decompose at temperatures above about 75 ℃, partial condensation curing should be performed at lower temperatures.

In some embodiments, the textile fibers are washed within 30 minutes, within 20 minutes, within 15 minutes, within 10 minutes, within 5 minutes, within 3 minutes, within 2 minutes, or within 1 minute after the coating of the oil-in-water emulsion is completed.

In some embodiments, after washing, the curing is further carried out by only or substantially only humidity or ambient humidity.

In some embodiments, within at least half a day, within at least one day, within at least two days, within at least three days, within at least five days, or within at least one week after said washing, all further curing is performed without adding a non-cationic surfactant to the textile fibers.

In some embodiments, the textile fibers may be treated with the cationic surfactant-containing textile formulation within at least half a day, within at least one day, within at least two days, within at least three days, within at least five days, or within at least one week after said washing.

In some embodiments, the rinse liquid is (i) water, or (ii) a cationic rinse liquid comprising a cationic surfactant, or (iii) a rinse liquid free of non-cationic surfactants, degreasers, and/or swelling agents capable of degreasing and swelling, respectively, the at least partially cured film.

In some embodiments, the cationic surfactant is a primary, secondary, tertiary, or quaternary ammonium compound or polymer.

In some embodiments, the total concentration of the reactive condensation curable aminosilicone component in the oil phase is at least 45%, at least 55%, at least 60%, or at least 65% by weight of the pigment-free. In some embodiments, the total concentration of reactive components is in the range of 50-100%, 50-95%, 50-90%, 50-85%, 50-80%, 55-95%, 55-85%, 60-95%, 60-85%, 65-95%, 65-90%, or 70-95%.

In some embodiments, the aminosilicone prepolymer includes reactive groups selected from alkoxy-silane reactive groups, silanol reactive groups, and combinations thereof.

In some embodiments, the solubility of the at least one reactive condensation curable film-forming aminosilicone prepolymer in water is less than 0.5% or less than 0.25% by weight.

In some embodiments, the total concentration of aminosilicone oil in the oil phase is at most 40%, at most 35%, at most 30%, at most 20%, at most 15%, at most 10%, or at most 5% by weight.

In some embodiments, the total concentration of aminosilicone oil in the oil phase ranges from 1% to 40%, 5% to 40%, 10% to 40%, 20% to 40%, 1% to 30%, 5% to 30%, 10% to 30%, 15% to 30%, 20% to 35%, or 20% to 30% by weight.

In some embodiments, the total concentration of non-aminosilicone oil in the oil phase is at most 15%, at most 12%, at most 10%, at most 7%, or at most 5% by weight, subject to the oil-in-water emulsion having a surface electromotive force greater than zero, or at least +1mV, at least +2mV, at least +3mV, at least +5mV, at least +7mV, or at least +10 mV.

In some embodiments, the total concentration of non-aminosilicone oil in the oil phase ranges from 1% to 15%, 3% to 15%, 5% to 15%, 8% to 15%, 1% to 12%, 3% to 12%, 5% to 12%, 3% to 10%, 3% to 8%, or 2% to 5% by weight.

In some embodiments, the non-amino crosslinking agent comprises, consists essentially of, or consists of a reactive condensation curable film-forming non-amino silicone monomer.

In some embodiments, the non-amino crosslinking agent comprises, consists essentially of, or consists of: ethyl silicate, poly (dimethoxysiloxane), poly (diethoxysiloxane), methyltrimethoxysilane, isocyanate, and bisphenol a diglycidyl ether.

In some embodiments, the total concentration of non-aminosilicone oil in the oil phase is at most 35%, at most 30%, at most 20%, at most 15%, at most 10%, or at most 5%, and the surface electromotive force experienced by the oil-in-water emulsion is greater than zero, or is at least +1mV, at least +2mV, at least +3mV, at least +5mV, at least +7mV, or at least +10 mV.

In some embodiments, the total concentration of prepolymer, non-amino crosslinker, solid hydrophobic reactive inorganic filler, aminosilicone oil, and non-aminosilicone oil (including any pigment particles and dispersants for pigment particles) in the oil phase is at least 90%, at least 93%, at least 95%, at least 97%, at least 98%, or at least 95% by weight of the oil phase.

In some embodiments, the aqueous phase further comprises an oil-in-water emulsifier, optionally non-ionic, having an HLB value of from 12 to 18, from 12 to 17, from 12 to 16, from 12 to 15 or from 13 to 16. In some embodiments, the total concentration of water and any emulsifier in the aqueous phase is at least 90%, at least 95%, at least 97%, or at least 99% by weight.

In some embodiments, the aqueous phase further comprises a pH adjuster. In some embodiments, a pH adjusting agent is added to the aqueous phase to provide the oil-in-water emulsion with a suitable pH and/or a suitable surface potential as described herein.

In some embodiments, the textile fibers coated thereon with the oil-in-water emulsion are dry or unwetted textile fibers, or pre-dyed textile fibers. In some embodiments, the textile fibers coated thereon with the oil-in-water emulsion are at least one of non-degreased, non-washed, and unbleached.

In some embodiments, the oil phase further comprises at least one pigment selected from a plurality of submicron pigment particles or a plurality of metallic pigments.

In some embodiments, the oil-in-water emulsion further comprises a dispersant, the submicron pigment particles dispersed in the dispersant.

In some embodiments, the aqueous phase comprises a pigment in the oil phase in an amount of at most 20%, at most 10%, at most 5%, or at most 2% by weight. In some embodiments, the aqueous phase is free of the pigment.

In some embodiments, at a relative humidity of 30% to 50% and a temperature of 23 ℃, the at least partially cured film achieves permanence within 24 hours after coating the oil-in-water emulsion on textile fibers, and optionally within 12 hours, within 4 hours, within 2 hours, or within 1 hour. In particular embodiments, the persistence is achieved within 45 minutes, within less than 30 minutes, within less than 15 minutes, within less than 10 minutes, or within less than 5 minutes.

Pretreatment of reactive oil phase

Hydrolysis of various silicone-based molecules may be required prior to condensation curing of the aminosilicone layer. The inventors have found that the condensation cure rate of the aminosilicone layer may be significantly affected, or even controlled, by the extent of this hydrolysis, and that this hydrolysis-particularly in the region of the film closest to the outer surface of the textile fibre-is diffusion controlled (i.e. limited by the diffusion of water/moisture from the environment through the overlying film, if any), regardless of the thickness of the AS coating (typically 0.5 microns). The inventors believe that incomplete curing in the region of the film closest to the surface of the textile fibre may significantly reduce the durability of the colouration: when mechanical shear, drag, or other forces are applied to the fibers, the weak bonds between the film and the fibers may weaken or otherwise be compromised, resulting in the film deteriorating and at least partially falling off the textile fibers. Perhaps even more importantly, this incomplete curing can allow detergent powders, textile detergents, soaps and other anionic and/or nonionic surfactant-containing materials to penetrate through the AS membrane to the fiber surface, or to reach the fiber surface through the AS, in which case they can successfully compete with the anionic functional groups of the fiber surface, thereby weakening the bond between the textile fibers and the AS membrane at the interface (similar to a "degreasing" operation). This degradation "window" may occur within one week after initial film formation due to the overall slow kinetics of the condensation cure reaction (e.g., including diffusion limitations), especially at the textile fiber-AS interface.

The inventors have further found that partial condensation curing of one or more aminosilicone substances ex vivo (invitro) prior to application to textile fibres can significantly improve various properties of the aminosilicone films obtained. This ex vivo step may be referred to as pretreatment, and the time allowed for this step to occur may be referred to as incubation time, i.e., pretreatment duration or pretreatment duration. The properties improved by a suitable pretreatment for a sufficient period of time include, in particular, the adhesion of the aminosilicone film. The extent of this partial hydrolysis and pre-curing should be sufficient to trigger the formation of "reactive lumps" while retaining sufficient reactivity to adhere to the textile fibers and effect additional curing thereon. Without wishing to be bound by any particular theory, it is believed that the formation of the elastic network of the cured aminosilicone initially proceeds in an "exponential" manner. The rate of cure and the degree of pre-cure at any point in time of pre-treatment contemplated are particularly commensurate with the number of reactive condensable curing groups in the participating prepolymers, the number of reactive prepolymers, and the number of pre-treatment solutions in the reactants in the case of pre-treating the oil phase. For simplicity, the formation of the network can be assimilated as a chain reaction, gaining momentum at a slow rate over time early until a plateau is reached, at which time the rate of solidification is significantly reduced.

When the oil phase is emulsified soon after preparation (without any special pre-treatment) and the resulting oil-in-water emulsion is applied to the textile fibres quickly (e.g. in less than 30 minutes), the ex vivo curing process is almost non-existent. Thus, the in situ cure must start with an essentially natural amino silicone material. Thus, when the polymerization reaction proceeds at a relatively slow initial rate, partial condensation curing on the textile fibers begins at the lag phase of curing. The pretreatment allows partial curing to reach the accelerated "exponential" stage of the network formation process. It is believed that after coating an oil-in-water emulsion prepared from such a pre-treated oil phase, the reactive lumps generated ex vivo can act as nuclei for continued solidification on the fibers. Thus, in situ curing may continue on the textile fibers rather than being initiated, thereby providing a further starting point for the formation of a bonded network.

The duration of the pretreatment may be sufficient depending on the oil phase being pretreated. A 20% or more increase in oil phase viscosity compared to the initial viscosity of the same oil phase at the beginning of the pretreatment may indicate a sufficient pretreatment duration.

The extent of such partial pre-cure should be sufficient to be detected by FTIR analysis of the pre-treatment composition to detect hydroxyl peaks. During the stages of partial hydrolysis and pre-cure, the pre-treatment composition does not contain a fully cured polymer in an amount detectable by the glass transition temperature of formation, and therefore lacks a Tg. The ex vivo pre-cure is sufficiently short to prevent formation of a 3D network with a detectable Tg. In some embodiments, the viscosity of the partially pre-cured pretreatment composition (independent of the viscosity of the reactants isolated from the initial mixture) is 100m Pas or less, or 50m Pas or less, or 25m Pas or less. In some embodiments, the viscosity of the partially pre-cured pretreatment composition is at least 1 m-Pas, or at least 5 m-Pas, or at least 10 m-Pas.

Pretreatment of the reactive oil phase further reduces the mass transfer limitations described above. The inventors have found that advantageously, as long as condensation curing can be carried out on the textile fibres, the colouring is not affected by this prehydrolysis step. Therefore, this additional step does not substantially impair the target optical density, and the durability of the film, and the time required to obtain such durability, can be advantageously further improved.

The inventors have found that the crosslinking density and the crosslinking speed can be increased by using reactive silicones, and that the density and speed can be further increased by using suitable crosslinking agents for these reactive silicones. Crosslinking can contribute significantly to the three-dimensional bonding and strength of the polymer film. This is particularly important for reinforcing or fixing the membrane on the surface of the textile fibres. Also, without wishing to be bound by theory, the inventors believe that the bond strength to textile fibers (associated with "permanence") can be significantly improved by the interaction and/or bonding between silanol groups from the reactive silicone and the individual functional groups (e.g., -OH) on the fiber surface. In addition, the enhanced entanglement throughout the volume of the membrane improves the bonding strength of the membrane and may contribute to the stability of the fiber-membrane bond (e.g., by steric hindrance).

In some embodiments, these reactive silicone reinforcing fillers are encapsulated in the formulation. The reinforcing filler may comprise, consist essentially of (greater than 50% by weight or volume), or consist essentially of a three-dimensional reactive filler such as fumed silica. Fumed silica is hydrophobic in the sense that it is not self-dispersing in water. However, in the reactive AS-containing phase, the hydrophobic three-dimensional reactive filler is preferably selected and/or adapted to have at least some self-dispersibility (e.g., dispersion to a sub-micron average particle size (e.g., 200 nanometers by volume to D50) or less in the reactive AS-containing phase) so that the hydrophobic three-dimensional reactive filler particles can readily serve AS nucleation centers to rapidly promote strong three-dimensional crosslinking.

It must be emphasized that the presence of such fillers per se in the formulation does not in itself indicate any function as three-dimensional reactive fillers. For example, fumed silica can be used as a thickener in various industrial applications known in the art. In this case, the fumed silica is naturally hydrophilic, provided that the thickening is directed to an aqueous medium. However, in order to function as a reactive three-dimensionally crosslinked filler, it is necessary to place the filler (e.g., hydrophobic fumed silica) in the reactive phase of the formulation (in this case, in the non-aqueous phase containing the reactive aminosilicone material).

The inventors have further discovered that such fillers can be used to overcome or significantly mitigate mass transfer limited kinetics throughout the condensation curing process. In general, such fillers are characterized by an extremely high specific surface area. The total specific surface area and internal surface area of a porous solid (e.g., fumed silica) can be determined by measuring the amount of physisorbed gas according to the Brunauer, Emmett, and teller (bet) method. The specific surface area may be determined according to ISO9277, and in one embodiment, the surface area is at least 25m²A/g of at least 50m²/g or at least 75m²A/g, more typically at least 100m²A,/g²/g or at least 120m²/g, and/or in the range from 25 to 400m²/g、60-400m²/g、60-300m²/g、80-400m²/g、80-350m²/g、80-300m²/g、90-400m²/g、90-350m²/g、90-300m²Per g or 100-350m²In the range of/g. These packing materials may have a low concentration of adsorbed water that is uniformly distributed (e.g., about 0.5%). Thus, when the packing material is placed in the reactive phase of the formulation, this low, but uniformly distributed and available water content may partially bypass or circumvent the mass transport limitation of water diffusing out of the environment, through the membrane, to the surface of the textile fibers.

This effect can be enhanced by using reactive filler materials with higher water concentrations (e.g., as close to the saturation point as possible at room temperature, and/or by using reactive filler materials with particularly high specific surface areas). Indeed, in some embodiments, the inventors have introduced a pre-treatment step in which a solid reactive filler material is exposed to saturated water vapor to significantly increase its water concentration. A corresponding improvement in the durability of the film was observed.

The inventors have further found that water may additionally or alternatively be added to the liquid component of the reactive oil phase to achieve similar improvements. One method of introducing a known amount of a pretreatment solution (e.g., water) into the reactants of a condensation-curable aminosilicone emulsion is described with reference to fig. 5. For purposes of this specification, the term "reactant" refers to any material that participates in the pretreatment, whether or not the condensation cure is reactive relative to the final emulsion prepared using the water-rich or pretreated reactant (i.e., the water-rich reactant). Thus, the term "reactants" may include reactive condensation curable aminosilicone prepolymers, as well as aminosilicone oils, non-aminosilicone oils, crosslinkers, solid reactive fillers and pigment dispersants present in the reactive oil phase. Depending on the initial amount of water in the reactants supplied, a preliminary optional drying step S101 may be required. Such a step may help to better control the amount of pretreatment solution added to reactants that may have fluctuating natural water content, reducing variations caused by such natural water content.

Various methods of drying the reactant (e.g., water-rich reactant) to remove excess water are known to the skilled artisan. The drying method can be chosen and adapted to the reactants to be dried. For example, a solid reactant of a reactive filler such as hydrophobic fumed silica can be dried in an oven to evaporate excess water. For liquid reactants such as reactive condensation curable amino silicone prepolymers, certain crosslinkers or silicone oils, molecular sieves with appropriate pore size can be used to selectively capture water to remove excess water. After step S101 (if desired), the corresponding dried reactant is substantially dry with a minimal amount of residual water (if any). The dried or dried reactants are typically kept in a desiccator under a dry inert atmosphere or vacuum to ensure that their water content, if any, is maintained at a respective minimum level until use. When the reactants comprise less than or equal to 0.5 wt.%, or less than 0.1 wt.%, or less than 0.05 wt.%, or less than 0.01 wt.% water, by weight of the reactants, the reactants are substantially dry.

In step S102, the dried reactants are supplemented with a known amount of water or any desired aqueous pretreatment solution. This step S102 of controlling the addition of water may also be referred to as a humidification step, the humidified reactants also being referred to as premixed or pre-treated reactants. In some embodiments, the amount of water added exceeds the amount of water that the reactants normally absorb in their naturally supplied state (e.g., by at least 25% or more, even by at least an order of magnitude). For a particular pretreatment, it is sufficient to humidify the single reactant of the pretreatment composition. However, according to other embodiments, more than one reactant may be separately humidified for use in preparing the composition. In step S103, reactants comprising at least one humidified reactant are mixed to form a pretreatment composition at time point 0. Alternatively, at least one of the humidified reactants may be separately humidified and pretreated, with such separately performed pretreatment being followed by the formation of a "pretreatment" mixture. If the amount of water added is sufficiently small, the pretreatment composition forms a homogeneous oil phase (no visible separated aqueous phase). The pre-treated oil phase was clear (no turbidity) further confirming that the water addition was sufficiently low. The aqueous pretreatment solution is typically added gradually to the dried or dried reactants, thereby making the adsorption of water more gradual and uniform, and thus reducing the risk of phase separation.

In some embodiments, the pretreatment solution consists essentially of distilled water having a pH of 6.5 to 7.5.

In some embodiments, the water (or aqueous pretreatment solution) constitutes 10 wt.% or less, or less than 5 wt.%, or less than 4 wt.%, or less than 3 wt.%, or less than 1 wt.% of the weight of the reactants; optionally at least 0.1 wt.%, or at least 0.2 wt.%, or at least 0.3 wt.% of the weight of the reactants.

In some embodiments, 15 wt.% or less, 12.5 wt.% or less, 10 wt.% or less, or less than 5 wt.%, or less than 4 wt.%, or less than 3 wt.%, or less than 1 wt.% of water (or aqueous pretreatment solution), by weight of the reactants, is added to the reactants; optionally, at least 0.1 wt.%, or at least 0.2 wt.%, or at least 0.3 wt.% water (or aqueous pretreatment solution) by weight of the reactants is added to the reactants. In some embodiments, water (or aqueous pretreatment solution) in the range of 0.1 wt.% to 15 wt.%, 0.2 wt.% to 15 wt.%, or 0.3 wt.% to 12.5 wt.% by weight of the reactants is added to the reactants.

In some embodiments, the water (or aqueous pretreatment solution) is present in an amount of 8 wt.% or less, 6.7 wt.% or less, 5 wt.% or less, 2.5 wt.% or less, 2 wt.% or less, 1 wt.% or less, or 0.5 wt.% or less, based on the weight of the oil phase. In some embodiments, the amount of water (or aqueous pretreatment solution) is at least 0.01 wt.%, or at least 0.05 wt.%, or at least 0.1 wt.%, or at least 0.15 wt.%, or at least 0.2 wt.%, or at least 0.25 wt.%, or at least 0.5 wt.%, or at least 0.75 wt.%, or at least 1 wt.% based on the weight of the oil phase. In some embodiments, the amount of water (or aqueous pretreatment solution) in the oil phase ranges from 0.01 wt.% to 8 wt.%, from 0.1 wt.% to 8 wt.%, or from 0.2 wt.% to 6.7 wt.%, based on the weight of the oil phase.

In some embodiments, 8 wt.% or less, 7 wt.% or less, 5 wt.% or less, 2.5 wt.% or less, 2 wt.% or less, 1 wt.% or less, or 0.5 wt.% or less of water (or aqueous pretreatment solution), based on the total weight of the oil phase, is added to the at least one reactant in the oil phase. In some embodiments, at least 0.01 wt.%, or at least 0.05 wt.%, or at least 0.1 wt.% water (or aqueous pretreatment solution), based on the weight of the oil phase, is added to the at least one reactant. In some embodiments, between 0.01 wt.% to 8 wt.%, 0.05 wt.% to 8 wt.%, or 0.1 wt.% to 5 wt.% water (or aqueous pretreatment solution), by weight of the oil phase, is added to the at least one reactant.

In some embodiments, the volume ratio of oil phase to water phase in the oil phase or the pretreated oil phase is at least 9: 1. at least 9.33: 0.67 (14: 1), at least 9.5: 0.5 (19: 1) or at least 9.75: 0.25 (39: 1), optionally the oil phase or the pre-treated oil phase is completely free of aqueous phase.

It should be noted that the amount of aqueous pre-treatment solution added to the reactants is negligible compared to the amount of water or aqueous medium surrounding the droplets after emulsification of the oil phase. The inventors have determined that the aqueous phase of the emulsion only slightly contributes to the process triggered by the ex vivo pretreatment. It is believed that the surrounding water can only interact with the outer surface of the oil droplets and that further diffusion towards the droplet contents is in fact very slow. For similar reasons, water present on the textile fibres or further added as a humectant does not function in a comparable manner to the pretreatment. In this particular case, it is further believed that the oil droplets, after deposition on the textile fibres, tend to repel such water (making it unusable for film formation). The presence of water in the oil phase is believed to mitigate slow diffusion of such molecules from the outside/surroundings.

The pretreatment composition of step S103 may then be incubated in step S104 for any predetermined amount of time. Incubation can be carried out at room temperature (about 23 ℃) or at any other temperature (typically not more than 50 ℃ when the temperature is above ambient temperature). It is believed that during the incubation time of the pretreatment composition, the amount of water is sufficient to initiate hydrolysis of at least a portion of the hydrolyzable portion of the associated reactant. Although complete hydrolysis is not required during pretreatment, it is understood that even in this case, the prepolymer may remain reactive with respect to condensation cure. The fact that the pretreatment composition is still liquid and/or lacks a glass transition temperature can readily demonstrate the fact that the prepolymer is still reactive.

After incubation, the pre-treated oil phase may be added to the desired aqueous phase (e.g., with or without the addition of an emulsifier) for emulsification in step S105. After this step, an emulsion of reactive condensation curable aminosilicone may be used for coating. The actual coating of the textile fibers S106 can usually be done within 30 minutes after emulsification.

Without wishing to be bound by any particular theory, it is believed that the trace amount of water (or aqueous pretreatment solution) present in the pretreatment composition (e.g., in the reactive oil phase) can promote hydrolysis of the hydrolyzable portion of the reactive reactants. This partial bulk hydrolysis, in turn, can promote condensation curing of the hydrolyzed portions of the reactive reactants (e.g., the aminosilicone prepolymer). The inventors have found that the initiation of the ex vivo condensation curing of the aminosilicone prepolymer, once applied to the textile fibre, accelerates its continued condensation, generally shortening the length of time required for complete curing. The incubation time of the pretreatment composition (which may depend on factors such as temperature, type of aqueous pretreatment solution, amount and total amount of each reactant added, and the like) should be sufficient to provide such triggering, but short enough to ensure that the aminosilicone prepolymer being coated after emulsification is still reactive and capable of condensation curing on the textile fibers after coating.

Fig. 3A is a schematic illustrating the change in hydroxyl concentration over time in an ex vivo pretreatment reaction of a reactive aminosilicone formulation (e.g., an oil-in-water emulsion), according to an embodiment of the present invention. The times shown (along the X-axis) are qualitative and illustrative, as absolute times may be slower or faster, depending on the particular prepolymer, formulation components, and operating parameters.

According to some embodiments of the invention, the reaction is carried out at a pH in the range of 7.5 to 12, and more typically between 8 and 11 or between 8 and 10.5. The inventors believe that the initial increase in hydroxyl concentration results from hydrolysis of the hydrolysable groups (typically alkoxy, acyloxy, and/or oxime) to form silanol groups. This initial rise may begin to flatten out as the rate of hydroxyl generation decreases. Over time, a relatively slow curing reaction then occurs, and the silanol groups polymerize through a condensation reaction to produce siloxane bonds (and release water). This condensation reaction consumes hydroxyl groups, so that the hydroxyl group concentration decreases as the reaction time progresses.

Fig. 3B is a graph illustrating the coloring effect of the partially reacted aminosilicone formulation of fig. 3A coated on textile fibers as a function of the ex vivo reaction time (function) of the pretreatment formulation prior to coating the partially reacted formulation on the textile fibers. As described in further detail herein, the produced partially reacted aminosilicone formulation is then emulsified with water (with or without other additives, such as emulsifiers or pH adjusters) to produce a textile fiber treatment emulsion that can be applied directly to textile fibers. As is evident from the qualitative curve provided in fig. 3B, an efficient coloration of the textile fibers can be achieved even at t ═ 0, which corresponds to no ex vivo reaction of the reactive aminosilicone formulation prior to application of the formulation to the textile fibers. The inventors have found that the textile colouring effect can be maintained at a high level for a long time until a relatively high degree of cross-linking is achieved. Then, as the degree of crosslinking continues to increase, the coloring effect of the textile may decrease or significantly decrease. The inventors believe that when applying the partially cured aminosilicone formulation to textile fibres, the highly crosslinked material achieves poor wetting of the fibres and that when removing excess material, much of the pigment-containing polymer is simply washed away. This state is represented, for example, by point a in fig. 3B.

The results of using highly cross-linked materials appear to be evidenced by the fact that satisfactory initial dyeing of hair fibers cannot be achieved using various disclosed non-reactive aminosilicone-based hair dyes and methods. The same results are expected when coloring textile fibers. Such cross-linked silicones unsuitable for the teachings of the present invention are generally referred to as silicone resins, and as explained, are characterized by at least one of a high molecular weight, a high viscosity (or solid at ambient temperature), or a glass transition temperature (Tg).

Furthermore, even if a satisfactory initial coloration is obtained by means of a formulation comprising a material having a low degree of crosslinking which is sufficient to wet the surface of the textile fibres, such a formulation may obviously not exhibit a coloration permanence (for example washing fastness). This state is represented, for example, by point B in fig. 3B. Also indicated in fig. 3C is point B, which illustrates a schematic of the durability of coloration of textile fibers AS a function of the ex vivo reaction time of the partially reacted AS formulation prior to emulsification and application of the formulation to the textile fibers. Clearly, for the ex vivo reaction time of point B, the staining appeared satisfactory, but the persistence was lower.

As discussed in further detail herein, the durability of the coloration is measured after removing excess coated formulation from the textile and then curing the coated formulation on the textile fibers under ambient conditions (e.g., 24 hours). Fig. 3C schematically shows the durability as assessed by the wash durability at 24 hours after coating. As described below and in the examples, in some embodiments, the pretreatment of the reactive oil phase creates persistence of coloration at an earlier time point within 24 hours after coloration.

AS described substantially above, the inventors believe that incomplete curing in the region of the membrane closest to the outer surface of the textile fibre may be due to mechanical forces at the interface between the AS membrane and the outer surface of the fibre and susceptibility to insertion and chemical attack, significantly reducing the permanent coloration.

It must be emphasized that the various aminosilicone formulations considered to be "reactive" are in practice substantially non-reactive, since these formulations are already highly crosslinked before coating, and therefore the degree of additional crosslinking that may occur after coating may be small (especially under ambient conditions) and may not be sufficient to achieve a satisfactory (initial) coloration. Alternatively, the initial coloration may be satisfactory, but the persistence may be poor or less satisfactory.

Referring again to fig. 3C, it is evident from this qualitative curve that the durability of coloration of the textile fibers at t ═ 0 may be less satisfactory, corresponding to the absence of ex vivo reaction of the reactive aminosilicone formulation prior to application of the formulation to the textile fibers. Although effective coloration of textile fibers can be achieved with short ex vivo reaction times, the inventors have found that the coloration durability may be less satisfactory, AS noted above, in part because of the extremely low level of crosslinking at the interface between the AS membrane and the outer surface of the fiber. As the level of crosslinking at the interface increases, so does the durability, as shown by the first shoulder region C. As the level of crosslinking at the interface increases, the durability may tend to level or substantially level, as shown by the durable land region D.

Fig. 3D is a schematic illustrating the tackiness of the partially reacted aminosilicone formulation of fig. 3A coated on textile fiber fabric as a function of the ex vivo reaction time of the formulation prior to coating the formulation on the textile fiber.

The inventors believe that as crosslinking increases, the adhesion to the textile fibres decreases.

Thus, by controlling the ex vivo reaction time and operating conditions, the method of the present invention is capable of operating within an overlapping range of coloration, tack and durability "time windows" ("windows") to achieve sufficient textile coloration (e.g., characterized by optical density, etc.) and coloration durability.

In addition, the inventors have surprisingly found that the pH of the reactant pretreatment solution used to humidify the ex vivo reaction mixture can be controlled to accelerate the hydrolysis and condensation reactions, thereby actually immediately reducing the stickiness (e.g., and low ex vivo reaction times of up to 10 minutes) and/or to extend the overlap of the coloration, stickiness, and persistence time windows. More specifically, the pH of the pretreatment solution should be at most 2.5, at most 2, and more typically at most 1.8, at most 1.6, at most 1.4, or at most 1.2. The pH should be in the range of 0.5 to 2.5, 0.5 to 2.0, 0.7 to 1.8, 0.7 to 1.6, 0.7 to 1.4, 0.7 to 1.2, 0.9 to 2.0, 0.9 to 1.7, 0.9 to 1.5, 0.9 to 1.3, or 0.9 to 1.2.

However, the inventors have found that typical acids used to lower the pH can contribute a "permanent" ionic content to the reactive mixture, which can ultimately compromise the properties of the aminosilicone membrane.

Surprisingly, the inventors have found that by lowering the pH using a volatile acid (preferably, concentrated acetic acid, e.g., comprising at least 30%, at least 40%, at least 50%, at least 60%, or at least 80%), the pH of the pretreatment solution can be lowered sufficiently to favorably alter the time window of the ex vivo reaction, and can also be volatilized such that there is no residual ionic content in the acid. Therefore, without introducing contaminants by the acidifying agent, the necessary ex vivo reaction time can be reduced, reaction control can be relaxed, and process stability can be improved.

Fig. 4 provides a schematic illustrating the degree of hydrolysis (detectable by hydroxyl/silanol concentration), coloring effect, tack and durability of coloration of textile fibers as a function of ex vivo reaction time (prior to application of a portion of the reactive formulation to the textile fibers) of the reactive aminosilicone formulation based on fig. 3A with an aqueous pretreatment solution with pH adjustment.

Thus, the duration of the pretreatment (or pretreatment duration, pretreatment time) may depend, inter alia, on the type and onset of the desired result, as well as the type of pretreatment solution and its total concentration in the reactive oil phase, based on the presence of the respective pretreatment reactant. In some embodiments, the duration of the pretreatment is no more than 24 hours, or less than 12 hours, less than 8 hours, less than 6 hours, or less than 4 hours. Advantageously, the duration of the pretreatment may be 120 minutes or less, less than 90 minutes, less than 60 minutes, less than 30 minutes, less than 20 minutes, less than 10 minutes, or less than 5 minutes.

Since the rate of (partial) condensation curing and/or hydrolysis may depend on the temperature, the duration of the pretreatment may be shortened as the pretreatment temperature is increased. Although the pretreatment may conveniently be carried out at ambient temperature, it may also be carried out at higher temperatures, typically not exceeding 75 ℃. In some embodiments, the pretreatment is carried out at a temperature of 15-75 deg.C, 15-70 deg.C, 15-65 deg.C, 15-60 deg.C, 15-55 deg.C, 15-50 deg.C, 18-45 deg.C, 20-40 deg.C, 20-35 deg.C, 20-30 deg.C, or 20-25 deg.C.

The reactive oil phase according to the present teachings can then be emulsified to prepare an oil-in-water emulsion of the reactive condensation curable aminosilicone prepolymer which meets the teachings regarding the emulsion applied to textile fibers according to the present invention.

According to some embodiments, the concentration of the reactive condensation curable amino silicone prepolymer is in the range of about 0.001 to 20% by total weight of the composition, e.g., oil-in-water emulsion), for example in the range of about 0.005 to 10%, f about 0.005 to 5%, about 0.005 to 2.5%, or about 0.01 to 1% by total weight.

According to some embodiments, the concentration of the reactive condensation curable amino-functional silicone composition is at least 45 wt.%, at least 55%, at least 60%, or at least 65%, and optionally in the range of 50-100 wt.%, 50-95 wt.%, 50-90 wt.%, 50-85 wt.%, 50-80 wt.%, 55-95 wt.%, 55-85 wt.%, 60-95 wt.%, 60-85 wt.%, 65-95 wt.%, 65-90 wt.%, or 70-95 wt.%, by weight of the oil phase.

According to some embodiments, suitable non-aminosilicone oils may be linear, branched or cyclic organosiloxanes, such as decamethylcyclopentasiloxane (D5), octamethylcyclotetrasiloxane (D4) or hexamethyldisiloxane (M2).

According to some embodiments, the total concentration of non-amino silicone oil is at most 15 wt.%, at most 12 wt.%, at most 10 wt.%, at most 7 wt.%, or at most 5 wt.%, by weight of the oil phase.

According to some embodiments, the sub-micron pigment particles comprise an organic pigment, such as an organic pigment selected from the group consisting of perylene pigments, phthalocyanine pigments, quinacridone pigments and imidazolinone (imidazolone) pigments.

According to some embodiments, the sub-micron pigment particles comprise an inorganic pigment, such as an inorganic pigment selected from titanium dioxide, cadmium sulfoselenide, iron oxide, bismuth vanadate, cobalt titanate, sodium aluminosilicate, mixed iron-magnesium-titanium oxide, manganese ferrite, and metal or alloy pigments.

In some embodiments, submicron organic or inorganic pigments (or combinations thereof) are used as color imparting agents (colorizing agents). Submicron pigments may also be referred to as light absorbing pigments or simply absorbing pigments.

According to some embodiments, the sub-micron pigment is an organic or inorganic pigment selected from the following colors: CI10006, CI10020, CI10316, CI11680, CI11710, CI11725, CI11920, CI12010, CI12085, CI12120, CI12370, CI12420, CI12480, CI12490, CI12700, CI13015, CI14270, CI14700, CI14720, CI14815, CI15510, CI15525, CI15580, CI15620, CI15630, CI15800, CI15850, CI15865, CI15880, CI15980, CI15985, CI16035, CI16185, CI16230, CI16255, CI16290, CI17200, CI18050, CI18130, CI18690, CI 18718736, 18820, CI18965, CI19140, CI20040, CI20470, CI21100, CI21108, CI21230, CI24790, CI27755, CI 40755, CI 40440, CI 42048, CI 420520, CI 420420, CI 420520, CI 4280, CI 4206047520, CI 420420, CI 4280, CI 4206047520, CI42080, CI 42048, CI42080, CI 4206047520, CI42080, CI 42048, CI20470, CI42080, CI 42048, CI42080, CI 42048, CI42080, CI 20480, CI42080, CI 20480, CI 42048, CI 20480, CI42080, CI 42048, CI 20480, CI 42048, CI 20480, CI 53, CI 42048, CI 42095, CI 20480, CI 42095, CI 53, CI 20480, CI 42095, CI 20480, CI 42048, CI 20480, CI420, capsorubin (capsanthin), capsaicin (capsorubin), beetroot red, anthocyanins, bromothymol blue, bromocresol green, and acid red 195.

According to some embodiments, the sub-micron pigment is selected from the following organic pigments:

d & C Black No.2, D & C Black No.3, FD & C blue No.1, D & C blue No.4, D & C Brown No.1, FD & C Green No.3, D & C Green No.5, D & C Green No.6, D & C Green No.8, D & C orange No.4, D & C orange No.5, D & C orange No.10, D & C orange No.11, FD & C Red No.4, D & C Red No.6, D & C Red No.7, D & C Red No.17, D & C Red No.21, D & C Red No.22, D & C Red No.27, D & C Red No.28, D & C Red No.30, D & C Red No.31, D & C Red No.33, D & C Red No.34, D & C Red No.36, FD & C Red No.40, Ext.Red No.40, yellow & C Red No.7, yellow & C Red No.11, D & C Red No.7, D & C Red No.11, yellow & C Red No.7, and D & C Red No. 7.

In some embodiments, the pigments of the present invention provide special visual effects in place of or in addition to coloring effects and/or metallic appearance. By way of non-limiting example, special effects include fluorescent effects, sparkling effects, pearlescent effects, pearlescence effects, and phosphorescence effects. These effects may be visible under normal lighting or may require (or further increase) special viewing conditions to be visible, e.g. as a function of lighting conditions, viewing angle. For example, fluorescent pigments may become visible or may provide a fluorescent effect when illuminated with Ultraviolet (UV) light. At the other end of the spectrum, upconverting pigments are luminescent materials capable of converting Near Infrared (NIR) light into Visible (VIS) light. Other colorants that provide less typical colorations also include, as non-limiting examples, thermochromic pigments or dyes that cause compositions containing them to change color due to temperature changes, and pH-dependent pigments that change color with pH.

Any of the above pigments may be further surface treated, for example with an organic agent, to further improve any desired properties of the pigment (e.g., visual effect, chemical stability, dispersibility, charge, adhesion to fibers, ability to interact with the amino silicone matrix, etc.). Surface treatment techniques need not be described in detail herein, and surface treated (e.g., nonionic, cationic, anionic, positively charged, negatively charged, or substantially uncharged) pigments are commercially available in the desired form. The surface treatment of the pigment particles may be a chemical coating, for example a fatty acid such as oleic acid, stearic acid, an adhesion promoting polymer coating such as an acrylic polymer, a silane polymer or an amino-silane polymer, and such chemical coatings as are known in the pigment art.

All of these pigments can be used in all aspects and embodiments of the textile colouring method and kit of the invention to adapt the pigment to the substrate into which it is incorporated. In one embodiment, when it is desired to use pigments in the aminosilicone coating, the pigment particles may be surface treated (e.g., by acid groups) to improve the interaction between the pigments and the aminosilicone prepolymer embedding them during formation of the 3D aminosilicone network on the textile fibers. However, such pigment treatment may be redundant or even undesirable because of the different manner in which pigments are incorporated into polymeric materials having acid-neutralizable moieties when incorporated into polymeric coatings. The color-imparting agents used in the present invention are pigments, which may optionally be combined with or replaced by dyes in certain cases (e.g., for coloring hair). However, even if dyes are used as color-imparting agents for compositions or pigment coatings, they are not oxidative dyes. In some embodiments, the compositions according to the present teachings are substantially free of oxidative dyes and any chemical agents typically used in combination with oxidative dyes, including, but not limited to, couplers and oxidizers of dyes (e.g., hydrogen peroxide developers).

In some embodiments, the pigment is reduced in size and/or dispersed prior to incorporation into the reactive oil phase of the emulsion of the present invention. In this case, the size reduction and/or dispersion step may be carried out in the presence of a pigment dispersant.

According to some embodiments, the pigment dispersant is present in the oil-in-water emulsion in an amount of 25% to 400% by weight of the submicron pigment particles. In some embodiments, the relative weight ratio of dispersant to pigment particles is in the range of 0.5: 1 to 2:1, 0.75: 1 to 1.5: 1, or 0.8: 1 to 1.2: 1.

According to some embodiments, a dispersant suitable for dispersing pigments is compatible with condensation curable formulations. By compatible, it is meant, for example, that the pigment dispersant is miscible with the reactive oil phase of the formulation, that the pigment dispersant does not retard, reduce, or prevent condensation curing, and that the pigment dispersant is stable (e.g., non-reactive) during the size reduction of the pigment. Preferably, the pigment dispersant may have a positive charge.

Such dispersants may have a silicone backbone, for example, silicone polyether and silicone amine dispersants. Suitable pigment dispersants include, for example, silicone amines, such as BYKLPX21879 from BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1 from Genesee Polymers, silicone acrylates, such as those of Evonik

And

PDMS silicones with carboxyl functionality, such as X-22162 and X-22370 from Shin-Etsu, silicone epoxies, for exampleSuch as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682 and GP-695 of Genesepolymmers or EvonikOr a polyglycerin-modified silicone such as KF-6106 of Shin-Etsu. Silicone amine dispersants are positively charged and may be advantageous in some embodiments according to the present teachings.

In some embodiments, the pigment dispersant is an amino silicone having an amine number of 3 to 1000, 3 to 500, or 3 to 200.

The pigment dispersants having functional moieties capable of reacting with the reactants of the reactive oil phase, in addition to the pigment dispersion itself, may advantageously further improve the aminosilicone 3D network structure formed thereby. For example, a silicone epoxy pigment dispersant may advantageously interact with the amino groups of the aminosilicone prepolymer, thereby further improving the binding of the pigmented aminosilicone film.

In general, a material used in a composition according to the present teachings should be compatible with another material if it does not interfere with the activity of the other material or reduce it to a degree that significantly affects the intended purpose. For example, if the condensation curable aminosilicone prepolymer is prevented from curing, or curing is reduced or delayed to the point where the aminosilicone film does not sufficiently and/or rapidly adhere to the substrate fibers, among other things, the pigment dispersant will be incompatible or detrimental to the pigment and cause any similar adverse effects. In some embodiments, compatibility may additionally mean that materials considered compatible have common characteristics, such as based on common chemical properties or similar physical parameters of silicon. For example, materials having similar refractive indices (RI; within + -10% of each other) are believed to produce a clearer cured film than materials having relatively different refractive indices that may appear more hazy.

According to some embodiments, the plurality of pigment particles present in the reactive oil phase may be a mixture of different pigments, each pigment providing a different color or a different shade of the same color.

Depending on itMorphology, particles (e.g., submicron (absorbing) pigments, reinforcing fillers, etc.) may be characterized by their length, width, thickness, diameter, or their X-, Y-, and Z-dimensions. Typically, such dimensions are provided as an average of the population of particles, and are provided by the manufacturer of such materials. These dimensions can be determined by any technique known in the art, such as microscopy and Dynamic Light Scattering (DLS). In DLS techniques, the particles approximate spheres of equivalent behavior and may be sized according to hydrodynamic diameter. DLS also allows the size distribution of the population to be assessed. The same applies to droplets and may for example help to characterize emulsion droplets which are generally all spherical. As used herein, a particle, for example, having a size of 1 micron or less, is equal to or less than 1 micron in at least one dimension thereof, and equal to or less than 1 micron in two or even three dimensions thereof, depending on the shape. When referring to emulsion droplets, for example having a size of 5 microns or less, the droplets are understood to have an average diameter (D) equal to or less than 5 microns_V50)。

Although not required, any particular species of particle or emulsion droplet preferably can be symmetrically distributed and/or uniformly shaped within a relatively narrow size distribution range with respect to the population and/or median value of that particular species. Hereinafter, unless the context indicates otherwise, the term "particle" refers to both solid particles (e.g., pigments, etc.) and liquid droplets (e.g., emulsion droplets, micelles, etc.).

The Particle Size Distribution (PSD) is relatively narrow if at least one of the following two conditions is met:

A) the difference between the hydrodynamic diameter of 90% of the particles and the hydrodynamic diameter of 10% of the particles is equal to or less than 150 nm, or equal to or less than 100 nm, or equal to or less than 50 nm, expressed as: (D90-D10) is less than or equal to 150 nanometers, and the like; and/or

B) The ratio between a) the difference between 90% and 10% of the hydrodynamic diameter of the particles and b) the hydrodynamic diameter of 50% of the particles is not more than 2.0, or not more than 1.5, or not more than 1.0, can be expressed by the following mathematical formula: (D90-D10)/D50. ltoreq.2.0, and the like.

D10, D50 and D90 can be assessed by the number of particles in the population, in which case they can be assessed as D _N10、D_N50 and D_N90 or in the volume of particles, in which case it may be provided as D _V10、D_V50 and D_V90 is provided in the form of a cup. When the sample to be studied is suitably a fluid, the aforementioned measurements can be obtained by DLS techniques; or when the particles to be investigated are in dry form, the aforementioned measurements can be carried out by means of a microscope. As used herein, D50 may also be referred to as the "average measured particle size" or simply as the "average particle size", depending on the method of measurement best suited to the particle and its medium under consideration, and may refer to D_V50 (measured by DLS or the like) or the volume average particle size of particles found in the field of view of a microscope suitable for analysis of particle size. Accordingly, D90 is related to the measurement for 90% of the population and is therefore also referred to as the "primary measured particle size" or simply as the "primary particle size", e.g. as D which can be assessed by DLS techniques_V90。

As noted above, for some applications, such a relatively uniform distribution may not be necessary. For example, submicron pigment particles having a population of relatively heterogeneous sizes may allow relatively smaller particles to be present in the interstices formed by relatively larger particles in a coating formed therefrom, thereby together providing a relatively uniform coating.

Particles can be characterized by an aspect ratio, e.g., a dimensionless ratio between the smallest dimension of the particle and the longest dimension or equivalent diameter in the largest plane orthogonal to the smallest dimension, related to its shape. The equivalent diameter (Deq) is defined by the arithmetic mean between the longest and shortest dimensions of the largest orthogonal plane. The aspect ratio of the nearly spherical particles and the emulsion droplets therein is about 1: the aspect ratio of rod-like particles is higher, whereas the aspect ratio of plate-like particles is even as high as 1: 100 or even higher.

Such characteristic dimensions are generally provided by the supplier of such particles and can be measured with representative particles by methods known in the art, for example by microscopy, in particular by lightChemical microscopy detects particles of a few microns or as small as about 200 nanometers in size, and smaller particles less than 200 nanometers in size are detected by scanning electron microscopy, SEM (SEM is particularly well suited for planar dimensions) and/or by focused ion beam, FIB (preferably for the thickness and length (length) dimensions of the submicron particles, also referred to herein as nanoparticles or nano-sized particles). In selecting a representative particle or set of representative particles that can accurately characterize a population (e.g., by diameter, longest dimension, thickness, aspect ratio, and similar measures characterizing the particle), it will be appreciated that a more statistical approach may be desirable. When using a microscope for particle size characterization, a comprehensive analysis of the field of view of the image acquisition device (e.g., optical microscope, SEM, FIB-SEM, etc.) will be performed. Typically, the magnification is adjusted so that at least 5 particles, at least 10 particles, at least 20 particles, or at least 50 particles are within a single field of view. Naturally, the field of view should be a representative field of view as assessed by one skilled in the art of microscopic analysis. The average value characterizing such a group of particles in such a field of view is obtained by volume averaging. In this case, D_V50＝Σ[(Deq(m))³/m]^1/3Where m denotes a particle in the field of view and all m particles are summed. As mentioned above, when this method is selected for large scale quantities of particles under investigation or media in which they need to be considered, such a measurement may be referred to as D50.

According to some embodiments, the submicron pigment comprises D on average_V50 is a particle of at most 1000 nanometers, at most 750 nanometers, at most 500 nanometers, at most 250 nanometers, at most 150 nanometers, or at most 100 nanometers, and optionally, D is included_V10 are particles of at least 10 nanometers, at least 25 nanometers, or at least 50 nanometers. In some embodiments, the submicron pigment particles have a D in the range of at least 10 nanometers _V10 and D of at most 2500 nm_VBetween 90, or D of at least 25 nm _V10 and D of at most 1,500 nm_VD between 90, or at least 50 nm_VBetween 10 and DV90 up to 1000 nanometers.

According to some embodiments, the sub-micron pigment comprises predominantly D_VParticles 90 of up to 1000 nanometers, up to 750 nanometers, up to 500 nanometers, up to 250 nanometers, up to 150 nanometers, or up to 100 nanometers, and optionally, comprising D_V50 is a particle of at most 300 nanometers, at most 250 nanometers, at most 200 nanometers, at most 150 nanometers, at most 100 nanometers, or at most 75 nanometers. In some embodiments, D of the submicron pigment particles _V10 is at least 10 nanometers, at least 25 nanometers, or at least 50 nanometers. In some embodiments, the submicron pigment particles have a D in the range of at least 10 nanometers _V10 and D of at most 1000 nm_VBetween 90, or D of at least 25 nm _V10 and D of at most 750 nm_VD between 90, or at least 50 nm_VBetween 10 and DV90 up to 500 nanometers.

According to some embodiments, the compositions or kits disclosed herein further comprise a crosslinker, for example, an organosilicon compound capable of reacting through all non-amino reactive groups of the reactive silicone, and a crosslinker comprising a mercapto, epoxy, or acrylate group, all of which are capable of reacting through the amino reactive groups of the reactive silicone.

Typically, the crosslinking agent includes at least three reactive groups to form a network of oligomers and polymers to form an elastic network.

The organosilicon crosslinker must have hydrolyzable groups (Y).

After hydrolysis, the resulting silanol groups can undergo a condensation reaction with the reactive amino silicone prepolymer to give siloxane linkages.

The silicone crosslinker may comprise:

tetra-functional hydrolyzable groups, e.g. of the type having Q units (SiO)_4/2) Of silanes, e.g. SiY₄，

-or a trifunctional hydrolyzable group of the formula R^aSiO_3/2Of T units, e.g. R^aSiY₃

Or a difunctional hydrolyzable group of the formula R^b ₂SiO_2/2A silane or siloxane oligomer of the D unit of (a),such as R^b ₂SiY₂As long as the crosslinking agent has at least three hydrolyzable groups in total,

or monofunctional hydrolyzable groups having M units, provided that the crosslinking agent has a total of at least three hydrolyzable groups, wherein the hydrolyzable group (Y) may be selected from

Alkoxy (e.g. methoxy, ethoxy, propoxy, isopropoxy, methoxyethoxy, etc.)

Oximes (e.g. methyl ethyl ketoxime)

-acyloxy (e.g. acetoxy);

wherein R is^aAnd R^bThe substituents being selected from

-C₁-C₆Or C₁-C₄An alkyl group, a carboxyl group,

alkenyl (vinyl, allyl, etc.),

aminoalkyl radicals (e.g. aminopropylNH)₂(CH₂)₃A mono-amino group of (a); for example aminoethylaminopropyl NH₂(CH₂)₂NH(CH₂)₃The bisamino group of (1); or a triamino group),

epoxy groups (e.g. glycidoxypropyl)

Acrylate groups (e.g. methacryloxypropyl)

Mercapto (e.g. mercaptopropyl).

According to some embodiments, the cross-linking agent may be a branched or linear polyorganosiloxane comprising at least one of Q units, T units, D units, and M units, provided that the total amount of hydrolyzable groups and/or silanols in the cross-linking agent is at least three, such that a 3D network structure may be formed. When a mixture of crosslinking agents is used, at least one crosslinking agent in the mixture must contain a total of at least three silanol and/or hydrolyzable groups.

According to some embodiments, the crosslinking agent may be an ethyl silicate, such as tetraethyl silicate (CAS number 78-10-4), a poly (diethoxysiloxane) oligomer, such as one having a silica content of about 40-42% after complete hydrolysis

The silica content after complete hydrolysis being about 48%Ethyl silicate 48(CAS number 11099-06-2), poly (dimethoxysiloxane) (CASNO.25498-02-6), 3-glycidyloxypropyltrimethoxysilane by Evonik, Carbodilite emulsion E-05 with 40% polyfunctional polycarbodiimide in anionic emulsion and Carbodilite eV02-B with 100% polyfunctional polycarbodiimide.

According to some embodiments, the cross-linking agent may be a reactive aminosilicone monomer, such as aminopropyltriethoxysilane (CAS No. 919-30-2), bis (triethoxy-silylpropyl) amine (CAS No. 13497-18-2), or mixtures thereof.

According to some embodiments, the cross-linking agent is a non-amino silicone having a molecular weight of less than 1000 grams/mole, and thus comprises, consists essentially of, or consists of non-amino silicone monomers that are reactive condensation curable to form a film. In some embodiments, the total concentration of non-amino crosslinking agents is at most 35 wt.%, at most 30 wt.%, at most 20 wt.%, at most 15 wt.%, at most 10 wt.%, or at most 5 wt.%, by weight of the oil phase.

As used herein in the specification and in the claims section that follows, the term "consisting essentially of, generally with respect to a component in a formulation, means at least 50% by weight of that component.

According to some embodiments, the reactive condensation curable film-forming aminosilicone prepolymer, the amino or non-amino silicone oil, the non-amino crosslinker, and the reactive filler, including any pigment particles and dispersant for the pigment particles, are present in the oil phase at a total concentration of at least 90 wt.%, at least 93 wt.%, at least 95 wt.%, at least 97 wt.%, at least 98 wt.%, or at least 95 wt.%, based on the total weight of the composition.

According to some embodiments, the oil-in-water emulsion is prepared in the presence of a non-ionic emulsifier, preferably having a Hydrophilic Lipophilic Balance (HLB) between 12 and 18, 12 and 17, 12 and 16, 12 and 15 or 13 and 16 on the griffin scale. Emulsions may be prepared by a variety of emulsification techniques known to the skilled artisan. While manual shaking is sufficient, various devices may be used, such as vortexers, overhead stirrers, magnetic stirrers, ultrasonic dispersers, high shear homogenizers, sonicators, and planetary centrifugal mills, which generally provide a more uniform population of oil droplets in the aqueous phase. The emulsion can be easily used for coating after preparation or for coating within a period of time that remains suitably stable. For example, the emulsion may be used for coating as long as the oil droplets are within their desired size range and the emulsified aminosilicone prepolymer remains reactive. Since the thickness of the coating is believed to be proportional to the average diameter of the droplets, if a thin coating is desired, too large droplets should be avoided, while on the other hand too small droplets will not contain particles of sufficient size to provide the desired visual effect. The time window may vary with the components of the emulsion and their respective amounts, and the presence of the emulsifier generally extends the time window. In some embodiments, the emulsion is applied to the textile fibers within at most 30 minutes, or within at most 20 minutes, at most 10 minutes, or at most 5 minutes after emulsification.

According to some embodiments, the aqueous carrier comprises at least 60% water, or comprises at least 65 wt.%, or at least 70 wt.%, or at least 75 wt.%, or at least 80 wt.%, or at least 85 wt.%, or at least 90 wt.%, or at least 95 wt.% water, by weight of the liquid carrier. In some embodiments, the total concentration of water and any emulsifier is at least 90 wt.%, at least 95 wt.%, at least 97 wt.%, at least 99 wt.%, by weight of the aqueous phase.

In cases where the amount of pigments and/or their density is high, although the liquid carrier will contain primarily water, the water may comprise only 30% by weight of the total composition.

In some embodiments, after curing, the thickness or average thickness of the aminosilicone coating or average thickness of the plurality of substrates is at least 20 nanometers, at least 50 nanometers, or at least 100 nanometers, and optionally at most 3000 nanometers, at most 2000 nanometers, at most 1,200 nanometers, at most 800 nanometers, at most 500 nanometers, at most 400 nanometers, at most 300 nanometers, at most 200 nanometers, at most 150 nanometers, or at most 120 nanometers, and further optionally in a range from 20 nanometers to 3000 nanometers, 20 nanometers to 1000 nanometers, 20 nanometers to 500 nanometers, 20 nanometers to 300 nanometers, 20 nanometers to 200 nanometers, 20 nanometers to 150 nanometers, 50 nanometers to 500 nanometers, 50 nanometers to 350 nanometers, 50 nanometers to 250 nanometers, or 50 nanometers to 200 nanometers.

As used herein, the term "average thickness," generally with respect to one or more coatings or layers, refers to the arithmetic average of the thickness of one or more coatings or layers measured along the length of the outer surface of a textile substrate (e.g., a thread, yarn, or even a woven or nonwoven cloth). As is known in the art, the measurement of each individual thickness may be performed using Focused Ion Beam (FIB) techniques. Ten points equally spaced along the length of the coated substrate were determined for each individual thickness measurement, and the arithmetic mean of the ten measurements defined the average thickness associated with each substrate.

The coated textile fibres of or produced by the present invention may exhibit a coating thickness which is quite consistent, largely independent of the specific topographical features of the textile fibre substrate. Also, individually coated threads or yarns may exhibit similar coating thicknesses. However, it will be appreciated that a more statistical approach to coating thickness may be better utilized to distinguish the present invention from the various teachings in the art. Thus, in some embodiments of the invention, the "multi-substrate average thickness" of multiple longitudinal samples of textile substrate is defined as the "average thickness" as defined above for a single coated fiber, but applies to at least ten samples of the coating of such textile substrate, such as thread, yarn or cloth samples, randomly selected from samples that are coated together and arithmetically averaged over the multiple samples used.

Outer polymer layer

The polymer layer is formed from an aqueous dispersion comprising a plurality of polymer particles formed from a hydrophilic polymer material having neutralized acid moieties, the hydrophilic polymer material optionally encapsulating pigment particles when present in the aqueous dispersion.

The polymer particles dispersed in the aqueous dispersion have a certain hydrophilicity when applied to textile fibres previously coated with an aminosilicone coating, for which purpose their acid moieties are neutralized in the presence of a neutralizing agent. However, prior to neutralization of the neutralizable acid moieties, the polymeric material is hydrophobic. After application of the aqueous dispersion on the outer surface of the aminosilicone precoated fibrous fabric, the neutralizing agent is eliminated (e.g. by evaporation), forming an overlying (optionally pigmented) polymer layer adhering to the outer surface of the aminosilicone coating (previously applied on the textile fibers).

As used herein in the specification and in the claims section that follows, the term "hydrophilic polymer" with respect to a polymeric material, such as a neutralized polymeric material, refers to a polymer having at least one of the following solubilities: (i) a solubility in pure deionized water of at least 1% (more typically, at least 1.5%, at least 2%, at least 3%, at least 5%, at least 10%, or at least 15%) by weight at 23 ℃; and (ii) a solubility in pure deionized water adjusted to a pH of 10 at 23 ℃ of at least 1% (more typically at least 1.5%, at least 2%, at least 3%, at least 5%, at least 10%, or at least 15%) by weight. The solubility of the polymer was evaluated in the absence of pigments or any other possible additives.

Typically, the conjugate acid of the hydrophilic neutralized polymeric material is a hydrophobic polymeric material.

As used herein in the specification and claims section that follows, the term "solubility" with respect to a polymeric material refers to the amount of polymeric material that can be introduced into the deionized water medium of (i) or (ii) while maintaining the clarity of the deionized water medium.

As used herein in the specification and in the claims section that follows, the term "clarity" with respect to a solution is intended to include a solution having at least one, and typically both, of the following properties: (I) a clear solution was observed by eye; and (ii) the average diameter or particle size (as determined by DLS) of any micelles disposed therein is at most 100 nanometers. More typically, such micelles will have an average diameter or particle size of at most 80 nanometers, at most 70 nanometers, or at most 50 nanometers. Removal of the volatile base from the aqueous dispersion results in re-acidification of the neutralized acidic moieties in the hydrophilic polymeric material to their conjugate acids. Thus, a hydrophobic polymeric material can be obtained after such removal.

Advantageously, the alkaline pH of the aqueous dispersion can restore the positive charge of the aminosilicone membrane (for example, by protonation of the amino groups) once coated on the textile fibers previously coated with the aminosilicone membrane. At the same time, the basic pH imparts a high negative charge to the polymeric material (e.g., by protonation of carboxyl groups). Thus, at the beginning of the process of coating the aminosilicone membrane with polymer particles, the basic pH of the aqueous dispersion favours a distinct gradient of charge, providing a strong initial electrostatic driving force.

In some embodiments, the neutralizable acid moieties of the hydrophobic polymeric material are up to at least 8%, at least 10%, at least 12%, at least 15%, at least 16%, at least 17%, at least 18%, at least 19%, at least 20%, at least 21%, or at least 22% by weight of the hydrophobic polymeric material. In some embodiments, the neutralizable acid moiety of the hydrophobic polymeric material is up to 8 to 30%, 10 to 30%, 12 to 28%, 12 to 26%, 15 to 30%, 15 to 28%, 15 to 26%, 17 to 22%, 17 to 23%, 18 to 30%, 18 to 28%, 18 to 26%, 20 to 30%, 20 to 28%, or 20 to 26% by weight of the hydrophobic polymeric material.

In some embodiments, the neutralizable acid moieties and/or neutralized acid moieties of the hydrophobic polymeric material are up to at least 8%, at least 10%, at least 12%, at least 15%, at least 16%, at least 17%, at least 18%, at least 19%, at least 20%, at least 21%, or at least 22% by weight of the hydrophobic polymeric material. In some embodiments, the neutralizable acid moieties and/or neutralized acid moieties of the hydrophobic polymeric material are up to 8 to 30%, 10 to 30%, 12 to 28%, 12 to 26%, 15 to 30%, 15 to 28%, 15 to 26%, 17 to 22%, 17 to 23%, 18 to 30%, 18 to 28%, 18 to 26%, 20 to 30%, 20 to 28%, or 20 to 26% by weight of the hydrophobic polymeric material. These values are also reported as the weight percent of monomers having acid moieties relative to the total weight of the polymeric material (e.g., acrylic acid in EAA copolymer (wt% AA) or methacrylic acid in EMAA (wt% MA)). Such properties of polymeric materials are typically provided by the manufacturer, but may be evaluated by standard methods, such as described in astm d 4094.

In some embodiments, the polymeric material (prior to neutralization) has an acid value of at least 100mgKOH/g, at least 115mgKOH/g, at least 130mgKOH/g, or at least 145 mgKOH/g. In some embodiments, the polymeric material has an acid value of at most 230mgKOH/g, at most 215mgKOH/g, at most 200mgKOH/g, or at most 185 mgKOH/g. In some embodiments, the acid value is in a range of 100 to 230mgKOH/g, 115 to 215mgKOH/g, 130 to 200mgKOH/g, 130 to 185mgKOH/g, 145 to 185mgKOH/g, or 145 to 170 mgKOH/g. Acid number (acid number) (also known as acid number or neutralization number) is used to estimate the number of carboxylic acid groups in a compound and corresponds to the number of milligrams of potassium hydroxide (KOH) mass required to neutralize one gram of polymeric material the acid number is typically provided by manufacturers of such polymers or can be independently estimated by standard methods, such as described in astm d 974-04.

In some embodiments, the amount of polymeric material dispersed in the aqueous dispersion is at least 1 wt.%, at least 2 wt.%, or at least 5 wt.%, by weight of the aqueous dispersion. In some embodiments, the amount of polymeric material dispersed in the aqueous dispersion is at most 45 wt.%, at most 30 wt.%, at most 25 wt.%, at most 20 wt.%, at most 15 wt.%, at most 12.5 wt.%, or at most 10 wt.% by weight of the aqueous dispersion.

In some embodiments, the aqueous dispersion is produced by:

(a) mixing in an aqueous carrier comprising water at least one hydrophobic polymeric material each independently having a neutralizable acid moiety, the hydrophobic polymeric material optionally being mixed with a pigment, thereby forming a neutralizable mixture comprising pellets of the hydrophobic polymeric material;

(b) adding a neutralizing agent to the neutralizable mixture, said adding being carried out under agitation at a temperature above the maximum softening temperature and/or the maximum melting temperature of the at least one hydrophobic polymeric material, the neutralizing agent being added in an amount sufficient to neutralize at least 75% of the neutralizable acid moieties of said polymeric material to form a neutralizable mixture comprising a portion of the hydrophilic polymeric material; and

(c) dispersing the neutralized mixture to form said aqueous dispersion, said aqueous dispersion comprising particles of at least one hydrophilic polymeric material.

In some embodiments, the aqueous dispersion is produced by:

a) mixing at least one hydrophobic polymeric material each independently having a neutralizable acid moiety in an aqueous carrier to form a neutralizable mixture comprising hydrophobic polymeric material pellets;

(b) adding a neutralizing agent to the neutralizable mixture, said adding being carried out with agitation at a temperature above the maximum softening temperature and/or the maximum melting temperature of the at least one hydrophobic polymeric material, the neutralizing agent being added in an amount sufficient to neutralize at least 75% of the neutralizable acid moieties of said polymeric material to form a neutralizable mixture comprising a portion of the hydrophilic polymeric material;

(c) adding at least one pigment to the neutralized mixture; and

(d) dispersing the neutralized mixture with a pigment to form the aqueous dispersion, the aqueous dispersion comprising particles of at least one hydrophilic polymeric material, a portion of the hydrophilic polymeric material at least partially encapsulating the at least one pigment.

The amount of neutralizing agent can be determined experimentally by simple means, at a concentration that allows self-dispersibility of the polymer particles and (in the absence of pigment) formation of a transparent dispersion of micelles, but can also be calculated by the following equation. For example, the amount of neutralizing agent to be added to a polymeric material having acid-neutralizable moieties (B-weight in grams) is:

B＝(W·A·N·E)/1000

wherein W is the weight of the polymer in grams,

a is the acidity of the polymeric material, in mEq/gram of polymeric material,

n is the desired percent neutralization, expressed in decimal numbers from 0 to 1, the latter representing 100% neutralization, an

E is the equivalent of the neutralizing agent used.

In some embodiments, the neutralizing agent used to prepare the aqueous dispersion is a volatile base. In this case, the resulting aqueous dispersion contains a volatile base. The volatile base may be chosen from ammonia ((NH)₃) Monoethanolamine, diethanolamine, triethanolamine and morpholine, or a metal base selected from sodium hydroxide and potassium hydroxide. When wash fastness is desired, the use of alkali metal bases as neutralizing agents is preferably avoided because the acid portion of the polymeric material may bind to the metal ion of the base, resulting in a decrease in the ionomer resistance to water.

In some embodiments, the hydrophilic polymeric material having neutralized acid moieties has a solubility of at least 2%, at least 5%, at least 10%, or at least 15% by weight, or wherein the solubility is in the range of 2 to 30%, 5 to 30%, 10 to 30%, or 15 to 30% by weight, at a pH of 10.

In some embodiments, the particles of the aqueous dispersion and hydrophilic polymeric material further comprise pigment particles dispersed therein, the pigment optionally being selected from the previously detailed list and further optionally satisfying structural characteristics (e.g., particle size) associated therewith.

In some embodiments, the pigment is present in the aqueous dispersion in an amount of at least 0.1 wt.%, at least 0.5 wt.%, at least 1 wt.%, at least 2 wt.%, or at least 5 wt.%, based on the weight of the hydrophilic polymeric material. In some embodiments, the pigment is present in the aqueous dispersion in an amount of up to 50 wt.%, up to 40 wt.%, up to 30 wt.%, up to 20 wt.%, up to 15 wt.%, or up to 10 wt.%, based on the weight of the hydrophilic polymeric material. In some embodiments, the pigment is present in the aqueous dispersion in a range from 0.1 wt.% to 50 wt.%, 1 wt.% to 30 wt.%, 2 wt.% to 20 wt.%, or 5 wt.% to 15 wt.%, by weight of the hydrophilic polymeric material.

In some embodiments, the pigment is present in the aqueous dispersion in an amount of at least 0.05 wt.%, at least 0.5 wt.%, or at least 1 wt.%, by weight of the aqueous dispersion. In some embodiments, the pigment is present in the aqueous dispersion in an amount of up to 15 wt.%, up to 10 wt.%, up to 7.5 wt.%, up to 5 wt.%, or up to 2.5 wt.%, by weight of the aqueous dispersion. In some embodiments, the pigment is present in the aqueous dispersion in a range of 0.05 wt.% to 15 wt.%, 0.5 wt.% to 10 wt.%, 1 wt.% to 7.5 wt.%, 1.5 wt.% to 5 wt.%, or 1.5 wt.% to 2.5 wt.%, by weight of the aqueous dispersion.

In some embodiments, the method of treating the outer surface of a textile fiber having an aminosilicone coating with an aqueous dispersion of an at least partially neutralized polymeric material further comprises volatilizing a volatile base associated with the overlying polymeric layer (optionally with pigment) to largely or predominantly or completely acidify the neutralized acid moieties.

After application of the aqueous dispersion, the method further includes converting a portion, a majority, or all of the hydrophilic polymeric material in the overlying polymeric layer with the pigment to its conjugate acid. In some embodiments, the transformation comprises, consists essentially of, or consists of: acidifying the neutralized acid moiety to form a conjugate acid.

Once the hydrophilic polymeric material is sufficiently converted to its conjugate acid, a hydrophobic polymeric material is obtained. Thus, a polymer layer in which the polymer material has been sufficiently converted from a form having acid moieties (hydrophilic) to a conjugated acid form (hydrophobic) by a base may form a sufficient adhesion to the aminosilicone coating. At this point, the outer polymer coating is a hydrophobic coating.

In some embodiments, the polymeric material having neutralized acid moieties comprises, consists essentially of, or consists of one or more neutralized copolymers selected from the group consisting of neutralized olefin-acrylic acid copolymers, neutralized olefin-methacrylic acid copolymers, and neutralized acrylamide/acrylate copolymers.

In some embodiments, the neutralized olefin-acrylic acid copolymer comprises, consists essentially of, or consists essentially of a neutralized ethylene-acrylic acid (EAA) copolymer. In some embodiments, the neutralized olefin-methacrylic acid copolymer comprises, consists essentially of, or consists essentially of a neutralized ethylene-methacrylic acid (EMAA) copolymer. In some embodiments, the neutralized olefin-methacrylic acid copolymer comprises, consists essentially of, or consists essentially of a neutralized acrylamide/acrylate copolymer (AAA).

Suitable hydrophilic polymeric materials are self-dispersible in water in the pH range of 7.5 to 11, without the presence of dispersants and all other additives in water.

In some embodiments, the aqueous dispersion of neutralized hydrophilic polymeric material further comprises a surfactant and/or a thickener. In some embodiments, the surfactant is a super wetting agent that can alter the surface tension of the aqueous dispersion, facilitating its wetting of the aminosilicone coating.

In some embodiments, a sufficient amount of surfactant or super wetting agent is selected and added such that the aqueous dispersion has a surface tension at 25 ℃ of at most 30, at most 28, at most 26, or at most 24 millinewtons per meter, and optionally at least 12, at least 14, or at least 16 millinewtons per meter (mN/m). In some embodiments, the aqueous dispersion has a surface tension in the range of 12 to 30, 15 to 30, 18 to 28, 18 to 26, 18 to 24, 19 to 24, or 20 to 24 mN/m.

Suitable hydrophobic polymeric materials having acid-neutralizable moieties such as Acrylic Acid (AA) or methacrylic acid (MAA), which are commercially available, including but not limited to some EAA, EMAA, and AAA polymeric materials commercialized under the trade names such as Primacor by the Dow Chemical Company, can be used to prepare aqueous dispersions according to the present invention^TMDuPont' sOf BASF

And

of Akzo Nobel

And Escor of Exxon Mobil Chemical^TM。

Suitably, the hydrophobic polymeric material having acid-neutralizable moieties is thermoplastic. The thermoplastic polymer may facilitate partial encapsulation of the pigment particles, for example, in a compounding process (e.g., hot melt compounding).

In some embodiments, after the aqueous dispersion is applied over the aminosilicone coating, the overlying polymer layer is treated to produce an overlying (e.g., pigmented) polymer coating that adheres to the pre-coated textile fibers. Post-coating treatment includes washing and/or carding the fibers to remove excess material therefrom, and optionally drying and/or carding the fibers thereafter.

The temperature at which the coated textile fibre is typically treated (e.g. washed and/or dried) depends on the softening or melting point of the polymer particles. The treatment of the coated textile fibres is generally carried out at temperatures of up to 45 ℃, 40 ℃, 35 ℃,30 ℃ or 25 ℃. In certain embodiments, these steps should be performed at a temperature of at least 5 ℃,10 ℃, 12 ℃, 15 ℃, 17 ℃, or 20 ℃, and optionally at a room or ambient temperature of 7 ℃,5 ℃, or 3 ℃.

In some embodiments, the washing of the fabric fibers should be performed within at most 20 minutes, at most 10 minutes, at most 5 minutes, at most 3 minutes, at most 2 minutes, at most 1 minute, or at most 30 seconds after the coating of the aqueous dispersion is complete.

In some embodiments, the drying of the textile fibers and the coating thereon is an active drying. In some embodiments, the total length of time to coat the aqueous dispersion, wash and/or actively dry the textile fiber is in a range of 2 to 90 minutes, 2 to 75 minutes, 2 to 60 minutes, 2 to 45 minutes, 2 to 30 minutes, 2 to 20 minutes, 2 to 10 minutes, or 2 to 5 minutes.

In certain embodiments, the overlying polymeric coating with pigment can achieve wash-fast, durable, or permanent coloration within 24-72 hours, within 24-48 hours, within 24-36 hours, or within 24-30 hours immediately after the overall length of time (e.g., after washing or drying), and while maintaining room or ambient temperature within 7 ℃,5 ℃,3 ℃, or 1 ℃ using textile fibers.

It is believed that this resistance of the overlying polymer coating is caused by the resistance of the underlying aminosilicone coating and its strength of adhesion to the underlying fibers. It may be noted that the overlying polymer coating is advantageously permeable to moisture as the curing of the aminosilicone coating may be carried out on the textile fibre, once such coating is encapsulated by the polymer layer, and as condensation curing may benefit from ambient humidity.

In some embodiments, the total thickness, the total average thickness, or the total multi-substrate average thickness of the aminosilicone coating and the overlying polymeric coating with pigments, when combined together in thickness of the overlying polymeric coating and the underlying aminosilicone coating, is at least 100 nanometers, at least 150 nanometers, at least 200 nanometers, at least 300 nanometers, at least 500 nanometers, at least 800 nanometers, at least 1,200 nanometers, or at least 2000 nanometers. In some embodiments, the total thickness, the total average thickness, or the total multi-substrate average thickness of the two coatings is at most 5000 nanometers, at most 3500 nanometers, at most 2500 nanometers, at most 2000 nanometers, at most 1700 nanometers, or at most 1400 nanometers. In some embodiments, the total thickness, the total average thickness, or the total multi-substrate average thickness of the two coatings is in a range from 100 nanometers to 5000 nanometers, 200 nanometers to 3500 nanometers, 200 nanometers to 2500 nanometers, 200 nanometers to 1000 nanometers, 200 nanometers to 700 nanometers, 200 nanometers to 500 nanometers, 200 nanometers to 450 nanometers, or 200 nanometers to 400 nanometers.

In some embodiments, the ratio of at least one of the total thickness and the total average thickness and the total multi-substrate average thickness of the two co-coatings to the thickness, average thickness, or multi-substrate average thickness of the underlying aminosilicone layer is in the range of 1.2:1 to 100:1, 1:4 to 100:1, 1:7 to 100:1, 2:1 to 100:1, 3:1 to 100:1, 4:1 to 100:1, 5:1 to 100:1, 7:1 to 100:1, 10:1 to 100:1, 2:1 to 30:1, 2:1 to 20:1, 3:1 to 30:1, 3:1 to 20:1, 5:1 to 30:1, 5:1 to 20:1, 7:1 to 30:1, 7:1 to 20:1, 10:1 to 50:1, 10:1 to 30:1, or 10:1 to 20: 1.

According to some embodiments, the composition (or kit capable of making and using the composition) according to the present teachings further comprises at least one additive selected from the group consisting of dispersants, pH adjusters, preservatives, bactericides, fungicides, viscosity modifiers, thickeners, chelating agents, vitamins, and fragrances. Depending on the manner of application, additional agents may be required, for example, a propellant may be added if the composition is applied in the form of a propellant spray.

According to some embodiments, the composition is in a form selected from the group consisting of a paste, a gel, a lotion, and a cream.