阅读说明：本技术 使用辐射固化油墨在非织造纺织品基材上印刷的方法 (Method of printing on nonwoven textile substrates using radiation curable inks ) 是由 C·阿伦斯 F·韦塞尔 S·皮昂泰克 S·乐博尔涅 R·范克尼彭伯格 A·海塞尔梅尔 于 2020-03-25 设计创作，主要内容包括：本发明涉及一种至少部分用油墨层(IL)涂覆非织造纺织品基材(S)的方法,所述方法包括至少三个步骤,即提供非织造纺织品基材(S),将特定的着色且优选水性的油墨组合物(AC)沉积在非织造纺织品基材(S)的至少一个表面的至少一部分上,以及干燥和/或至少部分地固化在非织造纺织品基材(S)上沉积的油墨组合物(AC)。此外,本发明涉及一种通过本发明方法获得至少部分涂覆有油墨层(IL)的非织造纺织品基材(S)。(The invention relates to a method for at least partially coating a nonwoven textile substrate (S) with an Ink Layer (IL), comprising at least three steps, namely providing the nonwoven textile substrate (S), depositing a specific pigmented and preferably aqueous ink composition (AC) on at least a part of at least one surface of the nonwoven textile substrate (S), and drying and/or at least partially curing the ink composition (AC) deposited on the nonwoven textile substrate (S). Furthermore, the invention relates to a nonwoven textile substrate (S) which is at least partially coated with an Ink Layer (IL) obtained by the method according to the invention.)

1. A method of at least partially coating a nonwoven textile substrate (S) with an Ink Layer (IL), the method comprising:

(1) providing a nonwoven textile substrate (S);

(2) optionally pretreating the nonwoven textile substrate (S);

(3) depositing on at least a portion of at least one surface of the nonwoven textile substrate (S) at least one ink composition (AC), preferably an aqueous ink composition (AC), the ink composition (AC) comprising:

(i) an aqueous dispersion of at least one polyurethane (meth) acrylate polymer,

(ii) at least one pigment and/or dye, and

(iii) optionally at least one photoinitiator;

(4) drying and/or at least partially curing the ink composition (AC) deposited on the nonwoven textile substrate (S) obtained after step (3).

2. The process of claim 1, wherein the nonwoven textile substrate (S) is selected from the group consisting of thermoplastic polyurethanes, polypropylenes, glass fibers, and mixtures thereof, preferably thermoplastic polyurethanes.

3. The process as claimed in claim 1 or 2, wherein the nonwoven textile substrate (S) has a weight average of from 50 to 1,000g/m²More preferably 80 to 700g/m²Even more preferably 100-²Very preferably 400-500g/m²Basis weight of (c).

4. The method of any one of the preceding claims, wherein the polyurethane (meth) acrylate polymer is obtained by reacting:

(a) at least one (cyclo) aliphatic di-and/or polyisocyanate,

(b1) at least one (cyclo) aliphatic diol having a molar mass of less than 700g/mol,

(b2) at least one polyester diol having a weight-average molar mass Mw of 700-2000 and preferably not more than 20mg KOH/g in a molar ratio in accordance with DIN 53240-2: an acid value of 2007-11 (g),

(c) at least one compound having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group,

(d) at least one compound having at least one isocyanate-reactive group and at least one acid group,

(e) at least one alkali metal base for at least partially neutralizing the acid groups of component (d),

(f) optionally, at least one monohydric alcohol having exactly one hydroxyl function, or at least one mono-and di-C₁-C₄An alkylamine, and

(g) at least one monofunctional polyoxyalkylene polyether alcohol.

5. The method of any preceding claim, wherein the polyurethane (meth) acrylate polymer comprises 1 to 5mol, preferably 2 to 4mol, (meth) acryloyl groups per 1,000g polyurethane (meth) acrylate.

6. The process as claimed in any of the preceding claims, wherein the ink composition (AC) comprises a total amount of from 15 to 95 parts, preferably from 20 to 50 parts, very preferably from 25 to 35 parts, of the aqueous dispersion (i) of the at least one polyurethane (meth) acrylate polymer, based on 100 parts of the ink composition.

7. The process as claimed in any of the preceding claims, wherein the ink composition (AC) comprises the at least one pigment and/or dye (ii) in a total amount of from 0.01 to 5 parts, preferably from 0.1 to 2.5 parts, very preferably from 0.2 to 0.5 parts, based on 100 parts of the ink composition.

8. The process as claimed in any of the preceding claims, wherein the ink composition (AC) comprises the at least one photoinitiator (iii) in a total amount of from 0.01 to 8 parts, preferably from 0.1 to 7 parts, more preferably from 0.2 to 5 parts, very preferably from 0.2 to 1.5 parts, based on 100 parts of the ink composition.

9. The process according to any one of the preceding claims, wherein the ink composition (AC) further comprises at least one surfactant (iv).

10. The process according to claim 9, wherein the ink composition (AC) comprises the at least one surfactant (iv), preferably the at least one nonionic surfactant and/or the at least one silicone surfactant, very preferably 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and/or polyether-modified siloxane in a total amount of from 0.01 to 1 part, preferably from 0.02 to 0.5 part, very preferably from 0.02 to 0.2 part, based on 100 parts of the ink composition.

11. The process as claimed in any of the preceding claims, wherein the ink composition (AC), preferably the aqueous ink composition (AC), has a solids content of from 8 to 40 parts, preferably from 20 to 40 parts, very preferably from 25 to 35 parts, based on 100 parts of the ink composition.

12. The process according to any one of the preceding claims, wherein the ink composition (AC) in step (3) is deposited by a digital printing device comprising a Drop On Demand (DOD) ink jet printer.

13. A method as claimed in claim 12, wherein the Drop On Demand (DOD) ink jet printer has at least one print head, wherein the at least one print head has one or more nozzles, the diameter of which is in each case from 1 to 52 μm, preferably from 15 to 40 μm, very preferably from 30 to 40 μm.

14. The method according to claim 13, wherein in step (3) the distance between the portion of the at least one surface of the nonwoven textile substrate (S) to be printed and the at least one nozzle of the at least one print head is from 0.1mm to 4cm, preferably from 0.5 to 1.5 mm.

15. A nonwoven textile substrate (S) at least partially coated with an Ink Layer (IL), said substrate being prepared by the method according to any one of claims 1-14.

Prior Art

The growing market for printing complex designs and images on almost every type of surface, especially on woven and non-woven textile surfaces, plasticized and laminated fabrics (soft signage), etc., has created a need for new and more versatile printing techniques and ink compositions. One such need is a need for ink compositions and printing techniques that will be suitable for printing durable, abrasion resistant, water resistant, detergent resistant and chemical resistant color images on a variety of materials that will not wear quickly when used, handled, washed and exposed to the environment. The apparel industry, which may be the most demanding in terms of high quality and durable prints of printed textiles, has increased some of the requirements of the products, such as comfortable feel of the printed area, flexibility (bendable without breaking), stretchable and inflatable printed areas, and guidelines that follow internationally accepted standards, such as Oeko-Tex standard 100 (an international textile testing and certification system, limiting the use of certain chemicals, which was developed in 1992) and GOTS (global organic textile standard).

One of the most promising technologies for printing high quality color images, especially small batches of varying content (short run of variable data), on a wide range of types and shapes of substrates, such as woven and non-woven substrates, is inkjet printing. Ink jet printing is a non-impact method in which small droplets of ink are directed from a nozzle onto a printable porous or non-porous substrate.

Inkjet printing methods fall into two main categories: continuous processes and Drop On Demand (DOD) ink jet processes. Continuous processes use conductive inks to produce a stream of electrically charged ink droplets that are deflected by an electric field into position on a substrate. In contrast, in the DOD method, individual ink drops are ejected from the nozzles of a printhead by vibration of a piezoelectric actuator (in piezoelectric inkjet printing) or by heating the ink to form bubbles (in thermal inkjet printing, also referred to as bubble jet printing). The jetting speed, the separation length of the droplets, the droplet size and the stability of the fluid stream are all greatly affected by the surface tension and viscosity of the ink. In contrast to screen printing, inks used in ink jet printing are required to have relatively low viscosity and small particle size in order to have satisfactory ejection characteristics.

Currently available ink compositions, including compositions suitable for ink jet printing, include water-based ink compositions and non-aqueous solvent-based ink compositions. The more commonly used inkjet compositions are solvent-based ink compositions, which typically include a solvent and a colorant, typically a dye or pigment dispersion, and may further comprise a number of additives to impart certain properties to the ink when applied (jetted), such as improved stability and flow, corrosion resistance, feathering and bleed resistance, as well as properties that affect its final curing properties, such as the ability to form chemical bonds with the substrate, improved adhesion to the substrate, flexibility, stretchability, softness, and the like.

To ensure high quality images for inkjet printing, the ink composition should be characterized by free passage through the nozzle, minimal bleeding, agitation and/or smearing, uniform printing on the surface of the object, wash fastness, simple system cleaning, and other chemical and physical properties. To meet these requirements, the ink composition should be characterized by, for example, suitable viscosity, solubility, volatility, surface tension, compatibility with other components of the printing system, and further applied using suitable devices, techniques, and methods.

In order to withstand wear and tear due to frequent use of printed fabrics (e.g. printed garments) and/or washing cycles, the printed image on the final product, as well as the final product itself, should exhibit the properties of an elastic but aerated film, and therefore the ink composition should also comprise components that can impart such compressibility (softness), plasticity, elasticity, flexibility and stretchability.

One of the challenges of printing on fabrics, especially nonwoven fabrics, is their low absorbency, which results in the need to optimize the print head and its controls and the ink in order to achieve high resolution of the printed image and durable fixation of the ink to the substrate.

Purpose(s) to

It is therefore an object of the present invention to provide a method of printing on nonwoven textile substrates that produces high resolution images and good performance of the printed substrate, for example in terms of tint strength, dye binding stability, moisture resistance, non-toxicity and flexibility. Preferably, the method should not have a negative impact on the feel and properties of the substrate or interfere with further processing of the substrate. Furthermore, the printing inks used in the process should not show any disadvantages in their viscosity, stability, surface tension and toxicity, to allow printing of high resolution images with excellent durability on substrates that can be used to make products suitable for skin contact.

It is another object of the present invention to provide a nonwoven textile substrate at least partially coated with an ink layer. The printing substrate should have good properties, in particular those mentioned above, and should be used without difficulty for further processing.

Technical scheme

This problem is solved by the subject matter claimed in the claims and by preferred embodiments of this subject matter described in the following description.

Accordingly, a first subject of the invention is a process for at least partially coating a nonwoven textile substrate (S) with an Ink Layer (IL), said process comprising:

(1) providing a nonwoven textile substrate (S);

(2) optionally pretreating the nonwoven textile substrate (S);

(3) depositing on at least a portion of at least one surface of the nonwoven textile substrate (S) at least one ink composition (AC), preferably an aqueous ink composition (AC), the ink composition (AC) comprising:

(i) an aqueous dispersion of at least one polyurethane (meth) acrylate polymer,

(ii) at least one pigment and/or dye, and

(iii) optionally at least one photoinitiator;

(4) drying and/or at least partially curing the ink composition (AC) deposited on the nonwoven textile substrate (S) obtained after step (3).

Another subject of the invention is a nonwoven textile substrate (S) at least partially coated with an Ink Layer (IL), said substrate being prepared by the process of the invention.

The method of the present invention allows images to be printed on nonwoven substrates at high resolution of 100dpi or higher without adversely affecting the properties or feel of the substrate. The printed image is durable, abrasion resistant, water resistant, detergent resistant and chemical resistant and does not wear quickly when used, handled, washed and exposed to the environment. In addition, they are non-toxic and flexible. Furthermore, the printed substrate can be used directly after printing for further processing without complicated handling.

The non-toxicity of the ink layer is obtained by using radiation curable printing inks that are free of ethylenically unsaturated monomers, such as (meth) acrylates, since undesired migration of residual monomers from the cured ink layer into the substrate may lead to skin irritation and/or odor nuisance.

Detailed Description

If in the context of the present invention an official standard is referred to, this of course means the version of the standard that was passed on the date of application, or the last passed version if no passed version existed on that date.

The method comprises the following steps:

according to the method of the invention, a nonwoven textile substrate (S) is at least partially coated with an Ink Layer (IL) by depositing a specific ink composition (AC) on at least a portion of at least one surface of the substrate and drying and/or curing the ink.

The term "nonwoven textile" means a textile that is neither spun from yarn nor woven or knitted. It is a fabric-like material that can be made of short or long fibers that are bonded together by chemical, mechanical, thermal or solvent treatment. To increase strength, these textiles may be densified or reinforced by a backing.

In the description of the present invention, "polymer" and "resin" are used interchangeably for convenience, and include resins, oligomers, and polymers.

The term "poly (meth) acrylate" denotes both polyacrylates and polymethacrylates. Thus, the poly (meth) acrylate may be composed of acrylates and/or methacrylates and may comprise other ethylenically unsaturated monomers, such as styrene or acrylic acid. The term "(meth) acryl" in the sense of the present invention includes methacryl compounds, acryl compounds and mixtures thereof.

In the context of the present invention, C₁-C₄Alkyl means methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably methyl, ethyl and n-butyl, more preferably methyl and ethyl, most preferably methyl.

Step (1):

in step (1) of the process of the present invention, a nonwoven textile substrate (S) is provided. The nonwoven substrate may be made entirely of nonwoven material, or at least on one surface thereof may include a coating made of nonwoven material. In the latter case, the core of the substrate may be made of glass, ceramic, metal, wood and/or plastic. The substrate used may be an already shaped article, for example a part of a shoe, such as an insole and/or an outsole and/or a quarter and/or a heel and/or an upper, or a part of a garment. Alternatively, the substrate may be unformed. In this case, the shaping of the substrate can be carried out after the printing process of the invention.

In principle, the nonwoven textile substrate used in the process of the invention may be selected from staple fiber nonwoven textiles, meltblown nonwoven textiles, spunlaid nonwoven textiles and flash-spun nonwoven textiles.

Staple fiber nonwovens are typically manufactured in four steps. The fibers are first spun, cut to a length of several centimeters, and baled. The staple fibers are then mixed, "opened", dispersed on a conveyor belt in a multi-step process and spread into a uniform web by wet-laid, air-laid, or carding/cross-lapping methods. Wet-laid operations typically use fibers that are 0.25 to 0.75 inches (0.64 to 1.91cm) long, but sometimes longer fibers are used if the fibers are rigid or thick. Airlaid processes typically use fibers of 0.5 to 4.0 inches (1.3 to 10.2 cm). Carding operations typically use 1.5"(3.8cm) long fibers. The short fiber nonwoven is bonded by thermal bonding or using a resin. The bonds may be through resin saturation or through thermal bonding or through resin printing or thermal point bonding in different patterns throughout the web.

Meltblown nonwoven textiles are produced by extruding molten polymer fibers through a spinneret or die consisting of up to 40 holes per inch to form elongated fibers which are drawn and cooled by passing hot air over the fibers as they fall from the die. The resulting web was collected into rolls and subsequently converted into finished products. Very fine fibers differ from other extruded, especially spunbond, fibers in that they have low intrinsic strength, but are much smaller in size, providing key properties. Meltblown nonwoven textiles and spunbond nonwoven textiles are often combined to increase strength, but retain the inherent benefits of fine fibers.

Spunlaid nonwoven textiles are produced in a continuous process. The fibers are spun and then dispersed by air flow directly into a web by a deflector. This technique results in faster belt speeds and cheaper costs. Spunlaid is bonded by the use of resins, heat or hydroentanglement.

Transient fabrics are nonwoven fabrics formed from the fibrillation of films by the rapid evaporation of solvent and subsequent bonding in an extrusion process. For example, a pressurized solution of a polymer such as TPU, HDPE or polypropylene in a solvent such as fluoroform is heated, pressurized and pumped through an orifice into the chamber. When the solution rapidly expands through the pores, the solvent evaporates, leaving behind a highly oriented nonwoven fiber network.

The nonwoven textile substrate or-if a coated substrate is used-the layer located on the surface of the substrate is preferably composed of at least one thermoplastic polymer, more particularly selected from the group consisting of polymethyl (meth) acrylate, polybutyl (meth) acrylate, polyethylene terephthalate, polybutylene terephthalate, polyvinylidene fluoride, polyvinyl chloride, polyesters, including polycarbonate and polyvinyl acetate, preferably polyesters such as PBT and PET, polyamides, polyolefins such as polyethylene, polypropylene, polystyrene and polybutadiene, polyacrylonitrile, polyacetal, polyacrylonitrile-ethylene-propylene-diene-styrene copolymer (a-EPDM), polyetherimide, phenolic resins, urea-formaldehyde resins, melamine resins, alkyd resins, epoxy resins, polyurethanes, including TPU, polyetherketone, polyphenylene sulfide, polyether, polyvinyl alcohol and mixtures thereof.

Particularly preferred nonwoven textile substrates (S) or layers located on their surface are selected from thermoplastic polyurethanes, polypropylenes, glass fibers and mixtures thereof, preferably Thermoplastic Polyurethanes (TPU).

The preparation of thermoplastic polyurethanes (hereinafter also referred to as TPUs) requires a mixture of at least one polyisocyanate and at least one compound having at least one isocyanate-reactive group. Further additions of chain extenders, chain transfer agents, additives and catalysts are optional and may be carried out individually or in all possible variations. Thus, the thermoplastic polyurethane is preferably prepared by reacting:

a) at least one polyisocyanate,

b) at least one compound having at least one isocyanate-reactive group,

c) optionally at least one chain-extending compound,

d) optionally at least one chain transfer agent, and

e) optionally at least one additive selected from the group consisting of,

f) optionally in the presence of at least one catalyst.

The polyisocyanate a) is preferably selected from aliphatic, cycloaliphatic and/or aromatic polyisocyanates, more preferably aliphatic, cycloaliphatic and/or aromatic diisocyanates, even more preferably aromatic diisocyanates, very preferably 4,4' -diphenylmethane diisocyanate and/or hexamethylene diisocyanate. Examples of other preferred diisocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2-methyl-1, 5-pentamethylene diisocyanate, 2-ethyl-1, 4-butylene diisocyanate, 1, 5-pentamethylene diisocyanate, 1, 4-butylene diisocyanate, 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane, 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 4-cyclohexane diisocyanate, 1-methyl-2, 4-cyclohexane diisocyanate, 1-methyl-2, 6-cyclohexane diisocyanate, 2 '-dicyclohexylmethane diisocyanate, 2,4' -dicyclohexylmethane diisocyanate, 4 '-dicyclohexylmethane diisocyanate, 2' -diphenylmethane diisocyanate, 2,4 '-diphenylmethane diisocyanate, 1, 5-naphthylene diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, diphenylmethane diisocyanate, 3' -dimethyldiphenyl diisocyanate, 1, 2-diphenylethane diisocyanate, phenylene diisocyanate and mixtures thereof.

In addition to the at least one polyisocyanate a), Thermoplastic Polyurethanes (TPU) are made from at least one compound having at least one isocyanate-reactive group b). Preferred compounds b) have an average functionality of 1.8 to 2.3, preferably 1.9 to 2.2, very preferably 2, wherein the isocyanate-reactive groups are selected from hydroxyl, amine and thiol groups, preferably hydroxyl groups. Mixtures of two or more compounds having these or other functionalities may also be used, and in proportions such that the average functionality of compound b) is within the above-mentioned ranges. Thus, small amounts of trifunctional polyhydroxy compounds may also be present in order to achieve the desired average functionality of the compounds b). The compounds b) preferably have a molecular weight of 500-10,000g/mol, determined by gel permeation chromatography. In the case of oligomers and polymers, the molecular weight corresponds to the weight-average molecular weight Mw.

Particularly preferred compounds b) are selected from the group consisting of polyesteramides, polythioethers, polycarbonates, polyacetals, polyolefins, polysiloxanes, polybutadienes, polyesterpolyols, polyetherpolyols and mixtures thereof, preferably polyetherdiols, polyesterdiols, polycarbonatediols and mixtures thereof, very preferably polyetherdiols and/or polyesterdiols. Other dihydroxy compounds, such as hydroxyl terminated styrene block copolymers, e.g., SBS, SIS, SEBS, or SIBS, may also be used. The molecular weight Mw of the compounds b) is preferably 500-8,000g/mol, more preferably 600-6,000g/mol, in particular 800-4,000g/mol, determined by gel permeation chromatography.

Polyether diols are particularly preferably used. Suitable polyether alcohols can be prepared by known processes, for example from one or more alkylene oxides having from 2 to 4 carbon atoms in the alkylene radical and, if appropriate, initiator molecules containing the two reactive hydrogen atoms in bonded form, by anionic polymerization using alkali metal hydroxides such as sodium hydroxide or potassium hydroxide or alkali metal alkoxides such as sodium methoxide, sodium ethoxide or potassium isopropoxide as catalysts, or by cationic polymerization using Lewis acids such as antimony pentachloride, boron fluoride etherate or the like or bleaching earth as catalysts. Examples of alkylene oxides are: ethylene oxide, 1, 2-propylene oxide, tetrahydrofuran, 1, 2-and 2, 3-butylene oxide. Preference is given to using ethylene oxide and also mixtures of 1, 2-propylene oxide and ethylene oxide. The alkylene oxides can be used individually, alternately in succession or as mixtures. Examples of suitable initiator molecules are: water, aminoalcohols such as N-alkyldialkanolamines, for example N-methyldiethanolamine, and diols, for example alkanediols or dialkylene glycols having from 2 to 12 carbon atoms, preferably from 2 to 6 carbon atoms, for example ethylene glycol, 1, 3-propanediol, 1, 4-butanediol and 1, 6-hexanediol. Mixtures of initiator molecules may also be used if desired.

Suitable polyether diols may also contain low unsaturation (i.e., less than 0.1 milliequivalents per gram of diol). Other diols that may be used include dispersions or solutions of addition or condensation polymers of the above types of diols. Such modified diols, commonly referred to as "polymeric" diols, have been fully described in the prior art and include products obtained by the in situ polymerization of one or more vinyl monomers, such as styrene and acrylonitrile, in polymeric diols, such as polyether diols, or by the in situ reaction of polyisocyanates with amino-and/or hydroxy-functional compounds, such as triethanolamine, in polymeric diols.

Particularly useful polyether diols are derived from 1, 2-propylene oxide and ethylene oxide, in which more than 50%, preferably 60 to 80%, of the OH groups are primary hydroxyl groups and in which at least part of the ethylene oxide is arranged as end blocks. In this connection, mention may be made of random copolymers having an ethylene oxide content of from 10 to 80%, block copolymers having an ethylene oxide content of up to 25% and random/block copolymers having an ethylene oxide content of up to 50%, based on the total weight of the alkylene oxide units. Such polyether alcohols can be obtained, for example, by first polymerizing 1, 2-propylene oxide onto the initiator molecule and subsequently polymerizing on ethylene oxide, or by first copolymerizing all 1, 2-propylene oxide with partial ethylene oxide and subsequently polymerizing on the remaining ethylene oxide, or stepwise, first polymerizing partial ethylene oxide onto the initiator molecule and then polymerizing on all 1, 2-propylene oxide and subsequently polymerizing on the remaining ethylene oxide.

Other particularly useful polyether diols are the hydroxyl-containing polymerization products of tetrahydrofuran (polyoxytetramethylene glycol). Thus, particularly preferred polyether diols are linear polyether diols selected from polyoxytetramethylene glycols, polyether diols based on 1, 2-propylene oxide, polyether diols based on ethylene oxide and mixtures thereof, wherein the polyether diols have a molecular weight Mw of 800-2,500g/mol, determined by gel permeation chromatography.

In an alternative, particularly preferred embodiment, polyester diols are used to prepare the thermoplastic polyurethanes. Such polyester diols can be prepared, for example, from dicarboxylic acids having from 2 to 12 carbon atoms, preferably from 4 to 8 carbon atoms, and polyhydric alcohols. Examples of suitable dicarboxylic acids are: aliphatic dicarboxylic acids such as succinic acid, glutaric acid, suberic acid, azelaic acid, sebacic acid and preferably adipic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can be used individually or as mixtures, for example in the form of succinic, glutaric and adipic acid mixtures. Also, mixtures of aromatic and aliphatic dicarboxylic acids may be used. For the preparation of the polyester diols, it may be advantageous to use the corresponding dicarboxylic acid derivatives, such as dicarboxylic acid esters having 1 to 4 carbon atoms in the alcohol radical, dicarboxylic acid anhydrides or dicarboxylic acid chlorides, instead of the dicarboxylic acids. Examples of polyols are alkanediols having from 2 to 10, preferably from 2 to 6, carbon atoms, such as ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 10-decanediol, 2-dimethylpropane-1, 3-diol and 1, 2-propanediol, and dialkylene ether glycols, such as diethylene glycol and dipropylene glycol. Depending on the desired properties, the polyols can be used individually or, if desired, as a mixture with one another.

Also suitable are esters of carbonic acid with the abovementioned diols, in particular those having from 4 to 6 carbon atoms, for example 1, 4-butanediol and/or 1, 6-hexanediol, condensation products of omega-hydroxycarboxylic acids, for example omega-hydroxycaproic acid, and preferably polymerization products of lactones, for example substituted or unsubstituted omega-caprolactones.

The polyester diols preferably used are selected from the group consisting of polyalkylene adipates having 2 to 6 carbon atoms in the alkylene radical, preferably polyethylene adipates, polyethylene adipates 1, 4-butanediol, polyethylene adipates 1, 6-hexanediol-neopentyl glycol esters, polycaprolactones and mixtures thereof, very preferably polyethylene adipates 1, 4-butanediol and/or polyethylene adipates 1, 6-hexanediol-1, 4-butanediol.

The polyester diol preferably has a molecular weight (weight average) of 500-6,000g/mol, more preferably 600-3,500g/mol, and very preferably 600-2,000g/mol, as determined by gel permeation chromatography.

When thermoplastic polyetheresters and/or polyesteresters are used, these are obtainable by esterification or transesterification of aromatic and aliphatic dicarboxylic acids having 4 to 20 carbon atoms and their esters, respectively, with suitable aliphatic and aromatic diols and polyols according to any customary literature method (see, for example, "Polymer Chemistry", Interscience publication, New York, 1961, p. 111-127; Kunststoffhandbuch, Vol. VIII, C. Hanser Verlag, Munich 1973 and Journal of Polymer Science, part A1, 4, p. 1851-1859 (1966)).

Useful aromatic dicarboxylic acids include, for example, phthalic acid, isophthalic acid and terephthalic acid or, respectively, esters thereof. Useful aliphatic dicarboxylic acids include, for example, 1, 4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid as saturated dicarboxylic acids, and maleic acid, fumaric acid, aconitic acid, itaconic acid, tetrahydrophthalic acid and tetrahydroterephthalic acid as unsaturated dicarboxylic acids.

Useful diol components include, for example:

general formula HO- (CH)₂)_nDiols of the formula-OH, where n is 2-20, such as ethylene glycol, 1, 3-propanediol, 1, 4-butanediol or 1, 6-hexanediol,

general formula HO- (CH)₂)_n-O-(CH₂)_mPolyether alcohols of-OH, where n and m are each from 2 to 20 and n and m may be identical or different,

unsaturated diols and polyether alcohols, for example 1, 4-butenediol,

diols and polyether alcohols comprising aromatic units,

-a polyesterol.

In addition to the carboxylic acids and esters thereof and the alcohols mentioned, any other common representatives of these compound classes can be used to provide the polyether and polyester esters preferably used.

The hard phase is generally formed from an aromatic dicarboxylic acid and a short-chain diol, while the soft phase is formed from a ready-to-use aliphatic difunctional polyester having a molecular weight of 500-3,000 g/mol.

When polyester esters are used, those obtained from Tojobo are preferably usedThe shape of the product (e.g.,s1001 orP70B). When polyetheresters are used, preference is given to using those from BASFShaped articles (e.g. of the typeA4512) Obtained from DSMShaped articles (e.g. of the typePL380 orEB463) available from DuPontType (e.g. H)3078) Obtained from TiconaShaped articles (e.g. of the type430 or635) Or obtained fromFrom Eastman ChemicalShaped articles (e.g. of the typeElastomer 9965 orElastomer 9965)。

Polycarbonate diols that can be used include those prepared by reacting a diol such as diethylene glycol, triethylene glycol, or hexanediol with formaldehyde. Suitable polyacetals can also be prepared by polymerization of cyclic acetals.

The thermoplastic polyetheramides may be obtained by reaction of amines and carboxylic acids or esters or other derivatives thereof according to any common known literature method. In this case, the amine and/or carboxylic acid further comprises ether units of the R-O-R type, wherein R is an aliphatic and/or aromatic organic group. Monomers selected from the following classes of compounds are generally used:

-HOOC-R'-NH₂wherein R' may be aromatic and aliphatic and preferably comprises ether units of the R-O-R type. Wherein R is an aliphatic and/or aromatic organic group,

aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid, or esters thereof, and aromatic dicarboxylic acids comprising ether units of the R-O-R type, where R is an aliphatic and/or aromatic organic radical,

aliphatic dicarboxylic acids, such as 1, 4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid as saturated dicarboxylic acids, and maleic acid, fumaric acid, aconitic acid, itaconic acid, tetrahydrophthalic acid and tetrahydroterephthalic acid as unsaturated dicarboxylic acids, and aliphatic dicarboxylic acids comprising ether units of the R-O-R type, where R is an aliphatic and/or aromatic organic radical,

general formula H₂N-R”-NH₂Wherein R' can be aromatic and aliphatic, preferably comprising ether units of the type R-O-R, wherein R is an aliphatic and/or aromatic organic radical,

lactams, e.g. epsilon-caprolactam, pyrrolidone or lauryllactam, and

-an amino acid.

In addition to the carboxylic acids and their esters and the amines, lactams and amino acids mentioned, any other common representatives of these compound classes can be used to provide the polyetheramines preferably used. Also known are mixed products of polytetrahydrofuran and amide synthons.

When polyetheramides are used, preference is given to using those from ArkemaShaped articles (e.g. of the type2533 or3533) Or from EvonikShaped articles (e.g. of the typeE4083)。

Polythioether glycols which may be used include products obtained by condensation of thiodiglycol, alone or with other glycols, alkylene oxides, dicarboxylic acids, formaldehyde, amino alcohols or aminocarboxylic acids.

Suitable polyolefin diols include hydroxy-terminated butadiene homopolymers and copolymers, and suitable polysiloxane diols include polydimethylsiloxane diols.

When chain extenders c) are used for the preparation of the thermoplastic polyurethanes, these are preferably aliphatic, araliphatic, aromatic and/or cycloaliphatic compounds which preferably have a molecular weight of from 50 to 500g/mol, more preferably from 60 to 300 g/mol. Suitable chain extenders c) are, for example, alkanediols having from 2 to 12 carbon atoms, preferably 2,4 or 6 carbon atoms, such as ethylene glycol, 1, 6-hexanediol and in particular 1, 4-butanediol; and dialkylene ether glycols such as diethylene glycol and dipropylene glycol. However, other suitable chain extenders are diesters of terephthalic acid with alkanediols having from 2 to 4 carbon atoms, such as bis (ethylene glycol) terephthalate or bis (1, 4-butanediol) terephthalate; hydroxyalkylene ethers of hydroquinone, such as 1, 4-bis (. beta. -hydroxyethyl) hydroquinone; (cyclo) aliphatic diamines such as 4,4 '-diaminodicyclohexylmethane, 3' -dimethyl-4, 4 '-diaminodicyclohexylmethane, 1-amino-3, 3, 5-trimethyl-5-aminomethylcyclohexane, ethylenediamine, 1, 2-and 1, 3-propanediamine, N-methylpropylene-1, 3-diamine and N, N' -dimethylethylenediamine; and aromatic diamines such as 2, 4-and 2, 6-toluenediamine, 3, 5-diethyl-2, 4-and-2, 6-toluenediamine and primary, ortho-dialkyl-, -trialkyl-and/or-tetraalkyl-substituted 4,4' -diaminodiphenylmethane. Mixtures of chain extenders c) may also be used if desired.

Preferred chain extenders c) are alkanediols having from 2 to 6 carbon atoms in the alkylene radical, more preferably 1, 4-butanediol and/or dialkylene glycols having from 4 to 8 carbon atoms.

In order to set the shore hardness of the thermoplastic polyurethane, the compound b) and the at least one chain extender c) can be varied within a relatively wide molar ratio. In a preferred embodiment, the molar ratio of the at least one compound b) to the at least one chain extender c) is from 10:1 to 1:10, preferably from 5:1 to 1:8, more preferably from 1:1 to 1:6.4, very preferably from 1:1 to 1: 4. The hardness and the vicat softening temperature or melting point of the thermoplastic polyurethane increase with increasing amount of chain extender c).

When chain transfer agents d) are used, these generally have molecular weights of from 30 to 500 g/mol. Chain transfer agents are compounds having only one isocyanate reactive group. Examples of chain transfer agents are monofunctional alcohols and/or monofunctional amines, preferably methylamine and/or monofunctional polyols. In particular, chain transfer agents may be used to control the flow characteristics of the mixture of components. In a preferred embodiment, the chain transfer agent is used in an amount of 0 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of compound b). Chain transfer agents may be used in addition to or in place of the chain extender.

In other preferred embodiments, the reaction to form the thermoplastic polyurethane is conducted at conventional indices. The index is defined as the ratio of the total number of isocyanate groups of the aromatic, aliphatic and/or cycloaliphatic diisocyanate a) to the total number of isocyanate-reactive groups (i.e. the number of active hydrogens in compound b), chain extender c) and chain transfer agent d)). If the index is 1, there is one active hydrogen atom, i.e.one isocyanate-reactive group, in components b), c) and d) for each isocyanate group in component a). If the index is greater than 1, more isocyanate groups are present than isocyanate-reactive groups. In a particularly preferred embodiment, the reaction to form the thermoplastic polyurethane is carried out at an index of from 0.6 to 1.2, more preferably at an index of from 0.8 to 1.1.

Particularly preferred thermoplastic polyurethanes are obtained by reacting:

(a) diphenylmethane 4,4' -diisocyanate (MDI) and/or hexamethylene diisocyanate,

(b) polyoxytetramethylene glycol, polyether glycols based on 1, 2-propylene oxide and ethylene oxide and/or polyester glycols based on polyalkylene adipates having 2 to 6 carbon atoms in the alkylene radical, and

(c)1, 2-ethanediol, 1, 4-butanediol and/or 1, 6-hexanediol,

wherein the ratio of isocyanate groups of component (a) to the sum of the isocyanate-reactive groups of components (b) and (c) is preferably from 1:0.8 to 1:1.1 and (b) and (c) are used in a molar ratio of from 1:1 to 1: 6.4.

Other embodiments use at least one catalyst f) to catalyze the reaction between the isocyanate groups, in particular diisocyanates, and the isocyanate-reactive compounds (preferably hydroxyl groups) of compound b) having at least two isocyanate-reactive groups, chain transfer agent c) and chain extender d). In a preferred embodiment, the catalyst is selected from tertiary amines such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N' -dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane and the like. In other preferred embodiments, the at least one catalyst is chosen from organometallic compounds, mention being made, by way of example, of titanates, iron compounds, such as iron (III) acetylacetonate, tin compounds, such as tin diacetate, tin dioctoate, tin dilaurate or the dialkyltin salts of aliphatic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate and the like.

Some embodiments use a single catalyst, while other embodiments use a mixture of catalysts. In a preferred embodiment the catalyst used is a mixture of catalysts in an amount of from 0.0001 to 0.1% by weight, based on the compound b).

In addition to the catalysts, it is also possible to add conventional auxiliaries and/or additives e) to the shaping components a) to d). Examples which may be mentioned are hydrolysis control agents, phosphorus compounds, surface-active substances, flame retardants, nucleating agents, oxidation inhibitors, stabilizers, lubricants and mold release agents, dyes and pigments, inhibitors, stabilizers against hydrolysis, light, heat or discoloration, inorganic and/or organic fillers, reinforcing materials and plasticizers.

Suitable hydrolysis control agents are, for example, polymers and low molecular weight carbodiimides and/or epoxides.

Suitable organophosphorus compounds are selected from trivalent phosphorus, such as phosphites and phosphonites. Examples of suitable phosphorus compounds are triphenyl phosphite, diphenylalkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2, 4-di-tert-butylphenyl) -4,4' -biphenylylene diphosphonite, triisodecyl phosphite, diisodecyl phenyl phosphite and diphenylisodecyl phosphite or mixtures thereof. In particular, phosphorus compounds are such compounds which are difficult to hydrolyze, since hydrolysis of phosphorus compounds to the corresponding acids can cause damage to polyurethanes, especially polyester urethanes. Thus, phosphorus compounds which are particularly difficult to hydrolyze are particularly suitable for polyester urethanes. Preferred embodiments of the difficult-to-hydrolyze phosphorus compounds are dipropylene glycol phenyl phosphite, diisodecyl phosphite, triphenylmonodecyl phosphite, triisononyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tetrakis (2, 4-di-tert-butylphenyl) -4,4' -biphenylene diphosphite and di (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite or mixtures thereof.

If desired, up to 10% by weight, based on the total weight of the TPU, of color pigments or color batches may be added to color the TPU. Suitable pigments may be colored, white and black pigments (coloring pigments) and inorganic pigments which are generally used as fillers. Suitable organic pigments are, for example, monoazo pigments, disazo pigments, anthraquinone pigments, benzimidazole pigments, quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone pigments, isoindoline pigments, metal complex pigments, perinone pigments, perylene pigments, phthalocyanine pigments, aniline black and mixtures thereof. Suitable inorganic pigments are, for example, titanium dioxide, zinc white, zinc sulfide, lithopone, black iron oxide, black iron manganese, spinel black, carbon black, ultramarine green, ultramarine blue, manganese blue, ultramarine violet, red iron oxide, molybdate red, ultramarine blue, brown iron oxide, mixed brown, spinel and corundum phases, yellow iron oxide, bismuth vanadate and mixtures thereof. As examples of inorganic pigments which are generally used as fillers, mention may be made of transparent silica, quartz powder, alumina, aluminum hydroxide, natural mica, natural and precipitated chalk, and barium sulfate.

The TPU may further comprise from 0.1 to 3% by weight of UV light absorbers and/or from 0.1 to 5% by weight of light stabilizers, in each case based on the total weight of the TPU. Suitable UV light absorbers are, for example, benzotriazoles. HALS compounds may be used as suitable UV light stabilizers.

Further, the TPU may comprise from 0.05 to 2 weight percent of an antioxidant, such as a phenolic antioxidant, based on the total weight of the TPU.

If desired, from 0.3 to 5% by weight, based on the total weight of the TPU, of lubricants and/or processing aids selected from ester waxes, polyolefin waxes, metal soaps, amide waxes, fatty acid amides or mixtures thereof may also be incorporated. However, preferred non-textile TPU substrates are free of such lubricants and/or processing aids, i.e., preferred TPU substrates comprise 0 wt% of lubricants and/or processing aids based on the total weight of the TPU, in order to improve adhesion of the printing ink to the substrate.

Suitable flame retardants, for example inorganic hydroxides such as aluminum hydroxide, inorganic phosphates such as ammonium polyphosphate or organic nitrogen compounds such as melamine or melamine derivatives, may also be included in the TPU.

TPUs suitable for preparing nonwoven substrates can be obtained by the so-called one-step, semi-prepolymer or prepolymer process, by casting, extrusion or any other process known to the person skilled in the art, and are usually provided as granules or pellets.

Optionally, small amounts, i.e. up to 30 wt%, preferably 20 wt%, most preferably 10 wt%, based on the total weight of the blend, of other conventional thermoplastic elastomers such as PVC, EVA or TR may be blended with the TPU.

Particularly suitable TPUs have the following characteristics:

-shore hardness of a44 to D80, more preferably a50 to a99, even more preferably a60 to a95, very preferably a70 to a90, especially preferably a80 or a83, according to DIN ISO 7619-1: 2012-02 is determined using a 3 second measurement time, and/or

-a vicat softening temperature of 40 to 160 ℃, more preferably 50 to 130 ℃, very preferably 80 to 120 ℃, according to DIN EN ISO 306: 2014-03 using a heating rate of 120 deg.C/hr and a load measurement of 10N, and/or

-a glass transition temperature Tg of from 100 ℃ to 20 ℃, more preferably from-80 ℃ to 20 ℃, even more preferably from-60 ℃ to 0 ℃, very preferably-44 ℃, according to DIN EN ISO 11357-1: 2017-02 is measured at a heating rate of 10 deg.C/min, and/or

-a tensile strength of 10 to 60MPa, more preferably 20 to 60MPa, even more preferably 30 to 60MPa, very preferably 45MPa or 55MPa, according to DIN 53504: 2009-10 determined using stretch strip S2, and/or

An elongation at break of-300-: 2009-10 determined using stretch strip S2, and/or

-a tear resistance of 27 to 240kN/m, more preferably 30 to 150kN/m, even more preferably 40 to 100kN/m, very preferably 55kN/m or 75kN/m, according to DIN EN ISO 34-1: 2004-07 determined using procedure (a) of method B, and/or

-25-165mm³More preferably 25 to 100mm³Even more preferably 25-50mm³Very preferably 30mm³Or 35mm³Wear loss according to DIN EN ISO 4649: 2010-09 was determined using method A.

The nonwoven textile substrate (S) preferably used according to the invention has a mass fraction of 50 to 1,000g/m²More preferably 80 to 700g/m²Even more preferably 100-²Very preferably 400-500g/m²Basis weight of (c). Step (2):

in optional step (2) of the process of the present invention, the nonwoven textile substrate (S) is pretreated.

By means of the pretreatment, the absorbency of the substrates used can be adjusted so as to prevent, for example, excessive penetration of the ink into the substrate, which can lead to an undesirable stiffness of the substrate after curing. The pretreatment may also improve the adhesion of the ink to the substrate, thereby improving the resolution of the printed image.

Preferably, the nonwoven textile substrate (S) is pretreated by applying at least one primer composition. This improves the adhesion of the ink composition (AC) to the substrate (S) covered with the primer composition. Suitable primer compositions are known in the art and may be aqueous, solvent based or 100% solids primer compositions. Such compositions comprise at least one resin selected from the group consisting of (meth) acrylates, polyurethanes, epoxides and radiation curable polymers and/or oligomers and mixtures thereof. In this case, the ink composition (AC) is applied to the substrate (S) coated with the primer composition. The primer composition may be dried and/or at least partially cured before applying the ink composition (AC).

And (3):

in step (3) of the process of the present invention, at least one specific ink composition (AC) is deposited on at least a portion of at least one surface of the nonwoven textile substrate (S) obtained after step (1) or (2).

Preferably, the ink composition (AC) is deposited directly on at least one surface of the nonwoven textile substrate (S). The direct application of the ink composition (AC) onto the nonwoven textile substrate (S) results in the ink composition (AC) being in direct contact with the nonwoven textile substrate (S). Thus, there is no further layer, preferably no primer layer, between the ink composition (AC) and the substrate (S).

If an already shaped article is used or a substrate comprising a suitable thickness is used, the substrate comprises four surfaces which can be printed. In this case, it may be advantageous if the ink composition (AC) is deposited on more than one surface of the substrate. This is particularly preferred if the image to be printed with the ink composition (AC) is located on at least two surfaces of the substrate. Thus, according to a preferred embodiment of step (3) of the present invention, the ink composition (AC) is deposited on at least two surfaces of the nonwoven textile substrate (S).

Ink composition (AC):

the ink composition (AC) used in step (3) of the process of the invention comprises, as essential components, an aqueous dispersion (i) of at least one polyurethane (meth) acrylate polymer and at least one pigment (ii). If the printing ink is cured by UV light, it further comprises at least one photoinitiator (iii). The ink composition (AC) used in the process of the present invention may be a water-based, solvent-based or high-solids (i.e. having a solids content of greater than 40% but less than 100%) ink composition. Preferably, the ink composition (AC) is an aqueous ink composition.

Aqueous dispersions of polyurethane (meth) acrylate polymers (i):

preferred urethane (meth) acrylate polymers are obtained by the reaction of:

(a) at least one (cyclo) aliphatic di-and/or polyisocyanate,

(b1) at least one (cyclo) aliphatic diol having a molar mass of less than 700g/mol,

(b2) at least one polyester diol having a weight-average molar mass Mw of 700-2000 and preferably not more than 20mg KOH/g in a molar ratio in accordance with DIN 53240-2: an acid value of 2007-11 (g),

(c) at least one compound having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group,

(d) at least one compound having at least one isocyanate-reactive group and at least one acid group,

(e) at least one alkali metal base for at least partially neutralizing the acid groups of component (d),

(f) optionally, at least one monohydric alcohol having exactly one hydroxyl function, or at least one mono-and di-C₁-C₄An alkylamine, and

(g) at least one monofunctional polyoxyalkylene polyether alcohol.

Component (a) is at least one, preferably 1 to 4, more preferably 1 to 3, (cyclo) aliphatic di-and/or polyisocyanates. These are monomers and/or oligomers of aliphatic or cycloaliphatic diisocyanates. The NCO functionality of the compounds is generally at least 1.8 and may be up to 8, preferably from 1.8 to 5, more preferably from 2 to 4. The di-and polyisocyanates which can be used preferably have an isocyanate group content (calculated as NCO, molecular weight 42) of from 10 to 60% by weight, preferably from 15 to 60% by weight, more preferably from 20 to 55% by weight, based on the di-and polyisocyanate (mixture).

Preferred are aliphatic and/or cycloaliphatic di-and polyisocyanates, collectively referred to in the context of this specification as aliphatic (cyclo) groups, examples being the above-mentioned aliphatic and/or cycloaliphatic diisocyanates, or mixtures thereof.

Component (a) is preferably a mixture of cycloaliphatic or aliphatic, preferably aliphatic, monomeric diisocyanates (a1) and polyisocyanates (a 2). In this context, component (a1) is preferably selected from the group consisting of hexamethylene diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 4 '-or 2,4' -bis (isocyanatocyclohexyl) methane and mixtures thereof, more preferably from the group consisting of isophorone diisocyanate and hexamethylene diisocyanate, most preferably hexamethylene-1, 6-diisocyanate.

In this context, component (a2) is preferably a polyisocyanate having isocyanurate groups, a uretdione diisocyanate, a polyisocyanate having biuret groups, a polyisocyanate having urethane groups or allophanate groups and mixtures thereof.

Most preferably, polyisocyanate (a2) is a polyisocyanate comprising at least one hydroxyalkyl (meth) acrylate linked via an allophanate group and satisfying formula (I):

wherein R is⁵Is a divalent alkylene radical having from 2 to 12 carbon atoms and optionally substituted by C₁-C₄Alkyl substituted and/or interrupted by one or more oxygen atoms, preferably having from 2 to 10 carbon atoms, more preferably from 2 to 8 carbon atoms, most preferably from 3 to 6 carbon atoms, R⁶Is a divalent alkylene or cycloalkylene radical having from 2 to 20 carbon atoms and optionally substituted by C₁-C₄Alkyl is substituted and/or interrupted by one or more oxygen atoms, preferably having from 4 to 15 carbon atoms, more preferably having from 6 to 13 carbon atoms, hydrogen or methyl, preferably hydrogen, and x is a positive number having a statistical average value of from 2 to 6, preferably from 2 to 4.

In a particularly preferred embodiment of the invention, R⁶Is 1, 6-hexylene, R⁵Selected from the group consisting of 1, 2-ethylene, 1, 2-propylene and 1, 4-butylene, preferably 1, 2-ethylene and 1, 4-butylene, more preferably 1, 2-ethylene. Wherein R is⁵1, 2-ethylene, R⁶Is 1, 6-hexylene and R⁷Commercial polyisocyanates which are hydrogen can be given the trade nameLR 9000 was obtained from BASF SE, Ludwigshafen and had an NCO content of 14.5 to 15.5% by weight.

Component (b1) is at least one, preferably 1 to 3, more preferably 1 to 2, most preferably exactly one (cyclo) aliphatic, especially aliphatic, diol having a molar mass of less than 700g/mol, preferably less than 600g/mol, more preferably less than 500g/mol, most preferably less than 400 g/mol. Cycloaliphatic diols are understood to mean those diols which comprise at least one saturated ring system.

Preferred diols (b1) are ethylene glycol, propane-1, 2-diol, propane-1, 3-diol, 2-dimethylethane-1, 2-diol, 2-dimethylpropane-1, 3-diol (neopentyl glycol), butane-1, 2-diol, butane-1, 3-diol, butane-1, 4-diol, hexane-1, 6-diol or diethylene glycol. Particularly preferred compounds (b1) are ethylene glycol, propane-1, 2-diol, propane-1, 3-diol, neopentyl glycol, butane-1, 4-diol and diethylene glycol. Very particularly preferred compounds (b1) are ethylene glycol, neopentyl glycol and butane-1, 4-diol, especially neopentyl glycol.

Component (b2) is at least one, preferably 1 to 3, more preferably 1 to 2, most preferably exactly one polyester diol having a weight average molar mass Mw of 700-2,000g/mol, preferably 750-1,500g/mol (determined, for example, by Gel Permeation Chromatography (GPC)), preferably having a molar mass ratio in accordance with DIN 53240-2: 2007-11 is an acid value of not more than 20mg KOH/g.

Preferably a polyester diol formed at least in part from cycloaliphatic diol and/or dicarboxylic acid units, more preferably a polyester diol formed at least in part from cycloaliphatic diol units, most preferably a polyester diol comprising only cycloaliphatic diol as diol units, in addition to any desired dicarboxylic acid units. Such polyester diols have increased stiffness compared to those formed from purely aliphatic units. Furthermore, aliphatic and cycloaliphatic units have a smaller tendency to yellowing than purely aromatic units. The dicarboxylic acid units may be free acids or derivatives thereof. Derivatives are preferably understood to mean the corresponding anhydrides, mono-or dialkyl esters, preferably mono-or di-C, in monomeric or polymeric form₁-C₄Alkyl esters, more preferably mono-or dimethyl esters or the corresponding mono-or diethyl esters, or mono-and divinyl esters, and mixed esters, preferably of different C₁-C₄Mixed esters of alkyl components, more preferably mixed methylethyl esters.

The diols preferably used are ethylene glycol, propane-1, 2-diol, propane-1, 3-diol, butane-1, 4-diol, pentane-1, 5-diol, hexane-1, 6-diol and octane-1, 8-diol.

Preferred cycloaliphatic diols are cyclohexane-1, 2-, -1, 3-and-1, 4-diol, 1, 3-and 1, 4-bis (hydroxymethyl) cyclohexane and bis (4-hydroxycyclohexane) isopropylidene. Examples of aliphatic dicarboxylic acids are oxalic acid, malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane-alpha, omega-dicarboxylic acid, dodecane-alpha, omega-dicarboxylic acid and derivatives thereof. Examples of cycloaliphatic dicarboxylic acids are cis-and trans-cyclohexane-1, 2-dicarboxylic acid (hexahydrophthalic acid), cis-and trans-cyclohexane-1, 3-dicarboxylic acid, cis-and trans-cyclohexane-1, 4-dicarboxylic acid, 1,2-, 1, 3-or 1, 4-cyclohex-4-enedicarboxylic acid (tetrahydrophthalic acid), cis-and trans-cyclopentane-1, 2-dicarboxylic acid, cis-and trans-cyclopentane-1, 3-dicarboxylic acid and derivatives thereof. Examples of aromatic dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and phthalic anhydride, preferably phthalic acid and isophthalic acid, particularly preferably phthalic acid.

Component (c) is at least one, preferably 1-3, more preferably exactly 1-2, most preferably exactly one compound having at least one, e.g. 1-3, preferably 1-2, more preferably exactly one isocyanate-reactive group and at least one, e.g. 1-5, preferably 1-3, more preferably one or two, most preferably exactly one free-radically polymerizable unsaturated group. The isocyanate-reactive groups may be, for example, -OH, -SH, -NH₂and-NHR⁸Wherein R is⁸Is an alkyl group containing 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. The isocyanate-reactive group may preferably be-OH, -NH₂or-NHR⁸More preferably-OH or-NH₂Most preferred is-OH.

In a preferred embodiment, component (c) is selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-or 3-hydroxypropyl acrylate and butane-1, 4-diol monoacrylate, 1, 2-or 1, 3-diacrylate of glycerol, trimethylolpropane diacrylate, pentaerythritol triacrylate, bis (trimethylolpropane) triacrylate and dipentaerythritol pentaacrylate, preferably from the group consisting of 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, preferably 2-hydroxyethyl acrylate.

In a preferred embodiment, at least a portion of compound (c) is linked to a diisocyanate or polyisocyanate (a), preferably polyisocyanate (a2), more preferably via allophanate groups. In this case, the molar ratio of the compound (c) linked to the polyisocyanate (a2) to the compound (c) used in free form for preparing the urethane (meth) acrylate of the present invention is, for example, from 90:10 to 10:90, preferably from 20:80 to 80:20, more preferably from 30:70 to 70: 30. Preferably, the compound (c) linked to the polyisocyanate (a2) and the compound (c) used in free form for preparing the urethane (meth) acrylates of the invention are the same compound (c), but they may also be different compounds (c).

Component (d) is at least one, preferably exactly one compound having at least one, e.g. one or two, preferably exactly two, isocyanate-reactive groups and at least one acid group. Acid groups are understood to mean carboxylic, sulfonic or phosphonic acid groups, preferably carboxylic or sulfonic acid groups, more preferably carboxylic acid groups. The compound (d) is preferably a compound having exactly two hydroxyl groups and exactly one acid group, preferably exactly one carboxylic acid group. Examples thereof are dimethylolpropionic acid, dimethylolbutyric acid and dimethylolvaleric acid, dimethylolpropionic acid and dimethylolbutyric acid being preferred, and dimethylolpropionic acid being particularly preferred as compound (d).

Component (e) is at least one alkali metal base which serves to at least partially neutralize the acid groups of component (d). Useful basic compounds (e) include alkali metal hydroxides, carbonates and bicarbonates. It is particularly preferred to neutralize at least partially, preferably completely, with sodium hydroxide or potassium hydroxide. The amount of chemically linked acid groups introduced and the degree of neutralization of the acid groups (generally from 40 to 100 mol%, preferably from 50 to 100 mol%, more preferably from 60 to 100 mol%, even more preferably from 75 to 100 mol%, in particular from 90 to 100 mol%, based on equivalents) should preferably be sufficient to ensure dispersion of the polyurethane in aqueous medium, as is well known to the person skilled in the art. The use of alkali metal hydroxides, carbonates and bicarbonates results in polyurethane (meth) acrylate polymers having high water redispersibility even after drying and before curing, since the salts are stable and compatible with water. This redispersibility makes it possible to easily clean the nozzles of the printer and prevent clogging during printing or in an idle state.

Preferably, 50 to 100 mol% of the acid groups obtained from (d) are neutralized. This leads to a monomodal particle size distribution of the dispersed particles and increases the stability of the dispersion.

Optional component (f) is at least one nucleophilic alcohol or amine, preferably a monohydric alcohol or a monoamine, which may act as a terminator of any free isocyanate groups still present in the urethane (meth) acrylate. Preferred terminators (f) are diethylamine, di-N-butylamine, ethanolamine, propanolamine, N-dipropanolamine and N, N-diethanolamine. The invention does not include having a ratio of C₁-C₄Monoalkylamines and dialkylamines with longer alkyl groups, since these reduce the hydrophilicity of the urethane (meth) acrylate. Also excluded are diamines and polyfunctional amines, as these act as chain extenders and increase the molecular weight of the urethane (meth) acrylates, which makes dispersion or solubility more difficult.

Up to 10% by weight, based on the polyurethane (meth) acrylate to be synthesized, of the terminating agent (f) can be used. The function of the compound (f) is to satisfy any unconverted isocyanate groups remaining during the preparation of the polyurethane (meth) acrylate polymer.

The essential compound (g) is at least one monofunctional polyoxyalkylene polyether alcohol, which can be obtained by alkoxylation of alcohols. Very particular preference is given to those based on polyoxyalkylene polyether alcohols which are prepared using saturated aliphatic alcohols having from 1 to 4 carbon atoms in the alkyl radical. Particularly preferred polyoxyalkylene polyether alcohols are those prepared starting from methanol. The monopolyoxyalkylene polyether alcohols contain, on average, usually up to 90, preferably up to 45, more preferably up to 40, most preferably up to 30, oxyalkylene units, preferably oxyethylene units, in copolymerized form per molecule.

Particularly preferred compositions of the polyurethane (meth) acrylate polymers are as follows:

(a)100 mol% of isocyanate functional groups in the sum of (a1) and (a2),

(b)5 to 35 mol%, preferably 15 to 35 mol%, of the hydroxyl functions of the sum of (b1) and (b2) (based on the isocyanate functions in (a)),

(c)20 to 80 mol%, preferably 30 to 70 mol%, of hydroxyl functions, based on the isocyanate functions in (a),

(d)20 to 60 mol%, preferably 25 to 50 mol%, of hydroxyl functions, based on the isocyanate functions in (a),

(e)60 to 100 mol%, preferably 80 to 100 mol%, of a base, based on the acid functions in (d),

(f)0 to 30 mol%, preferably 5 to 30 mol%, more preferably 10 to 25 mol%, of hydroxyl or amino functional groups which react with isocyanates, based on the isocyanate functional groups in (a),

(g)0.5 to 10 mol%, preferably 1 to 5 mol%, of hydroxyl functions, based on the isocyanate functions in (a),

with the proviso that the sum of the isocyanate-reactive groups in components (b), (c), (d) and (g) is from 70 to 100 mol%, preferably from 75 to 100 mol%, more preferably from 80 to 100 mol%, of isocyanate-reactive groups (based on isocyanate functional groups in (a)).

The reaction of components (b), (c), (d) and (g) can preferably be terminated by adding component (f) at an isocyanate group conversion of 60 to 100%, more preferably 70 to 100%, most preferably 75 to 100%.

When the isocyanate groups of component (a) are in the form of two different components (a1) and (a2), the ratio of (a1) to (a2) (based on the amount of isocyanate groups present therein) is from 4:1 to 1:4, preferably from 2:1 to 1:4, more preferably from 1:1 to 1:4, most preferably from 1:3 to 1: 4. Furthermore, the number of the sum of components (a1) and (a2) is of course based on only one component (a).

The molecular weight Mw of the polyurethane (meth) acrylate polymer may, for example, be from 1,000g/mol to a maximum of 50,000g/mol, preferably 3,000-30,000g/mol, more preferably 5,000-25,000g/mol, most preferably at least 5,000g/mol, as determined, for example, by Gel Permeation Chromatography (GPC) using polystyrene as internal standard.

In order to achieve a high degree of crosslinking during curing of the aqueous ink composition (AC), it is preferred that the polyurethane (meth) acrylate polymer contains 1 to 5mol, preferably 2 to 4mol, of (meth) acryloyl groups per 1,000g of polyurethane (meth) acrylate.

The polyurethane (meth) acrylate polymer preferably has a glass transition temperature of not more than 50 ℃, preferably not more than 40 ℃, as determined according to ASTM 3418/82(1988) at a heating rate of 10 ℃/minute.

In a preferred embodiment, the polyurethane (meth) acrylate polymer does not contain any free NCO groups.

The polyurethane (meth) acrylate polymer can be prepared from components (a) to (g) by first adding components (b) and (c) and optionally (d) at least partially, preferably completely, and adding isocyanate (a) to the mixture of the first added components. The reaction mixture is then reacted at a temperature of from 25 to 100 c, preferably from 40 to 90 c, for a period of from 3 to 20 hours, preferably from 4 to 12 hours, with stirring or pumped circulation. Typically, component (f) is added when the components present in the reaction mixture have substantially reacted, for example to an extent of at least 50%, preferably to an extent of at least 75%. The reaction is accelerated by the addition of suitable catalysts known from the literature. If unconverted isocyanate groups are still present, the reaction can be completed by reaction with the terminator (f) under the reaction conditions described above. After preparation, the reaction mixture is dispersed or diluted in water.

The dispersions (i) of polyurethane (meth) acrylate polymers generally have a solids content of from 35 to 45%, but the latter may also be up to 60%.

The average particle size in the dispersion (i) is generally from 10 to 150nm, preferably from 15 to 120nm, more preferably from 20 to 100nm, most preferably from 20 to 90 nm.

The ink composition (AC) preferably comprises the at least one aqueous dispersion of the polyurethane (meth) acrylate polymer (i) in a total amount of 15 to 95 parts, preferably 20 to 50 parts, very preferably 25 to 35 parts, based on 100 parts of the ink composition. The use of said amounts in the ink composition results in a high double bond conversion of at least 70%, more preferably at least 75%, still more preferably at least 80%, very preferably at least 85%, more particularly at least 90% and thus in a highly crosslinked ink layer with high adhesion to the substrate (S) and high stability against environmental influences. Furthermore, the high double bond conversion results in a non-toxic cured ink composition suitable for substrates (S) in direct contact with the skin.

Pigment and/or dye (ii):

the pigments are in fact water-insoluble, finely divided organic or inorganic colorants as defined in DIN 55944. The terms "colored pigment" and "color pigment" are interchangeable. In contrast, the term "dye" denotes a colorant that is soluble in the main solvent and/or the co-solvent present in the ink composition (AC).

The ink composition (AC) preferably used in the process of the invention comprises at least one pigment (ii) selected from: inorganic pigments, such as titanium dioxide, zinc white, zinc sulfide, lithopone, carbon black, iron manganese black, spinel black, chromium oxide, hydrated chromium oxide green, cobalt green, ultramarine green, cobalt blue, ultramarine blue, manganese blue, ultramarine violet, cobalt violet and manganese violet, iron oxide red, cadmium sulfoselenide, molybdate-chromium red and ultramarine red, iron oxide brown, mixed brown, spinel phases and corundum phases, and also chromium orange, iron oxide yellow, nickel titanium yellow, chromium titanium yellow, cadmium sulfide, zinc cadmium sulfide, chromium yellow and bismuth vanadate; organic pigments such as monoazo pigments, disazo pigments, anthraquinone pigments, benzimidazole pigments, quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone pigments, isoindoline pigments, isoindolinone pigments, azomethine pigments, thioindigo pigments, metal complex pigments, perinone pigments, perylene pigments, phthalocyanine pigments and/or aniline black; and mixtures thereof.

Useful effect pigments are, for example, platelet-shaped metallic effect pigments, such as lamellar aluminum pigments, gold bronzes, bronze oxides and/or iron oxide-aluminum pigments, pearlescent pigments, such as pearl powders, basic lead carbonates, bismuth oxychloride and/or metal oxide-mica pigments and/or other effect pigments, such as flake graphite, platelet-shaped iron oxides, multilayer effect pigments consisting of PVD films and/or liquid-crystalline polymer pigments. Particularly preferred are the flake-like metallic effect pigments, more particularly the flake-like aluminum pigments.

To prevent clogging of parts of used printers, it is desirable to use a particle size D₉₀Pigments smaller than 1 μm.

The dyes which can be advantageously used in the present invention are water-soluble direct dyes and/or water-soluble acid dyes and/or cationic dyes. Suitable direct dyes are, for example, c.i. direct yellow 1,8, 11, 12, 24, 26, 27, 33, 39, 44, 50, 58, 85, 86, 88, 98, 100, 110, c.i. direct red 1,2,4, 9, 11, 13, 17, 20, 23, 24, 28, 31, 33, 37, 39, 44, 62, 81, 83, 99, 227, c.i. direct blue 1,2,6, 8, 15, 22, 25, 71, 76, 78, 86, 98, 108, 120, 192, 193, 194, 195, 196, 199, 200, 201, 202, 203, 207, 236, 237, c.i. direct black 2,4, 17, 19, 22, 32, 38, 51, 56, 62, 71, 74, 75, 77, 105, 108, 112, 154 and mixtures thereof. Suitable acid dyes are, for example, c.i. acid yellow 7, 17, 23, 29, 42, 99, c.i. acid orange 56, 64, c.i. red 18, 87, 92, 94, c.i. acid blue 1,7, 9, 234, 236, c.i. acid green 12, 19, 27, 41, c.i. acid black 1,2, 7, 24, 94 and mixtures thereof. Types of cationic dyes that may be used include azo compounds, diphenylmethane compounds, triarylmethane compounds, xanthene compounds, acridine compounds, quinoline compounds, methine or polymethine compounds, thiazole compounds, indamine or indophenol compounds, azine compounds, oxazine compounds, thiazine compounds, and mixtures thereof.

The total amount of the at least one pigment and/or dye (ii) is preferably from 0.01 to 5 parts, more preferably from 0.1 to 2.5 parts, very preferably from 0.2 to 0.5 part, based on 100 parts of the ink composition. The amount does not interfere with the crosslinking of the polymer (i) during curing, allowing a high coverage of the substrate (S) and producing images with bright colours.

Photoinitiator (iii):

for curing by means of UV light, the ink composition (AC) used in step (3) preferably comprises at least one photoinitiator as component (iii). On the other hand, in the case of curing with electron beam or (N) IR, the presence of such a photoinitiator is not essential. The ink composition (AC) preferably comprises as component (iii) at least one photoinitiator which is decomposable by light of an irradiation wavelength to generate radicals which in turn are capable of initiating a radical polymerization.

Photoinitiators, such as UV photoinitiators, are known to the person skilled in the art. Those envisaged include, for example, phosphine oxides, benzophenones, thioxanthones, anthraquinones, acetophenones such as alpha-aminoarylketones and/or alpha-hydroxyalkylarylketones, benzoins and benzoin ethers, ketals, imidazoles or benzoylformic acids, and mixtures thereof.

The at least one photoinitiator (iii) is preferably selected from phosphine oxides, benzophenones, thioxanthones, anthraquinones, acetophenones, such as alpha-aminoarylketones and/or alpha-hydroxyalkylarylketones, benzoins and benzoin ethers, ketals, imidazoles or benzoylformic acids, and mixtures thereof.

Phosphine oxides are, for example, monoacyl-or bisacylphosphine oxides, examples being 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphinate or bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide. Examples of benzophenones are benzophenone, 4-aminobenzophenone, 4' -bis (dimethylamino) benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, Michler's ketone, o-methoxybenzophenone, 2,4, 6-trimethylbenzophenone, 4-methylbenzophenone, 2, 4-dimethylbenzophenone, 4-isopropyl benzophenone, 2-chlorobenzophenone, 2' -dichlorobenzophenone, 4-methoxybenzophenone, 4-propoxy benzophenone or 4-butoxy benzophenone; alpha-hydroxyalkylaryl ketones are, for example, 1-benzoylcyclohexane-1-ol (1-hydroxycyclohexyl phenyl ketone), 2-hydroxy-2, 2-dimethylacetophenone (2-hydroxy-2-methyl-1-phenylpropan-1-one), 1-hydroxyacetophenone, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methylpropan-1-one, or polymers comprising 2-hydroxy-2-methyl-1- (4-isopropen-2-ylphenyl) propan-1-one in copolymerized form. Xanthones and thioxanthones are, for example, 10-thioxanthone, thioxanth-9-one, xanthen-9-one, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, 2, 4-dichlorothioxanthone or chloroxanthone; the anthraquinones include, for example, β -methylanthraquinone, tert-butylanthraquinone, anthraquinone carboxylate, benzo [ de ] anthracen-7-one, benzo [ a ] anthracen-7, 12-dione, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone or 2-amylanthraquinone. Acetophenone, acetyl naphthoquinone, pentanone, hexanone, alpha-phenylbenzone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, p-diacetylbenzene, 4' -methoxyacetophenone, alpha-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indanone, 1,3, 4-triacetylbenzene, 1-acetonaphthalene, 2, 2-dimethoxy-2-phenylacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 1-hydroxyacetophenone, 2, 2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropanophenone -1-one, 2-dimethoxy-1, 2-diphenylethan-2-one or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one. Benzoins and benzoin ethers are for example 4-morpholinodeoxybenzoin, benzoin isobutyl ether, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin isopropyl ether or 7H-benzoin methyl ether. Ketals are, for example, acetophenone dimethyl ketal, 2-diethoxyacetophenone or benzil ketals, for example benzil dimethyl ketal. Typical mixtures include, for example, 2-hydroxy-2-methyl-1-phenylpropan-2-one and 1-hydroxycyclohexylphenyl ketone, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone and 1-hydroxycyclohexylphenyl ketone, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide and 1-hydroxycyclohexylphenyl ketone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4, 6-trimethylbenzophenone and 4-methylbenzophenone, or 2,4, 6-trimethylbenzophenone and 4-methylbenzophenone and 2,4, 6-trimethylbenzoyldiphenylphosphine oxide.

Preferred among these photoinitiators are 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphinate, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, benzophenone, 1-benzoylcyclohexane-1-ol, 2-hydroxy-2, 2-dimethylacetophenone and 2, 2-dimethoxy-2-phenylacetophenone, and particularly preferred is a mixture of bisacetylphosphine oxide and monoacetylphosphine oxide. Therefore, it is preferred to use at least one such photoinitiator as component (iii).

The total amount of the at least one photoinitiator (iii) is preferably from 0.01 to 8 parts, more preferably from 0.1 to 7 parts, even more preferably from 0.2 to 5 parts, very preferably from 0.2 to 1.5 parts, based on 100 parts of the ink composition. The use of said amount of photoinitiator (iii) results in an efficient curing of the ink composition (AC) when UV light is used, thus producing a cured Ink Layer (IL) with high adhesion to the substrate and high stability of the printed and cured image to the environmental impact.

Surfactant (iv):

the ink composition (AC) may further comprise at least one surfactant (iv).

Surfactants are compounds that lower the surface tension (or interfacial tension) between two liquids, between a gas and a liquid, or between a liquid and a solid. Surfactants are typically amphiphilic organic compounds, meaning that they contain both hydrophobic groups (their tails) and hydrophilic groups (their heads). Thus, surfactants comprise both a water-insoluble (or oil-soluble) component and a water-soluble component. The surfactant will diffuse in the water and, in the case of a mixture of water and oil, adsorb at the interface between air and water or at the interface between oil and water. The water-insoluble hydrophobic groups may extend out of the bulk of the aqueous phase, into the air or into the oil phase, while the water-soluble head groups remain in the aqueous phase.

Surfactants used in inkjet inks are classified as high HLB (typically HLB greater than 13) surfactants and low HLB (typically HLB less than 13) surfactants. The term "hydrophilic and lipophilic balance" or "HLB" as used herein means the value determined according to the method described in P.Becher et al, "Noninic Surfactant, Physical Chemistry", Marcel Dekker, New York (1987), page 439-456. The HLB value is an empirical value on an arbitrary scale that is conveniently and widely used in surfactant chemistry to provide a measure of the polarity of a surfactant or surfactant mixture.

High HLB surfactants are typically used to support the colloidal stability of the ink, while low HLB surfactants are used to reduce the surface tension so that the ink can wet the nozzle capillaries to establish and maintain a meniscus at the nozzle tip. The importance of maintaining the meniscus at the nozzle tip in both steady state and dynamic state is critical to start-up, reduce latency (defined as the number of ejections required before the ink builds up the first stable ejected drop), increase the elapsed time between ejections without refresh and ultimately long-term reliable continuous printing. For some printheads, reliable ejection or printing can only be achieved when the nozzle plate is wetted. Such low HLB surfactants are also a major factor in determining the interaction between the ink and the substrate, thus controlling or affecting wetting, bleeding, dot gain, dot quality and final image quality. Surfactants influence these properties by means of physical parameters, i.e. surface tension (static and dynamic). The surface tension is preferably from 10 to 70mN/m, more preferably from 15 to 60mN/m, very preferably from 20 to 50mN/m, in accordance with DIN EN 14210: 2004-03 (Ring method) at 23 ℃.

The at least one surfactant (iv) preferably has an HLB value of from 1 to 6, very preferably from 2 to 5. The above values refer to the HLB value of a single surfactant. Thus, if a mixture of surfactants is used, the HLB value is not the HLB value of the surfactant mixture, but the HLB value of at least one surfactant contained in the surfactant mixture.

Preferably, the at least one surfactant (iv) is selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, fluorinated surfactants, silicone surfactants and mixtures thereof, preferably nonionic acetylenic surfactants and/or silicon surfactants. Nonionic surfactants do not contain any anionic or cationic groups or groups that can form cations or anions at a particular pH. In contrast, anionic surfactants comprise at least one anionic group, such as carboxylate, sulfate, sulfonate or phosphate. Yang (Yang)The ionic surfactant comprises at least one cationic group, preferably a quaternized amine group. The fluorinated surfactant has at least one fluorine atom and the polysiloxane surfactant has at least one SiO atom in the molecule₂A group.

The nonionic surfactant is preferably selected from acetylenic surfactants such as 3, 6-dimethyl-4-octyne-3, 6-diol, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and ethoxylated acetylenic surfactants; poly (oxyalkylene glycol) and C₈-C₃₀Carboxylic acid, C₈-C₃₀Alcohol, C₈-C₃₀Reaction products of amines, sorbitan esters, alkanolamides, castor oil; c₈-C₃₀Amines and derivatives thereof; nonionic polymers, such as polyoxypropylene/polyoxyethylene copolymers, polyalkylene glycols, polyvinyl alcohols, polyacrylic acids, hydrophobically substituted polyacrylamides, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyoxyethylene alkyl ethers, polyoxyethylene nonylphenyl ethers, alkyl or dialkylphenoxypoly (ethyleneoxy) ethanol derivatives, antifoam silicon compounds, blends of organic esters in mineral oil bases, EO/PO block copolymers; and mixtures thereof, preferably 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol. Particularly suitable nonionic surfactants are relatively short chain ethylene glycol nonionic surfactants, such as Air Products Surfynol^TMProduct line, especially Surfynol^TM465. Surfactants based on acetylene glycol and ethoxylated acetylene glycol are particularly suitable because they improve the wetting of the ink and can inhibit coalescence of the initial ink drop immediately after impact of the ink. The drying process is also improved due to the increased surface area resulting from the improved wet spreading.

The anionic surfactant is preferably selected from the group consisting of sulfonated fatty acid esters, phosphorylated fatty acid esters, alkyl sulfoxides and alkyl sulfones, sodium alkyl sulfates, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate, sodium dodecyldiphenyloxide disulfonate, sodium alkyl sulfosuccinate, potassium N-methyl-N-oleoyl taurate, carboxymethyl amylose, and mixtures thereof. Anionic surfactants such as Aerosol are also used^TM OT。

The cationic surfactant is advantageously selected from the group consisting of dialkylphenylalkylammonium chlorides, alkylbenzylmethylammonium chlorides, cetylpyridinium bromides, alkyltrimethylammonium bromides, halide salts of quaternized polyoxyethylalkylamines, dodecylbenzyltriethylammonium chlorides, quaternary alkylsulfates compounds, fatty imidazolines and mixtures thereof.

Polysiloxane surfactants are built around a polydimethylsiloxane backbone to which various hydrophilic groups such as polyoxyethylene glycols can be attached. Siloxane surfactants are characterized by high chemical and thermal stability, effective reduction of surface tension, and also function as defoamers. At the same time, the surface tension of the solid/liquid may even become negative due to the high adsorption affinity of the siloxane surfactant to the hydrophobic surface, resulting in a positive spreading coefficient value. Suitable silicon surfactants are represented by the general formula (II) or (III) shown below.

In the general formula (II), p represents an integer of 0 or more, and q represents an integer of 1 or more. Furthermore, the radical R₂Is represented by C₁-C₆An alkyl group. Radical R₁Represents a group represented by the following general formula (IIa), wherein the symbol represents the bond between the general formula (IIa) and a silicon atom:

*-(CH₂)_m-(OC₂H₄)_n-(OC₃H₆)_o-R₃ (IIa)

in the general formula (IIa), m represents an integer of 1 to 6, n represents an integer of 0 to 50, and o represents an integer of 0 to 50, with the proviso that n + o is at least 1. R₃Represents a hydrogen atom, C₁-C₆Alkyl or (meth) acrylic groups.

In the general formula (III), R represents an integer of 1 to 80, R₁Is a group of the above general formula (IIa).

Commercial examples of silicon surfactants represented by formula (II) are produced by Dow Corning Toray as products SF8428, FZ-2162, 8032ADDITIVE, SH3749, FZ-77, L-7001, L-7002, FZ-2104, FZ-2110, F-2123, SH8400 and SH3773M, by BYK Chemie as products BYK-345, BYK-346, BYK-347, BYK-348 and BYK-349, by Evanik Degussa as products Tegowt 250, Tegowt 260, Tegowt 270 and Tegowt 280, by Shin-Etsu Chemical Co., Ltd. by KF-351-67352-353, KF-354L, KF, KF-36355-640, 642-643, by SAG-Na series. Commercially available products of the compounds represented BY the above general formula (III) are, for example, Dow Corning Toray Co., Ltd., products BY16-201 and SF8427, BYK Chemie products BYK-331, BYK-333 and BYK-UV3500, Evonik Degussa products Tegoglide410, Tegoglide432, Tegoglide435, Tegoglide440 and Tegoglide 450.

Preferred silicon surfactants have an HLB value of 2-5.

These silicon surfactants are generally slower to orient at the liquid surface, as are the preferred nonionic acetylene glycol-based surfactants. In addition, the silicon surfactant may also contribute to the improvement of water resistance and abrasion resistance of the printed substrate (S).

Preferred ink compositions (AC) comprise at least one surfactant (iv) comprising at least one non-ionic acetylene glycol based surfactant (iv-1), preferably 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, and at least one silicon surfactant (vi-2), preferably a polyether modified siloxane. Particularly preferred polyether-modified siloxanes are represented by the above formula (II).

In this connection, it is preferred that the at least one nonionic acetylene glycol-based surfactant (iv-1), preferably 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, and the at least one silicon surfactant (vi-2), preferably the polyether-modified siloxane of the general formula (I), are present in a weight ratio of from 2:1 to 1:2, very preferably 1: 1.6.

An example of a fluorinated surfactant suitable for use in the ink composition (AC) is F (CF)₂CF₂)_{3- 8}CH₂CH₂SCH₂CH₂COOLi、F(CF₂CF₂)_3-8CH₂CH₂PO₄(NH₄)₂、F(CF₂CF₂)_3-8CH₂CH₂(OCH₂CH₂)_1-10OH, anionic di-tail fluorosulfanyl surfactant (e.g., (C)₁₀F₂₁-CH₂-S)₂C(CH₃)CH₂CH₂COOLi) and mixtures thereof. Due to the exceptional chemical stability of fluorocarbon residues, fluorinated surfactants are able to withstand extreme temperature conditions and aggressive environments. Unlike many conventional surfactants, fluorinated surfactants retain their surface active properties in non-aqueous solutions. At the same time, they act as a desiccant for high energy surfaces. Since fluorinated surfactants are expensive, poorly biodegradable and may lead to undesirable residues on printed substrates designed for skin contact, preferred ink compositions (AC) do not contain any fluorinated surfactants, i.e. their amount is 0 wt% based on the total weight of the ink composition (AC).

In a preferred embodiment of the ink composition (AC), at least one nonionic and/or silicon surfactant is used to modify the surface tension of the ink composition. The ink composition (AC) therefore advantageously comprises the at least one surfactant (iv), preferably the at least one nonionic surfactant and/or the at least one silicon surfactant, very preferably 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and/or polyether-modified siloxane, in a total amount of from 0.01 to 1 part, preferably from 0.02 to 0.5 part, very preferably from 0.02 to 0.2 part, based on 100 parts of the ink composition. The use of said at least one nonionic surfactant, especially 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, and/or at least one silicone surfactant, especially a polyether modified siloxane of formula (I), in said amounts results in a surface tension which is neither too high nor too low, thus resulting in a printed image with high resolution.

Additive (v):

furthermore, the ink composition (AC) used in the process of the present invention may comprise at least one additive (v). The additive (v) is preferably selected from the group consisting of flow control agents, thickeners, thixotropic agents, plasticizers, lubricating additives, antiblocking additives and mixtures thereof. Very preferably, the ink composition (AC) further comprises at least one additive (v) selected from rheology modifiers (v-1), humectants (v-2), co-solvents (v-3), biocides (v-4) and mixtures thereof.

The rheology modifier (v-1) is an organic or inorganic additive that adjusts the rheological properties of the ink and enables control of damping and droplet formation. These can be divided into inorganic and organic materials; inorganic additives are typically clays and fumed silicas, while organic materials can be subdivided into natural materials such as cellulosics/xanthan and synthetic materials as associative or non-associative materials.

Inorganic rheology modifiers are typically dispersed into the coating and act as suspending or gelling agents. Generally, the viscosity of the formulation decreases with time and constant shear conditions because its gel structure is disrupted. If the shear is removed, the coating gradually returns to its original viscosity. Inorganic rheology modifiers are sometimes added to aqueous formulations as secondary thickeners to improve the sag resistance, settling resistance, syneresis resistance, and splash resistance of the ink. Suitable inorganic rheology modifiers are, for example, synthetic hectorite clays, which are commercially available, for example, from Southern Clay Products, Inc., and includeLuceniteLaponiteLaponiteLaponiteAnd Laponite

Organic rheology modifiers are more diverse in nature and are subdivided into many structural types. Non-associative rheology modifiers work by entanglement of soluble high molecular weight polymer chains, so their effectiveness is primarily controlled by molecular weight. These tend to have pseudoplastic rheology, providing good stability against settling and sagging. Associative thickeners function by the hydrophobic end groups forming a physical network with their own and non-specific interactions with the ink components. Suitable organic rheology modifiers include non-associative rheology modifiers and nonionic associative rheology modifiers, also known as nonionic associative thickeners. Examples of non-associative rheology modifiers include, but are not limited to, Alkali Swellable Emulsions (ASE), such as acrylic emulsions. Suitable associative rheology modifiers include, but are not limited to, hydrophobically modified alkali swellable emulsions (HASE), such as hydrophobically modified acrylic emulsions, hydrophobically modified polyurethanes (HEUR); hydrophobically Modified Polyethers (HMPE); or Hydrophobic Ethoxylated Aminoplast Technology (HEAT). Other suitable organic thickeners include glycerol and fatty acid modified polyesters.

The ink composition (AC) preferably comprises the at least one rheology modifier (v-1) in a total amount of 0.01 to 1 parts based on 100 parts of the ink composition.

The humectant (V-2) is a hygroscopic organic compound capable of binding water vapor from the air under given humidity and temperature conditions, so that drying of the ink is slowed or completely stopped. This is important to prevent drying of the ink on the nozzles and to prevent clogging of the nozzles during printing and in idle conditions.

Examples of the usable wetting agent (v-2) include polyhydric alcohols such as glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 3-butanediol, 2, 3-butanediol, 1, 4-butanediol, 3-methyl-1, 3-butanediol, 1, 5-pentanediol, tetraethylene glycol, 1, 6-hexanediol, 2-methyl-2, 4-pentanediol, polyethylene glycol, 1,2, 4-butanetriol, 1,2, 6-hexanetriol and thioethylene glycol; saccharides such as glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose; sugar alcohols such as sorbitol and sorbitan; hyaluronic acid; lower alkyl monoethers or diethers derived from alkylene glycols, such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol monoisopropyl ether; lactones, such as gamma-butyrolactone; glycerol acetate, glycerol diacetate and glycerol triacetate; nitrogen-containing cyclic compounds such as pyrrolidone, N-methyl-2-pyrrolidone, urea, bis-hydroxyethyl-5, 5-dimethylhydantoin, lactic acid monoethanolamide, l, 3-dimethyl-2-imidazolidinone; sulfur-containing compounds such as dimethyl sulfoxide and sulfolane; and mixtures thereof.

Some of the foregoing wetting agents (v-2) may also function as co-solvents (v-3), such as 2-pyrrolidone. In this case, the wetting agent will function as a co-solvent at the same time, and it may not be necessary to add another co-solvent. However, at least one other co-solvent (v-3) may also be added to prevent nozzle clogging.

The ink composition (AC) preferably contains the at least one humectant (v-2) in a total amount of 0.01 to 30 parts based on 100 parts of the ink composition.

The co-solvent is a substance added in a small amount to the main solvent in order to increase the solubility of the compounds present in the ink. This allows the use of compounds in the ink composition that are not completely soluble in the primary solvent and therefore clog printer nozzles.

Preferred co-solvents (v-3) are organic compounds which are completely or at least partially miscible with the main solvent, preferably water, at temperatures of from 20 to 60 ℃. Suitable cosolvents (v-3) are, for example, (1) alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, furfuryl alcohol and tetrahydrofurfuryl alcohol; (2) ketones or ketoalcohols such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol; (3) ethers such as tetrahydrofuran and dioxane; (4) esters such as ethyl acetate, butyl acetate, ethyl lactate, ethylene carbonate, and propylene carbonate; (5) polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, tetraethylene glycol, polyethylene glycol, glycerol, 2-methyl-2, 4-pentanediol, 1,2, 6-hexanetriol, and thiodiethylene glycol; (6) lower alkyl mono-or diethers derived from alkylene glycols, such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, propylene glycol monomethyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether, and diethylene glycol dimethyl (or ethyl) ether; (7) nitrogen-containing cyclic compounds such as pyrrolidone, N-methyl-2-pyrrolidone, and 1, 3-dimethyl-2-imidazolidinone; (8) sulfur-containing compounds, such as dimethyl sulfoxide and sulfolane, and mixtures thereof.

Some of the above-mentioned co-solvents (v-3) may also act as wetting agents (v-2), for example 2-pyrrolidone. In this case, the co-solvent will act as a humectant at the same time, and the addition of other humectants may not be required. However, at least one other wetting agent (v-2) may also be added to prevent clogging of the nozzle.

The ink composition (AC) preferably contains the at least one co-solvent (v-3) in a total amount of 0.01 to 30 parts based on 100 parts of the ink composition.

Any biocide (v-4) commonly used in inkjet inks can be used in the practice of the present invention, such as aqueous dipropylene glycol solutions of 1, 2-benzisothiazolin-3-one available under the trade name PROXEL from Avecia, Ltd., Manchester, UK, methyl paraben, 6-acetoxy-2, 2-dimethyl-1, 3-dioxane, glutaraldehyde, hemiformal ethyleneglycol (semyphlormal glycol0), isothiazolinones, and mixtures thereof.

The ink composition (AC) preferably comprises the at least one biocide (v-4) in a total amount of 0.01 to 1 part, based on 100 parts of the ink composition.

The inks used in step (3) of the process of the present invention are preferably non-toxic and therefore contain no or only very small amounts of (meth) acrylate compounds having a number average molecular weight Mn of less than 1,200 g/mol. These compounds, if left in the ink after curing, cause skin irritation and/or odor nuisance and their use is therefore not preferred. Thus, a highly preferred ink composition (AC) used in step (3) comprises (meth) acrylates having a number average molecular weight Mn of less than 1,200g/mol, in a total amount of from 0 to 2% by weight, preferably from 0 to 1% by weight, very preferably 0% by weight, based on the total weight of the ink composition (AC). The amount of these (meth) acrylates can be determined, for example, by gel permeation chromatography, calibrated against polystyrene standards.

The ink composition (AC) used in step (3) of the process of the present invention is preferably an aqueous ink composition. It is particularly preferred that the water fraction of the aqueous ink composition is 5 to 95 parts, preferably 35 to 90 parts, more preferably 50 to 90 parts, and very preferably 60 to 90 parts, based on 100 parts of the aqueous ink composition, based on the total weight thereof. The aqueous ink composition preferably does not contain an organic solvent.

If a liquid ink composition, preferably an aqueous ink composition (AC), is used in step (3), it preferably has a solids content of from 8 to 40 parts, preferably from 20 to 40 parts, very preferably from 25 to 35 parts, based on 100 parts of the aqueous ink composition.

In order to ensure that the ink composition (AC) can be printed in step (3) of the present invention, the ink composition (AC) advantageously has a viscosity of 0.01 to 100 mPas, more preferably 2 to 30 mPas, more preferably 4 to 20 mPas, very preferably 2 to 15 mPas, using a rotational viscometer at 23 ℃ and 1000s^-1Measured at shear rate. The viscosity is preferably measured at the jetting temperature to ensure that the ink has the correct viscosity during the printing process.

The aqueous ink composition (AC) used in step (3) of the process of the present invention does not cause clogging of the nozzles of an ink jet printer. This is because an aqueous dispersion of a urethane (meth) acrylate polymer is used, which has high water dispersibility even after thermal drying, thus allowing easy cleaning of nozzles of an inkjet printer.

In step (3) of the present invention, the ink composition (AC) is deposited onto a substrate. Preferably, the deposition is achieved by inkjet printing. There are two main techniques in use: continuous (CIJ) and Drop On Demand (DOD) inkjet.

In continuous ink jet technology, a high pressure pump directs a liquid solution of ink and a fast drying solvent from a reservoir through a gun body and a micro-nozzle, creating a continuous stream of ink droplets by virtue of Plateau-Rayleigh instability. The piezoelectric crystal generates sound waves when vibrated in the gun body and breaks up the stream into droplets at regular intervals. The ink droplets are subjected to an electrostatic field generated by a charging electrode as they are formed; the field varies depending on the desired degree of drop deflection. This results in a controlled, variable electrostatic charge on each droplet. The charged droplets are separated by one or more uncharged "guard droplets" to minimize electrostatic repulsion between adjacent droplets. The charged droplets pass through an electrostatic field and are directed (deflected) by an electrostatic deflection plate to print on a receptor material (substrate) or allowed to continue undeflected to a gutter for reuse. The higher the charge, the greater the degree of drop deflection. Only a small fraction of the droplets are used for printing and the majority are recycled. The ink system requires active solvent adjustment to counteract solvent evaporation during the time of flight (time between nozzle ejection and gutter recirculation) and from the discharge process, thereby expelling gas from the reservoir that is drawn into the gutter along with unused droplets. The viscosity was monitored and a solvent (or solvent mixture) was added to offset solvent loss.

Drop On Demand (DOD) can be classified as either a low resolution DOD printer that uses an electrically operated valve to eject relatively large ink droplets on a print substrate, or a high resolution DOD printer that ejects very small ink droplets by a method of discharging droplets using thermal DOD and piezoelectric DOD.

According to a very preferred embodiment of step (3) of the process of the present invention, the ink composition (AC) in step (3) is deposited by a digital printing device comprising a Drop On Demand (DOD) ink jet printer. The use of a DOD inkjet printer in combination with a nonwoven substrate (S) makes it possible to obtain high resolution images which show excellent adhesion to the substrate (S) and high stability to environmental influences. Furthermore, the printing does not adversely affect the properties of the substrate (S) with respect to the feel and flexibility.

In the thermal inkjet method, the print cartridge contains a series of cells, each containing a heater. To eject a droplet from each chamber, a current pulse is passed through the heating element causing the ink in the chamber to rapidly evaporate to form a bubble, which results in a large pressure increase, pushing the droplet onto the substrate. The surface tension of the ink and the condensation and hence contraction of the vapor bubble pulls further charge of ink into the chamber through a narrow channel connected to the ink reservoir. The inks used are usually water-based and use pigments or dyes as colorants. The ink used must have a volatile component to form vapor bubbles, otherwise no droplet ejection can occur.

Piezoelectric DOD printers use a piezoelectric material, rather than a heating element, in an ink-filled chamber behind each nozzle. When a voltage is applied, the piezoelectric material changes shape, which creates a pressure pulse in the fluid that forces an ink droplet out of the nozzle. The DOD method uses software that directs the print head to apply 0-8 drops per dot. This means that a single pixel or dot can have 8 ink volume levels. These multiple levels of ink are typically generated by multiple pulses (piezo voltages on and off) shortly after each other. This will result in the ejection of a plurality of droplets. These droplets, while still in air, will form a single larger droplet which will land on the substrate.

In this regard, a DOD inkjet printer having at least one print head with at least one nozzle is used. Preferably, a Drop On Demand (DOD) ink jet printer has at least one print head, wherein the at least one print head has one or more nozzles, the diameter of which is in each case 1 to 52 μm, more preferably 15 to 40 μm, very preferably 30 to 40 μm. In this context, it is advantageous if the print head has 1 to 1024, preferably 50 to 500, very preferably 110 and 140 nozzles. The nozzle spacing distance of the nozzle rows in the printhead is preferably 10-200 μm, more preferably 10-85 μm, and most preferably 10-45 μm.

Very preferably, printingThe head is a piezoelectric print head. The drop formation device of the piezoelectric printhead controls a set of piezoelectric ceramic transducers to apply a voltage to change the shape of the piezoelectric ceramic transducers. The droplet forming device may be a squeeze mode actuator, a bend mode actuator, a push mode actuator, or a shear mode actuator, or other type of piezoelectric actuator. Suitable commercially available piezoelectric printheads are available, for example, from TOSHIBA TEC^TMTOSHIBA TEC^TMCK1 and CK1L from XAAR^TMXAAR of^TM1002, Spectra SE/SM/SL 128AA from Fujifilm, Polaris, Sapphire, Emmerild and Starfire from Dimatix Spectra, series 512 and 1024 from Konica Minolta, and series W from Xerox.

The liquid channels in the piezoelectric printhead are also referred to as pressure chambers. Between the liquid channels and the main inlet of the piezoelectric printhead there is a manifold connected to store liquid to be supplied to the liquid channel groups.

The piezoelectric printhead is preferably a through-flow piezoelectric printhead. In a preferred embodiment, the recirculation of liquid in the flow-through piezoelectric printhead flows between a set of liquid channels and the inlets of the nozzles, wherein the set of liquid channels corresponds to the nozzles.

In a preferred embodiment, the printhead discharges ink composition (AC) at a single drop size of 1 to 200pl, in a more preferred embodiment the minimum drop size is 15 to 100pl, and in a most preferred embodiment the minimum drop size is 25 to 35 pl.

The angle of the print head is preferably 0-90 deg., more preferably 0-45 deg., and very preferably 0 deg..

In a preferred embodiment, the printhead has a drop velocity of 3-15 m/s, in a more preferred embodiment 5-10 m/s, and in a most preferred embodiment 6-8 m/s.

The printing speed of the DOD printer is advantageously 50-500mm/s, preferably 100-300mm/s, very preferably 150-250 mm/s.

In a preferred embodiment, the print head has a native printing resolution of 25-3,600DPI, in a more preferred embodiment, the print head has a native printing resolution of 50-2,400DPI, and in a most preferred embodiment, the print head has a native printing resolution of 150 DPI and 2,400 DPI.

The throw-distance, i.e. the distance between the at least one nozzle of the print head and the substrate (S), may be up to 5mm, thus also allowing printing on already formed substrates. Preferably, in step (3), the distance between the portion to be printed of said at least one surface of the nonwoven textile substrate (S) and said at least one nozzle of said at least one print head is from 0.1mm to 4cm, preferably from 0.5 to 1.5 mm.

Step (3) of the process of the invention is preferably carried out at a temperature of from 15 to 50 deg.C, preferably from 20 to 30 deg.C, very preferably 23 deg.C. This temperature is also known as the jetting temperature and ensures that the substrate is not damaged during the printing process.

A DOD inkjet printer suitable for use in step (3) of the present invention is, for example, Pixdro LP50 with a Spectra SE 128AA print head available from Fujifilm.

And (4):

in step (4) of the process of the present invention, the ink composition (AC) deposited in step (3) of the process of the present invention is dried and/or cured.

Drying is understood to mean the passive or active evaporation of the solvent from the applied ink composition. Although the ink is no longer flowable after drying, it is still soft and/or tacky. However, drying does not result in the Ink Layer (IL) being in a ready-to-service state, i.e. does not result in the cured Ink Layer (IL) described below.

Curing of the ink composition is therefore understood to be the conversion of the composition into a ready-to-service state, i.e. a state in which the substrate provided with the Ink Layer (IL) can be transported, stored and used in its intended manner. Thus, the cured Ink Layer (IL) is no longer soft or tacky but is adjusted to a solid Ink Layer (IL) whose properties, such as hardness or adhesion to the substrate, no longer exhibit any substantial change even upon further exposure to the curing conditions described below.

The drying of the ink composition (AC), preferably the aqueous ink composition (AC) in step (4), is preferably carried out at 30 to 100 ℃, very preferably 50 to 70 ℃ for 1 to 60 minutes, preferably 5 to 30 minutes, very preferably 5 to 20 minutes. As previously mentioned, drying of the ink composition results in loss of solvent from the ink composition, thereby fixing the printed image to the substrate. However, the image has not yet had sufficient stability to environmental influences, which is only obtained after curing the ink composition to form the Ink Layer (IL).

The curing of the ink composition (AC) in the step (4) is preferably performed under a nitrogen atmosphere. The atmosphere preferably contains an oxygen content of less than 0.1%.

According to a preferred embodiment of step (4), the ink composition (AC) deposited in step (3) is dried as described above and then cured. The curing of the ink composition (AC) in step (4) is preferably carried out by radiation curing, preferably by UV light and/or Electron Beam Curing (EBC), very preferably by UV light. Accordingly, the corresponding apparatus for carrying out step (4) preferably comprises at least one radiation source for irradiating the ink composition applied to the substrate with curing radiation.

Examples of suitable radiation sources for radiation curing are low, medium and high pressure mercury emitters, but also fluorescent tubes, pulse emitters, metal halide emitters (halogen lamps), lasers, LEDs, and also electronic flash devices, which enable radiation curing without photoinitiators, or excimer emitters. Radiation curing is accomplished by exposure to high energy radiation, i.e., UV radiation, or by bombardment with high energy electrons. Of course, curing can also be carried out using two or more radiation sources, for example 2 to 4. These sources may also each emit in a different wavelength range.

Electron beam processing is typically accomplished with an electron accelerator. Individual accelerators are characterized by their energy, power and type. The low energy accelerator provides a beam energy from about 150keV to about 2.0 MeV. The intermediate energy accelerator provides a beam energy of about 2.5 to about 8.0 MeV. The high energy accelerator provides a beam energy greater than about 9.0 MeV. The accelerator power is the product of the electron energy and the beam current. The power is about 5 to about 300 kW. The main types of accelerators are: electrostatic Direct Current (DC), electric DC, Radio Frequency (RF) linear accelerators (LINACS), magnetic induction LINAC, and Continuous Wave (CW) machines.

If curing is carried out by UV radiation, the intensity used for curing in step (4) is preferably from 1 to 10W/cm²More preferably 1 to 6W/cm². The dosage is preferably 1-20J/cm²More preferably 1 to 12J/cm²。

If curing is carried out by electron beam curing, the intensity used for curing in step (4) is preferably 30-80kGy, more preferably 40-60kGy, very preferably 50 kGy.

However, the above statements do not exclude that the ink composition (AC) may additionally be cured under other curing conditions, for example thermal curing conditions.

The method of the present invention allows a nonwoven textile substrate to be at least partially coated with an Ink Layer (IL) having excellent adhesion to the substrate without adversely affecting the properties of the printed substrate, particularly the feel. Further, the Ink Layer (IL) is very stable against environmental influences generated when the substrate is used, and is non-toxic, so that the printed substrate can be used even in contact with the skin. Furthermore, the method of the invention produces high resolution images and allows printing already shaped substrates, thus providing the possibility of personalizing the garment in a simple and efficient way immediately before sale.

Nonwoven textiles of the invention:

the result after the end of step (4) of the process of the invention is a nonwoven textile substrate (S) which is at least partially coated with an Ink Layer (IL).

Thus, a second subject of the invention is a nonwoven textile substrate (S) at least partially coated with an Ink Layer (IL), said substrate being prepared by the process of the invention.

The statements made with respect to the process of the present invention apply, mutatis mutandis, to a further preferred embodiment of the nonwoven textile substrate of the present invention.

In particular, the invention is described by the following embodiments:

according to a first embodiment, the invention relates to a method for at least partially coating a nonwoven textile substrate (S) with an Ink Layer (IL), said method comprising:

(1) providing a nonwoven textile substrate (S);

(2) optionally pretreating the nonwoven textile substrate (S);

(3) depositing on at least a portion of at least one surface of the nonwoven textile substrate (S) at least one ink composition (AC), preferably an aqueous ink composition (AC), the ink composition (AC) comprising:

(i) an aqueous dispersion of at least one polyurethane (meth) acrylate polymer,

(ii) at least one pigment and/or dye, and

(iii) optionally at least one photoinitiator;

(4) drying and/or at least partially curing the ink composition (AC) deposited on the nonwoven textile substrate (S) obtained after step (3).

According to a second embodiment, the invention relates to the method according to embodiment 1, wherein the nonwoven textile substrate (S) is selected from the group consisting of thermoplastic polyurethane, polypropylene, glass fibers and mixtures thereof, preferably thermoplastic polyurethane.

According to a third embodiment, the present invention relates to the process of embodiment 2, wherein the thermoplastic polyurethane is prepared by reacting:

a) at least one polyisocyanate,

b) at least one compound having at least one isocyanate-reactive group,

c) optionally at least one chain-extending compound,

d) optionally at least one chain transfer agent, and

e) optionally at least one additive selected from the group consisting of,

f) optionally in the presence of at least one catalyst.

According to a fourth embodiment, the present invention relates to the process according to embodiment 3, wherein the polyisocyanate a) is preferably selected from aliphatic, cycloaliphatic and/or aromatic polyisocyanates, more preferably aliphatic, cycloaliphatic and/or aromatic diisocyanates, even more preferably aromatic diisocyanates, very preferably 4,4' -diphenylmethane diisocyanate and/or hexamethylene diisocyanate.

According to a fifth embodiment, the present invention relates to the method according to embodiment 3 or 4, wherein the at least one compound b) having at least one isocyanate reactive group selected from the group consisting of hydroxyl, amine and thiol groups, preferably hydroxyl groups, has an average functionality of 1.8 to 2.3, preferably 1.9 to 2.2, very preferably 2.

According to a sixth embodiment, the present invention relates to the method according to any one of embodiments 3 to 5, wherein the at least one compound b) having at least one isocyanate reactive group is selected from polyesteramides, polythioethers, polycarbonates, polyacetals, polyolefins, polysiloxanes, polybutadienes, polyesterpolyols, polyetherpolyols and mixtures thereof, preferably polyetherdiols, polyesterdiols, polycarbonatediols and mixtures thereof, very preferably polyetherdiols and/or polyesterdiols.

According to a seventh embodiment, the present invention relates to the process according to embodiment 6, wherein the polyether diol is a linear polyether diol selected from the group consisting of polyoxytetramethylene glycol, polyether diols based on 1, 2-propylene oxide, polyether diols based on ethylene oxide and mixtures thereof, wherein the polyether diols have a molecular weight Mw of 800-.

According to an eighth embodiment, the present invention relates to the method according to embodiment 6 or 7, wherein the polyester diol is selected from the group consisting of polyethylene adipate, polyethylene 1, 4-butanediol adipate, polyethylene 1, 6-hexanediol-neopentyl glycol adipate, polycaprolactone and mixtures thereof, very preferably polyethylene 1, 4-butanediol adipate and/or polyethylene 1, 6-hexanediol-1, 4-butanediol adipate, wherein the polyester diol has a molecular weight (weight average) of 500-.

According to a ninth embodiment, the present invention relates to the process according to any one of embodiments 3 to 8, wherein the at least one chain extender c) is selected from alkanediols having 2 to 6 carbon atoms in the alkylene radical, more preferably 1, 4-butanediol and/or dialkylene glycols having 4 to 8 carbon atoms, very preferably 1, 4-butanediol and/or 1, 6-hexanediol.

According to a tenth embodiment, the present invention relates to the process according to any one of embodiments 3-9, wherein the molar ratio of the at least one compound b) to the at least one chain extender c) is from 10:1 to 1:10, preferably from 5:1 to 1:8, more preferably from 1:1 to 1:6.4, very preferably from 1:1 to 1: 4.

According to an eleventh embodiment, the present invention relates to the method according to any one of embodiments 4 to 11, wherein the at least one chain transfer agent d) is selected from monofunctional alcohols and/or monofunctional amines, preferably methylamine and/or monofunctional polyols.

According to a twelfth embodiment, the present invention relates to the method according to any of embodiments 3 to 11, wherein the ratio of the total number of isocyanate groups of the aromatic, aliphatic and/or cycloaliphatic diisocyanate a) to the total number of active hydrogens in the compound b) and the chain extender c) is between 0.6 and 1.2, more preferably between 0.8 and 1.1.

According to a thirteenth embodiment, the present invention relates to the method according to any one of embodiments 3 to 12, wherein the thermoplastic polyurethane is obtained by reacting:

(a) diphenylmethane 4,4' -diisocyanate (MDI) and/or hexamethylene diisocyanate,

(b) polyoxytetramethylene glycol, and/or polyether glycols based on 1, 2-propylene oxide and ethylene oxide and/or polyester glycols based on polyalkylene adipates having 2 to 6 carbon atoms in the alkylene radical, and

(c)1, 2-ethanediol, 1, 4-butanediol and/or 1, 6-hexanediol,

wherein the ratio of isocyanate groups of component (a) to the sum of the isocyanate-reactive groups of components (b) and (c) is preferably from 1:0.8 to 1:1.1 and (b) and (c) are used in a molar ratio of from 1:1 to 1: 6.4.

According to a fourteenth embodiment, the present invention is directed to the method of any one of embodiments 3-13, wherein the thermoplastic polyurethane has:

-shore hardness of a44 to D80, more preferably a50 to a99, even more preferably a60 to a95, very preferably a70 to a90, especially preferably a80 or a83, according to DIN ISO 7619-1: 2012-02 is determined using a 3 second measurement time, and/or

-a vicat softening temperature of 40 to 160 ℃, more preferably 50 to 130 ℃, very preferably 80 to 120 ℃, according to DIN EN ISO 306: 2014-03 using a heating rate of 120 deg.C/hr and a load measurement of 10N, and/or

-a glass transition temperature Tg of from 100 ℃ to 20 ℃, more preferably from-80 ℃ to 20 ℃, even more preferably from-60 ℃ to 0 ℃, very preferably-44 ℃, according to DIN EN ISO 11357-1: 2017-02 is measured at a heating rate of 10 deg.C/min, and/or

-a tensile strength of 10 to 60MPa, more preferably 20 to 60MPa, even more preferably 30 to 60MPa, very preferably 45MPa or 55MPa, according to DIN 53504: 2009-10 determined using stretch strip S2, and/or

An elongation at break of-300-: 2009-10 determined using stretch strip S2, and/or

-a tear resistance of 27 to 240kN/m, more preferably 30 to 150kN/m, even more preferably 40 to 100kN/m, very preferably 55kN/m or 75kN/m, according to DIN EN ISO 34-1: 2004-07 determined using procedure (a) of method B, and/or

-25-165mm³More preferably 25 to 100mm³Even more preferably 25-50mm³Very preferably 30mm³Or 35mm³Wear loss according to DIN EN ISO 4649: 2010-09 was determined using method A.

According to a fifteenth embodiment, the present invention relates to the method according to any one of the preceding embodiments, wherein the nonwoven textile substrate (S) has a weight per square meter of from 50 to 1,000g/m²More preferably 80 to 700g/m²Even more preferably 100-²Very preferably 400-500g/m²Basis weight of (c).

According to a sixteenth embodiment, the present invention relates to the method according to any one of the preceding embodiments, wherein the nonwoven textile substrate (S) is pre-treated in step (2) by applying at least one primer composition.

According to a seventeenth embodiment, the present invention is directed to the method according to any one of the preceding embodiments, wherein the ink composition (AC) is deposited directly onto at least one surface of the nonwoven textile substrate (S).

According to an eighteenth embodiment, the present invention relates to the method according to any one of the preceding embodiments, wherein the ink composition (AC) is deposited on at least two surfaces of the nonwoven textile substrate (S).

According to a nineteenth embodiment, the present invention relates to the method according to any one of the preceding embodiments, wherein the polyurethane (meth) acrylate polymer is obtained by reacting:

(a) at least one (cyclo) aliphatic di-and/or polyisocyanate,

(b1) at least one (cyclo) aliphatic diol having a molar mass of less than 700g/mol,

(b2) at least one polyester diol having a weight-average molar mass Mw of 700-2000 and preferably not more than 20mg KOH/g in a molar ratio in accordance with DIN 53240-2: an acid value of 2007-11 (g),

(c) at least one compound having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group,

(d) at least one compound having at least one isocyanate-reactive group and at least one acid group,

(e) at least one alkali metal base for at least partially neutralizing the acid groups of component (d),

(f) optionally, at least one monohydric alcohol having exactly one hydroxyl function, or at least one mono-and di-C₁-C₄An alkylamine, and

(g) at least one monofunctional polyoxyalkylene polyether alcohol.

According to a twentieth embodiment, the present invention is directed to the method of embodiment 19, wherein component (a) is a mixture of a cycloaliphatic or aliphatic monomeric diisocyanate (a1) and a polyisocyanate based on a cycloaliphatic or aliphatic monomeric diisocyanate (a 2).

According to a twenty-first embodiment, the present invention relates to the process according to embodiment 20, wherein component (a1) is selected from the group consisting of hexamethylene diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 4 '-or 2,4' -bis (isocyanatocyclohexyl) methane and mixtures thereof, preferably from the group consisting of isophorone diisocyanate and hexamethylene diisocyanate, very preferably from the group consisting of hexamethylene diisocyanate.

According to a twenty-second embodiment, the present invention is directed to the method of embodiment 20 or 21, wherein the polyisocyanate (a2) is a polyisocyanate having isocyanurate groups, a uretdione diisocyanate, a polyisocyanate having biuret groups, a polyisocyanate having urethane or allophanate groups, and mixtures thereof.

According to a twenty-third embodiment, the present invention relates to the method of any one of embodiments 20 to 22, wherein the polyisocyanate (a2) is a compound of formula (I):

wherein:

R⁵is a divalent alkylene group having 2 to 12 carbon atoms, preferably having 2 to 10 carbon atoms, more preferably having 2 to 8 carbon atoms, most preferably having 3 to 6 carbon atoms, very preferably a1, 2-ethylene group,

R⁶is a divalent alkylene or cycloalkylene radical having from 2 to 20 carbon atoms, preferably having from 4 to 15 carbon atoms, more preferably having from 6 to 13 carbon atoms, very preferably 1, 6-hexylene,

R⁷is hydrogen or methyl, preferably hydrogen, and

x is a positive number with a statistical mean value of 2 to 6, preferably 2 to 4.

According to a twenty-fourth embodiment, the present invention relates to a process according to any one of embodiments 19 to 23, wherein component (b1) is selected from the group consisting of ethylene glycol, propane-1, 2-diol, propane-1, 3-diol, butane-1, 2-diol, butane-1, 3-diol, butane-1, 4-diol, butane-2, 3-diol, pentane-1, 2-diol, pentane-1, 3-diol, pentane-1, 4-diol, pentane-1, 5-diol, pentane-2, 3-diol, pentane-2, 4-diol, hexane-1, 2-diol, hexane-1, 3-diol, hexane-1, 4-diol, Hexane-1, 5-diol, hexane-1, 6-diol, hexane-2, 5-diol, heptane-1, 2-diol, heptane-1, 7-diol, octane-1, 8-diol, octane-1, 2-diol, nonane-1, 9-diol, decane-1, 2-diol, decane-1, 10-diol, dodecane-1, 2-diol, dodecane-1, 12-diol, 1, 5-hexadiene-3, 4-diol, neopentyl glycol, 2-butyl-2-ethylpropane-1, 3-diol, 2-methylpentane-2, 4-diol, 2, 4-dimethylpentane-2, 4-diol, 2-ethylhexane-1, 3-diol, 2, 5-dimethylhexane-2, 5-diol, 2, 4-trimethylpentane-1, 3-diol, pinacol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, and mixtures thereof.

According to a twenty-fifth embodiment, the present invention relates to the process according to any one of embodiments 19 to 24, wherein component (b2) is a mixture having a weight average molar mass Mw of 700-2000g/mol and a molar mass according to DIN 53240-2: 2007-11 polyester diol having an acid value of not more than 20mg KOH/g.

According to a twenty-sixth embodiment, the present invention relates to the method according to any one of embodiments 19 to 25, wherein component (c) is selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-or 3-hydroxypropyl acrylate and butane-1, 4-diol monoacrylate, 1, 2-or 1, 3-diacrylate of glycerol, trimethylolpropane diacrylate, pentaerythritol triacrylate, bis (trimethylolpropane) triacrylate, dipentaerythritol pentaacrylate and mixtures thereof, preferably 2-hydroxyethyl acrylate.

According to a twenty-seventh embodiment, the present invention relates to the method of embodiments 19-26, wherein component (d) is dimethylolpropionic acid.

According to a twenty-eighth embodiment, the present invention relates to the method according to embodiments 19-27, wherein component (f) is selected from the group consisting of diethylamine, di-N-butylamine, ethanolamine, propanolamine, N-dipropanolamine, N-diethanolamine and mixtures thereof.

According to a twenty-ninth embodiment, the present invention relates to a process according to any one of the preceding embodiments, wherein the weight average molecular weight Mw of the polyurethane (meth) acrylate polymer is 1,000-50,000, more particularly 3,000-30,000, very preferably 5,000-25,000g/mol, determined by gel permeation chromatography using tetrahydrofuran and polystyrene as standard.

According to a thirtieth embodiment, the present disclosure relates to the method according to any one of the preceding embodiments, wherein the polyurethane (meth) acrylate polymer comprises 1 to 5mol, preferably 2 to 4mol of (meth) acryloyl groups per 1,000g of polyurethane (meth) acrylate.

According to a thirty-first embodiment, the present invention relates to a process according to any one of the preceding embodiments, wherein the ink composition (AC) comprises a total amount of from 15 to 95 parts, preferably from 20 to 50 parts, very preferably from 25 to 35 parts, of the aqueous dispersion (i) of the at least one polyurethane (meth) acrylate polymer, based on 100 parts of the ink composition.

According to a thirty-second embodiment, the present invention relates to a method according to any one of the preceding embodiments, wherein the at least one pigment (ii) is selected from inorganic pigments, such as titanium dioxide, zinc white, zinc sulfide, lithopone, carbon black, iron manganese black, spinel black, chromium oxide, hydrated chromium oxide green, cobalt green, ultramarine green, cobalt blue, ultramarine blue, manganese blue, ultramarine violet, cobalt violet and manganese violet, iron oxide red, cadmium sulfoselenide, molybdate-chrome red and ultramarine red, iron oxide brown, mixed brown, spinel phases and corundum phases, and chromium orange, iron oxide yellow, nickel titanium yellow, chromium titanium yellow, cadmium sulfide, zinc sulfide, chromium yellow and cadmium bismuth vanadate; organic pigments such as monoazo pigments, disazo pigments, anthraquinone pigments, benzimidazole pigments, quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone pigments, isoindoline pigments, isoindolinone pigments, azomethine pigments, thioindigo pigments, metal complex pigments, perinone pigments, perylene pigments, phthalocyanine pigments and/or aniline black; and mixtures thereof.

According to a thirty-third embodiment, the present invention relates to the method according to any one of the preceding embodiments, wherein the ink composition (AC) comprises the at least one pigment and/or dye (ii) in a total amount of 0.01 to 5 parts, preferably 0.1 to 2.5 parts, very preferably 0.2 to 0.5 parts, based on 100 parts of the ink composition.

According to a thirty-fourth embodiment, the present invention relates to a process according to any one of the preceding embodiments, wherein the at least one photoinitiator (iii) is selected from phosphine oxides, benzophenones, thioxanthones, anthraquinones, acetophenones, such as α -aminoarylketones and/or α -hydroxyalkylarylketones, benzoins and benzoin ethers, ketals, imidazoles or benzoylformic acids, and mixtures thereof.

According to a thirty-fifth embodiment, the present disclosure relates to the method according to any one of the preceding embodiments, wherein the at least one photoinitiator (iii) is selected from a mixture of bisacetyl phosphine oxide and monoacylphosphine oxide.

According to a thirty-sixth embodiment, the present invention relates to the method according to any one of the preceding embodiments, wherein the ink composition (AC) comprises the at least one photoinitiator (iii) in a total amount of 0.01 to 8 parts, preferably 0.1 to 7 parts, more preferably 0.2 to 5 parts, very preferably 0.2 to 1.5 parts, based on 100 parts of the ink composition.

According to a thirty-seventh embodiment, the present disclosure relates to the method according to any one of the preceding embodiments, wherein the ink composition (AC) further comprises at least one surfactant (iv).

According to a thirty-eighth embodiment, the present invention relates to the method according to embodiment 37, wherein the at least one surfactant (iv) is selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, fluorinated surfactants, silicone surfactants and mixtures thereof, preferably nonionic acetylenic surfactants and/or silicon surfactants.

According to a thirty-ninth embodiment, the present invention relates to the method of embodiment 38, wherein the non-ionic surfactant is selected from the group consisting of acetylenic surfactants, such as 3, 6-dimethyl-4-octyne-3, 6-diol, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and ethoxylated acetylenic surfactants; poly (oxyalkylene glycol) and C₈-C₃₀Carboxylic acid, C₈-C₃₀Alcohol, C₈-C₃₀Trans-reaction of amines, sorbitan esters, alkanolamides, castor oilsReacting the product; c₈-C₃₀Amines and derivatives thereof; nonionic polymers, such as polyoxypropylene/polyoxyethylene copolymers, polyalkylene glycols, polyvinyl alcohols, polyacrylic acids, hydrophobically substituted polyacrylamides, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyoxyethylene alkyl ethers, polyoxyethylene nonylphenyl ethers, alkyl or dialkylphenoxypoly (ethyleneoxy) ethanol derivatives, antifoam silicon compounds, blends of organic esters in mineral oil bases, EO/PO block copolymers; and mixtures thereof, preferably 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol.

According to a fortieth embodiment, the present invention relates to the method of embodiment 38 or 39, wherein the anionic surfactant is selected from the group consisting of sulfonated fatty acid esters, phosphorylated fatty acid esters, alkyl sulfoxides and alkyl sulfones, sodium alkyl sulfates, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate, sodium dodecyldiphenyloxide disulfonate, sodium alkyl sulfosuccinate, potassium N-methyl-N-oleoyl taurate, carboxymethyl amylose, and mixtures thereof.

According to a forty-first embodiment, the present invention relates to the method of any one of embodiments 38-40, wherein the cationic surfactant is selected from the group consisting of dialkyl benzenealkyl ammonium chlorides, alkyl benzyl methyl ammonium chlorides, cetyl pyridinium bromides, alkyl trimethyl ammonium bromides, halide salts of quaternized polyoxyethylalkylamines, dodecyl benzyl triethyl ammonium chlorides, alkyl sulfate quaternary compounds, fatty imidazolines, and mixtures thereof.

According to a forty-second embodiment, the present invention relates to the method according to any one of embodiments 37 to 41, wherein the ink composition (AC) comprises at least one surfactant (iv) comprising at least one non-ionic acetylene glycol-based surfactant (iv-1), preferably 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, and/or at least one silicon surfactant (vi-2), preferably a polyether-modified siloxane.

According to a forty-third embodiment, the present invention relates to the method according to any one of embodiments 37 to 42, wherein the ink composition (AC) comprises the at least one surfactant (iv), preferably the at least one nonionic surfactant and/or the at least one silicon surfactant, very preferably 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and/or polyether modified siloxane in a total amount of 0.01 to 1 part, preferably 0.02 to 0.5 part, very preferably 0.02 to 0.2 part, based on 100 parts of the aqueous ink composition (AC).

According to a forty-fourth embodiment, the present invention relates to a process according to any one of the preceding embodiments, wherein the ink composition (AC) further comprises at least one additive (v) selected from rheology modifiers (v-1), humectants (v-2), co-solvents (v-3), biocides (v-4) and mixtures thereof.

According to a forty-fifth embodiment, the present invention is directed to the method of embodiment 44, wherein the ink composition (AC) comprises the at least one rheology modifier (v-1) in a total amount of 0.01 to 1 part based on 100 parts of the ink composition.

According to a forty-sixth embodiment, the present invention is directed to the method of embodiment 44 or 45, wherein the ink composition (AC) comprises the at least one humectant (v-2) in a total amount of 0.01 to 30 parts based on 100 parts of the ink composition.

According to a forty-seventh embodiment, the present invention relates to the method according to any one of embodiments 44 to 46, wherein the ink composition (AC) comprises said at least one co-solvent (v-3) in a total amount of 0.01 to 30 parts, based on 100 parts of the ink composition.

According to a forty-eighth embodiment, the present invention relates to the method according to any one of embodiments 44 to 47, wherein the ink composition (AC) comprises the at least one biocide (v-4) in a total amount of 0.01 to 1 part, based on 100 parts of the ink composition.

According to a forty-ninth embodiment, the present invention relates to a process according to any one of the preceding embodiments, wherein the ink composition (AC) comprises (meth) acrylates having a number average molecular weight Mn of less than 1,200g/mol in a total amount of 0 to 2 wt. -%, preferably 0 to 1 wt. -%, very preferably 0 wt. -%, based on the total weight of the ink composition (AC).

According to a fifty-fourth embodiment, the present invention relates to a process according to any one of the preceding embodiments, wherein the ink composition (AC) is an aqueous ink composition and comprises water in a total amount of 5 to 95 parts, preferably 35 to 95 parts, more preferably 50 to 90 parts, very preferably 60 to 90 parts, based on 100 parts of the aqueous ink composition (AC).

According to a fifty-first embodiment, the present invention relates to the method according to any one of the preceding embodiments, wherein the ink composition (AC), preferably the aqueous ink composition (AC), has a solid content of 8-40 parts, preferably 20-40 parts, very preferably 25-35 parts, based on 100 parts of the ink composition.

According to a fifty-second embodiment, the present invention relates to a process according to any one of the preceding embodiments, wherein the viscosity of the ink composition (AC), preferably the aqueous ink composition (AC), is from 0.01 to 100mPa · s, preferably from 5 to 30mPa · s, more preferably from 4 to 20mPa · s, very preferably from 2 to 15mPa · s, using a rotational viscometer at 23 ℃ and 1000s^-1Measured at shear rate.

According to a fifty-third embodiment, the present invention relates to the method according to any one of the preceding embodiments, wherein the ink composition (AC), preferably the aqueous ink composition, has a viscosity according to DIN EN 14210: 2004-03 (Ring method) a surface tension of 10 to 70mN/m, more preferably 15 to 60mN/m, and very preferably 20 to 50mN/m, measured at 23 ℃.

According to a fifty-fourth embodiment, the present disclosure relates to the method of any one of the preceding embodiments, wherein the ink composition (AC) in step (3) is deposited by a digital printing device comprising a Drop On Demand (DOD) ink jet printer.

According to a fifty-fifth embodiment, the invention relates to the method according to embodiment 54, wherein the Drop On Demand (DOD) ink jet printer has at least one print head, wherein the at least one print head has one or more nozzles, the diameter of which is in each case 1 to 52 μm, more preferably 15 to 40 μm, very preferably 30 to 40 μm.

According to a fifty-sixth embodiment, the invention relates to the method according to embodiment 55, wherein the print head has 1 to 1024 nozzles, preferably 50 to 500 nozzles, very preferably 110 and 140 nozzles.

According to a fifty-seventh embodiment, the present disclosure is directed to the method of embodiment 55 or 56, wherein the printhead discharges the aqueous ink composition at a droplet size of 1 to 200pl, preferably 15 to 100pl, very preferably 25 to 35 pl.

According to a fifty-eighth embodiment, the invention relates to the method according to any one of embodiments 55 to 57, wherein the angle of the print head is 0 to 90 °, more preferably 0 to 45 °, and very preferably 0 °.

According to a fifty-ninth embodiment, the present invention relates to the method according to any one of embodiments 55 to 58, wherein in step (3) the distance between the portion to be printed of the at least one surface of the nonwoven textile substrate (S) and the at least one nozzle of the at least one print head is from 0.1mm to 4cm, preferably from 0.5 to 1.5 mm.

According to a sixteenth embodiment, the present invention relates to a method according to any one of the preceding embodiments, wherein the printing speed is between 50 and 500mm/s, preferably 100 and 300mm/s, very preferably 150 and 250 mm/s.

According to a sixteenth embodiment, the present invention relates to a method according to any one of the preceding embodiments, wherein the printing in step (3) is carried out at a jetting temperature of 15-50 ℃, preferably 20-30 ℃, very preferably 23 ℃.

According to a sixty-second embodiment, the present invention relates to a process according to any one of the preceding embodiments, wherein the drying of the ink composition (AC), preferably the aqueous ink composition (AC) in step (4) is carried out at 30-100 ℃, preferably 50-70 ℃ for a time period of 1-60 minutes, preferably 5-30 minutes, very preferably 5-20 minutes.

According to a sixty-third embodiment, the present invention is directed to the method of any one of the preceding embodiments, wherein the curing of the ink composition (AC) in step (4) is performed under a nitrogen atmosphere.

According to a sixty-fourth embodiment, the present invention relates to a process according to any one of the preceding embodiments, wherein the curing of the ink composition (AC) in step (4) is performed by radiation curing, preferably by UV-light and/or Electron Beam Curing (EBC), very preferably by UV-light.

According to a sixty-fifth embodiment, the present invention relates to the method according to any one of the preceding embodiments, wherein the curing of the ink composition (AC) in step (4) is performed by UV light using 1-10W/cm²Preferably 1 to 6W/cm²And/or 1-20J/cm²More preferably 1 to 12J/cm²The dosage of (a).

According to a sixty-sixth embodiment, the present invention relates to the method according to any one of embodiments 1 to 64, wherein the curing of the ink composition (AC) in step (4) is performed by electron beam curing, using an intensity of 30-80kGy, preferably 40-60kGy, very preferably 50 kGy.

According to a sixty-seventh embodiment, the present invention relates to a nonwoven textile substrate (S) at least partially coated with an Ink Layer (IL), said substrate being prepared by the method according to any one of embodiments 1 to 64.

Examples

The invention will now be explained in more detail using working examples, to which the invention is in no way limited. In addition, the terms "part(s)", "%" and "proportion(s)" in the examples represent "part(s) by mass", "% by mass" and "mass ratio", respectively, unless otherwise specified.

The determination method comprises the following steps:

1. solid content (solids, non-volatiles)

Unless otherwise stated, the solids content, also referred to below as solids fraction, is in accordance with DIN EN ISO 3251: 2018-07 at 120 ℃ for 60 minutes, initial mass 1.0 g.

2. Viscosity of the oil

Viscosity Using a rotational viscometer (rheometer MCR302, measurement geometry DG42) at 23 ℃ for 1000s^-1The shear rate of (2).

3. Surface tension

Surface tension according to DIN EN 14210: 2004-03 (Ring method), using a Krusstensometer K100 with ptlr rings at 23 ℃.

Examples of the invention

The following examples of the invention are intended to illustrate the invention but should not be construed as imposing any limitation thereon.

Unless otherwise indicated, the figures for parts are parts by weight and the figures for percentages are percentages by weight in each case.

1. Preparation of aqueous ink composition AC

Aqueous ink compositions AC-1 to AC-6 were prepared according to table 1 below by mixing the components described therein.

Table 1: radiation curable ink composition AC (amount in% by weight)

¹⁾ UA 9122Aqua (BASF SE; solids content 37-39% by weight)

²⁾Dispers blue 70-0507(BASF SE; 40% by weight pigment)

³⁾Omnirad 2100(IGM Resins; phosphine oxides)

⁴⁾TMDD BG 52(BASF SE; 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol)

⁵⁾BYK 346 (BYK; polyether-modified siloxanes of the general formula (I))

2. Base material

The substrate S1 is made of1180A 10 preparation having a basis weight of 400g/m²；

The substrate S2 is made ofB85A 10 preparation with a basis weight of 500g/m²。

1180A 10: thermoplastic polyurethane based on (a)4,4' -diphenylmethane diisocyanate (MDI), (b) polytetrahydrofuran (poly-THF) and (c)1, 4-butanediol, which has the following properties: a Shore hardness of 80A (DIN ISO 7619-1: 2012-02, measurement time of 3 seconds),

-a glass transition temperature of 44 ℃ (11357-1: 2017-02, heating rate 10 ℃/min),

a Vicat softening temperature of 90 ℃ (DIN EN ISO 306: 2014-03, heating rate 120 ℃/h,

the load is 10N),

a tensile strength of 45MPa (DIN 53504: 2009-10, tensile bar S2),

an elongation at break of 650% (DIN 53504: 2009-10, stretch strip S2),

tear Strength of 55kN/m (DIN EN ISO 34-1: 2004-07, method B, procedure (a)), and

-30mm³abrasion loss (DIN EN ISO 4649: 2010-09, method A).

B85A 10: thermoplastic polyurethane based on (a)4,4' -diphenylmethane diisocyanate and/or hexamethylene 1, 6-diisocyanate, (b)1, 4-butanediol and/or 1, 6-hexanediol polyadipate and (c)1, 2-ethanediol, 1, 4-butanediol and/or 1, 6-hexanediol, having the following properties:

-a Shore hardness of 83A (DIN ISO 7619-1: 2012-02, measurement time of 3 seconds),

-a glass transition temperature of 44 ℃ (DIN EN ISO 11357-1: 2017-02, heating rate 10 ℃/min),

-100-,

a tensile strength of 55MPa (DIN 53504: 2009-10, tensile bar S2),

an elongation at break of 600% (DIN 53504: 2009-10, stretch strip S2),

tear Strength of 75kN/m (DIN EN ISO 34-1: 2004-07, method B, procedure (a)), and

-35mm³abrasion loss (DIN EN ISO 4649: 2010-09, method A).

3. Printing method

The ink compositions AC-1 to AC-6 were each printed onto substrates S1 and S2, respectively, using a printer commercially available from Mayer Burger Technology AG, switzerland. The printer used was of the Pixdro LP50 type, having piezoelectric printheads, each 35 μm in diameter (Spectra SE 128AA from Fujifilm). The resolution was 800-1,600 dpi.

4. Drying method

After printing the ink compositions AC-1 to AC-6 onto the substrates S1 and S2, the printed substrates were dried at 60 ℃ for 10 minutes.

5. Curing method

Curing all printed substrates to provide a cured Ink Layer (IL) on the respective substrates was carried out by radiation curing using an IST curing belt and the following parameters:

-a UV lamp: 2 mercury lamps (Power 200W/cm)

-intensity: about 1W/cm²

-dose: about 6 to 8J/cm²

-atmosphere: nitrogen (< 0.1% oxygen) or ambient atmosphere

6. Results

All substrates were successfully printed at high resolution without adversely affecting the properties or feel of the substrate containing the cured ink layer.

The use of only the surfactant (iv-1) results in reduced color boundary bleeding as compared with the ink composition comprising the surfactants (iv-1) and (iv-2).

Curing of the printing ink may be enhanced by using a nitrogen atmosphere instead of an ambient atmosphere.