阅读说明：本技术 纤维用防水剂组合物、防水性纤维制品及防水性纤维制品的制造方法 (Water repellent composition for fibers, water repellent fiber product, and method for producing water repellent fiber product ) 是由 前田高辅 漆崎弓子 柘植好挥 于 2019-08-27 设计创作，主要内容包括：本发明的防水剂组合物含有：具有源自下述通式(A-1)所表示的(甲基)丙烯酸酯单体(A)的结构单元的丙烯酸系树脂和/或具有源自下述通式(I-1)所表示的多官能化合物的结构单元及源自下述通式(II-1)所表示的异氰酸酯化合物的结构单元的氨基甲酸酯树脂、下述通式(L-1)所表示的有机改性有机硅、及蜡。[式(A-1)中,R～1表示氢或甲基,R～2表示可具有取代基的碳数12以上的1价烃基。]R～(31)[-W～1-R～(32)]-d[-V～1]-e(I-1)[式(I-1)中,d表示1以上的整数,e表示2以上的整数,(d+e)为3～6,R～(31)表示(d+e)价的有机基团,W～1表示为酯基、酰胺基、氨基甲酸酯基或脲基的2价基团,R～(32)表示碳数8～24的直链或支链的1价烃基,V～1表示羟基、氨基或羧基。其中,e个V～1中的2个以上为羟基和/或氨基。]R～(33)[-NCO]-f(II-1)[式(II-1)中,R～(33)表示f价有机基团,f表示2～7的整数。][式(L-1)中,R～(220)、R～(221)及R～(222)各自独立地表示氢原子、甲基、乙基或碳数1～4的烷氧基,R～(223)表示具有芳香族环的碳数8～40的烃基、或碳数3～22的烷基,R～(230)、R～(231)、R～(232)、R～(233)、R～(234)及R～(235)各自独立地表示氢原子、甲基、乙基、碳数1～4的烷氧基、具有芳香族环的碳数8～40的烃基、或碳数3～22的烷基,a1表示0以上的整数,a2表示1以上的整数,(a1+a2)为10～200,在a1为2以上的情况下,存在多个的R～(220)及R～(221)各自可相同也可不同,在a2为2以上的情况下,存在多个的R～(222)及R～(223)各自可相同也可不同。]。(The water repellent composition of the present invention comprises: an acrylic resin having a structural unit derived from a (meth) acrylate monomer (A) represented by the following general formula (A-1) and/or a structural unit derived from a polyfunctional compound represented by the following general formula (I-1) and an isocyanate derived from the following general formula (II-1)A urethane resin which is a structural unit of an ester compound, an organic modified silicone represented by the following general formula (L-1), and a wax. [ in the formula (A-1), R 1 Represents hydrogen or methyl, R 2 Represents a C12 or higher valent hydrocarbon group which may have a substituent.]R 31 [‑W 1 ‑R 32 ] d [‑V 1 ] e (I-1) [ formula (I-1) wherein d represents an integer of 1 or more, e represents an integer of 2 or more, (d + e) is 3 to 6, R 31 An organic group having a valence of (d + e), W 1 A 2-valent radical which is an ester, amide, carbamate or urea group, R 32 V is a C8-24 linear or branched 1-valent hydrocarbon group 1 Represents a hydroxyl group, an amino group or a carboxyl group. Wherein e are V 1 2 or more of them are hydroxyl and/or amino.]R 33 [‑NCO] f (II-1) [ formula (II-1) wherein R 33 Represents a f-valent organic group, and f represents an integer of 2 to 7.] [ in the formula (L-1), R 220 、R 221 And R 222 Each independently represents a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms, R 223 Represents a C8-40 hydrocarbon group having an aromatic ring or a C3-22 alkyl group, R 230 、R 231 、R 232 、R 233 、R 234 And R 235 Each independently represents a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms, a1 represents an integer of 0 or more, a2 represents an integer of 1 or more, (a1+ a2) is 10 to 200, and when a1 is 2 or more, a plurality of R's are present 220 And R 221 Each of which may be the same or different, and when a2 is 2 or more, a plurality of R's are present 222 And R 223 Each may be the same or different.]。)

1. A water repellent composition for fibers, comprising: an acrylic resin having a structural unit derived from a (meth) acrylate monomer (A) represented by the following general formula (A-1) and/or a urethane resin having a structural unit derived from a polyfunctional compound represented by the following general formula (I-1) and a structural unit derived from an isocyanate compound represented by the following general formula (II-1),

An organically modified silicone represented by the following general formula (L-1), and

a wax;

[ solution 1]

In the formula (A-1), R¹Represents hydrogen or methyl, R²Represents a C12 or higher valent hydrocarbon group which may have a substituent,

R³¹[-W¹-R³²]_d[-V¹]_e (I-1)

in the formula (I-1), d represents an integer of 1 or more, e represents an integer of 2 or more, (d + e) is 3 to 6, R³¹An organic group having a valence of (d + e), W¹A 2-valent radical which is an ester, amide, carbamate or urea group, R³²V is a C8-24 linear or branched 1-valent hydrocarbon group¹Represents a hydroxyl group, an amino group or a carboxyl group; wherein e are V¹2 or more of them are hydroxyl and/or amino,

R³³[-NCO]_f (II-1)

in the formula (II-1), R³³Represents an f-valent organic group, f represents an integer of 2 to 7,

[ solution 2]

In the formula (L-1), R²²⁰、R²²¹And R²²²Each independently represents a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms, R²²³Represents a C8-40 hydrocarbon group having an aromatic ring or a C3-22 alkyl group, R²³⁰、R²³¹、R²³²、R²³³、R²³⁴And R²³⁵Each independently represents a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms, a1 represents an integer of 0 or more, a2 represents an integer of 1 or more, (a1+ a2) is 10 to 200, and when a1 is 2 or more, a plurality of R's are present²²⁰And R²²¹Each of which may be the same or different, and when a2 is 2 or more, a plurality of R's are present²²²And R²²³Each may be the same or different.

2. The water repellent composition for fiber according to claim 1, wherein the acrylic resin further has a structural unit derived from at least 1 monomer (E) of vinyl chloride and vinylidene chloride.

3. A water repellent composition for fibers according to claim 1 or 2, further comprising a crosslinking agent.

4. A water repellent fiber product comprising a fiber base material and the water repellent composition for fiber according to any one of claims 1 to 3 attached to the fiber base material.

5. A method for producing a water repellent fiber product, comprising a step of bringing a treatment liquid containing the water repellent composition for fiber according to any one of claims 1 to 3 into contact with a fiber base material.

Technical Field

The present invention relates to a water repellent composition for fibers, a water repellent fiber product, and a method for producing a water repellent fiber product.

Background

Conventionally, as a water repellent used for water repellent processing or the like, a fluorine-based water repellent having a fluoroalkyl group is known, and a fiber product having water repellency is obtained by treating a fiber surface with the fluorine-based water repellent. However, although fiber products treated with a fluorine-based water repellent exhibit excellent water repellency, a concern of environmental load of a long-chain fluoroalkyl compound used has become clear, and thus a non-fluorine-based water repellent exhibiting high water repellency comparable to that of fluorine-based water repellent without containing any fluorine-based compound is internationally required.

Therefore, studies have been made in recent years on a non-fluorine-containing water repellent containing no fluorine. For example, patent document 1 below discloses a fiber processing agent containing at least 1 of a silicon-based compound, a wax-based compound, and a wax-zirconium-based compound. Further, patent document 2 below proposes a soft water repellent containing an amino-modified silicone and a polyfunctional isocyanate. Further, patent document 3 below proposes a water repellent containing a specific non-fluorine-containing polymer containing, as a monomer unit, a (meth) acrylate ester having an ester moiety and having 12 or more carbon atoms.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2006-124866

Patent document 2: japanese patent laid-open publication No. 2004-59609

Patent document 3: japanese patent laid-open publication No. 2006-328624

Disclosure of Invention

Problems to be solved by the invention

However, although the conventional non-fluorine-based water repellent can confirm the initial water repellent effect by the spray method of JIS L1092 (2009), which is one of the usual water repellent evaluation tests, a sufficient result may not be obtained in the evaluation test assuming practical use and practical installation (shown in experimental results) of the fiber product. In view of practical use, durable water repellency is required which is less likely to decrease even if washing is repeated. For the actual installation, it is required to prevent water leakage for a long time. If the water permeation preventive property is insufficient, there are cases where: in the case where a water droplet stays on the surface of a fiber for a certain period of time or the like, a part of the water droplet penetrates into the interior of the fiber with the lapse of time, resulting in wetting of the opposite side. These practical and practical performances of the conventional non-fluorine-based waterproofing agents are still insufficient as compared with those of the fluorine-based waterproofing agents.

In addition, in a textile product or the like subjected to waterproof processing, a specific portion may be subjected to processing such as coating with a urethane resin or an acrylic resin. In this case, the fiber product has sufficient water resistance, but the coated portion is required to be less likely to peel off. The degree of resistance to peeling of the coating can be evaluated by measuring the stress (peel strength) required to peel the coating film from the water repellent-processed fiber base material, but conventional non-fluorine-based water repellents have not been sufficiently studied with respect to such peel strength, and there is room for further improvement in order to achieve both the above-mentioned performance in practical use and mounting and peel strength at a higher level.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a water repellent composition for fibers which can impart excellent initial water repellency, durable water repellency, and water repellency to a fiber base material and can provide a fiber base material having such properties with sufficient peel strength, a water repellent fiber product using the same, and a method for producing a water repellent fiber product.

Means for solving the problems

As a result of diligent research aimed at solving the above problems, the present inventors have found that a cloth subjected to water repellent processing using a water repellent composition in which a specific resin is combined with a specific silicone and a wax exhibits not only excellent initial water repellency but also good results in the evaluation of durable water repellency after washing, the evaluation of water repellency, and the evaluation of peel strength, and have completed the present invention based on this finding.

One aspect of the present invention relates to a water repellent composition for fibers, which contains: an acrylic resin having a structural unit derived from a (meth) acrylate monomer (A) represented by the following general formula (A-1), and/or a urethane resin having a structural unit derived from a polyfunctional compound represented by the following general formula (I-1) and a structural unit derived from an isocyanate compound represented by the following general formula (II-1), an organically modified silicone represented by the following general formula (L-1), and a wax.

[ solution 1]

[ in the formula (A-1), R¹Represents hydrogen or methyl, R²Represents a C12 or higher valent hydrocarbon group which may have a substituent.]

R³¹[-W¹-R³²]_d[-V¹]_e (I-1)

[ in the formula (I-1), d represents an integer of 1 or more, e represents an integer of 2 or more, (d + e) is 3 to 6, and R³¹An organic group having a valence of (d + e), W¹A 2-valent radical which is an ester, amide, carbamate or urea group, R³²V is a C8-24 linear or branched 1-valent hydrocarbon group¹Represents a hydroxyl group, an amino group or a carboxyl group; wherein e are V¹2 or more of them are hydroxyl and/or amino.]

R³³[-NCO]_f (II-1)

[ formula (II-1) wherein R³³F is an f-valent organic group, and f is an integer of 2 to 7]

[ solution 2]

[ in the formula (L-1), R²²⁰、R²²¹And R²²²Each independently represents a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms, R²²³Represents a C8-40 hydrocarbon group having an aromatic ring or a C3-22 alkyl group, R²³⁰、R²³¹、R²³²、R²³³、R²³⁴And R²³⁵Each independently represents a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, or an aromatic groupA C8-40 hydrocarbon group or C3-22 alkyl group in the aromatic ring, a1 represents an integer of 0 or more, a2 represents an integer of 1 or more, (a1+ a2) is 10-200, and when a1 is 2 or more, a plurality of R's are present²²⁰And R²²¹Each of which may be the same or different, and when a2 is 2 or more, a plurality of R's are present²²²And R²²³Each may be the same or different.]

According to the water repellent composition for fiber of the present invention, a fiber base material having excellent initial water repellency, durable water repellency, and water permeation resistance can be provided, and a fiber base material having sufficient peel strength can be obtained despite the provision of the above characteristics. Thus, a waterproof fiber product having performance suitable for practical use and mounting can be realized.

The water repellent composition for fibers of the present invention can impart excellent water repellency (effect of increasing the contact angle with water) although it does not contain a compound having a fluoroalkyl group or fluorine, and therefore can be used as a water repellent instead of a fluorine-based water repellent, and can eliminate the concern of influences on the environment and the like. Further, according to the water repellent composition for fiber of the present invention, a fiber base material which sufficiently maintains the texture of the fiber base material (FENG HE い) and imparts the above-described excellent initial water repellency, durable water repellency and water repellency but has sufficient peel strength can be obtained.

In the water repellent composition for fiber of the present invention, the acrylic resin may further have a structural unit derived from at least 1 monomer (E) of vinyl chloride and vinylidene chloride.

The water repellent composition for fiber of the present invention may further contain a crosslinking agent.

Another aspect of the present invention relates to a water repellent fiber product comprising a fiber base material and the water repellent composition for fiber of the present invention attached to the fiber base material.

The water repellent fiber product of the present invention can be provided with excellent initial water repellency, durable water repellency, and water permeation resistance by the water repellent composition for fiber of the present invention, and can have sufficient peel strength when subjected to coating processing. Therefore, the waterproof fiber product of the present invention can be a waterproof fiber product having properties suitable for practical use and packaging.

In a further aspect of the present invention, there is provided a method for producing a water repellent fiber product, comprising the step of bringing a treatment liquid containing the water repellent composition of the present invention into contact with a fiber base material.

According to the method for producing a water-repellent fiber product of the present invention, a water-repellent fiber product having excellent initial water repellency, durable water repellency, and water repellency and having sufficient peel strength can be obtained.

Effects of the invention

According to the present invention, it is possible to provide a water repellent composition for fibers which can impart excellent initial water repellency, durable water repellency, and water repellency to a fiber base material and can provide a fiber base material having such properties with sufficient peel strength, and a water repellent fiber product and a method for producing a water repellent fiber product using the same.

Detailed Description

Hereinafter, a preferred embodiment of the present invention will be described.

In the present specification, "(meth) acrylate" means "acrylate" or "methacrylate" corresponding thereto, and is synonymous with "(meth) acrylic acid", "meth) acrylamide", and the like.

In the present specification, an ester group means a group represented by-O-CO-. The amide group means a group represented by-NH-CO-. The urethane group means a group represented by-O-CO-NH-. Ureido means a group represented by-NH-CO-NH-. The isocyanate group means a group represented by — N ═ C ═ O. Carbonyl means a group represented by-CO-.

In the present specification, the fiber base material is a target to be subjected to water repellent processing by the water repellent composition, and may be a fiber product or a fiber material constituting the fiber product.

The water repellent composition for fibers of the present embodiment contains: an acrylic resin having a structural unit derived from a (meth) acrylate monomer (A) represented by the following general formula (A-1) (hereinafter, also referred to as "acrylic resin"), and/or a urethane resin having a structural unit derived from a polyfunctional compound represented by the following general formula (I-1) and a structural unit derived from an isocyanate compound represented by the following general formula (II-1) (hereinafter, also referred to as "urethane resin"), an organically modified silicone represented by the following general formula (L-1) (hereinafter, also referred to as "organically modified silicone"), and a wax.

[ solution 3]

[ in the formula (A-1), R¹Represents hydrogen or methyl, R²Represents a C12 or higher valent hydrocarbon group which may have a substituent.]

R³¹[-W¹-R³²]_d[-V¹]_e (I-1)

[ in the formula (I-1), d represents an integer of 1 or more, e represents an integer of 2 or more, (d + e) is 3 to 6, and R³¹An organic group having a valence of (d + e), W¹A 2-valent radical which is an ester, amide, carbamate or urea group, R³²V is a C8-24 linear or branched 1-valent hydrocarbon group¹Represents a hydroxyl group, an amino group or a carboxyl group. Wherein e are V¹2 or more of them are hydroxyl and/or amino.]

R³³[-NCO]_f (II-1)

[ formula (II-1) wherein R³³Represents a f-valent organic group, and f represents an integer of 2 to 7.]

[ solution 4]

[ in the formula (L-1), R²²⁰、R²²¹And R²²²Each independently represents a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms, R²²³Represents a C8-40 hydrocarbon group having an aromatic ring or an alkyl group having a C3-22 carbon atom,R²³⁰、R²³¹、R²³²、R²³³、R²³⁴and R²³⁵Each independently represents a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms, a1 represents an integer of 0 or more, a2 represents an integer of 1 or more, (a1+ a2) is 10 to 200, and when a1 is 2 or more, a plurality of R's are present²²⁰And R²²¹Each of which may be the same or different, and when a2 is 2 or more, a plurality of R's are present²²²And R²²³Each may be the same or different.]

Hereinafter, the acrylic resin and the urethane resin may be referred to as an "(α) component", the organic modified silicone may be referred to as a "(β) component", and the wax may be referred to as a "(γ) component".

The component (α) contained in the water repellent composition of the present embodiment will be described in detail below.

The component (. alpha.) is preferably an acrylic resin. When the component (α) is an acrylic resin, the initial water repellency, the durable water repellency, or both (hereinafter, also simply referred to as "water repellency") and the water impermeability are easily improved.

The acrylic resin will be described below.

The (meth) acrylate monomer (a) (hereinafter also referred to as "monomer (a)") represented by the general formula (a-1) used in the present embodiment has a 1-valent hydrocarbon group having 12 or more carbon atoms, which may have a substituent. The hydrocarbon group may be linear or branched, may be saturated or unsaturated, and may have an alicyclic or aromatic ring shape. Among these, from the viewpoint of water repellency and water repellency, a linear alkyl group is preferable, and a linear alkyl group is more preferable. When the 1-valent hydrocarbon group having 12 or more carbon atoms has a substituent, the substituent may be 1 or more of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, a (meth) acryloyloxy group, and the like. In this embodiment, in the general formula (A-1), R²Unsubstituted hydrocarbon groups are preferred.

The number of carbon atoms of the hydrocarbon group is preferably 12 to 24, more preferably 12 to 22. When the number of carbon atoms of the hydrocarbon group is in this range, it is easy to improve the water repellency and water impermeability imparted to the fiber base material while sufficiently maintaining the texture of the fiber base material. From the same viewpoint as above, the hydrocarbon group is more preferably a linear alkyl group having 15 to 22 carbon atoms, and still more preferably a linear alkyl group having 15 to 20 carbon atoms.

Examples of the monomer (a) include: stearyl (meth) acrylate, cetyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, behenyl (meth) acrylate, wax (meth) acrylate, and beeswax (メリシル) (meth) acrylate.

The monomer (a) may have at least 1 functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group, which is reactive with a crosslinking agent described below. In this case, the water repellency and water impermeability imparted to the fiber base material can be easily improved. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. In addition, in the case where the monomer (a) has an amino group, the texture of the obtained fiber product can be further improved.

The monomer (a) is preferably a monofunctional (meth) acrylate monomer having 1 polymerizable unsaturated group in 1 molecule.

The above-mentioned monomer (A) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

In view of improving the water repellency and water impermeability imparted to the fiber base material, it is preferable to use the acrylate monomer (a1) (hereinafter, also referred to as the "(a 1) component") in combination with the methacrylate monomer (a2) (hereinafter, also referred to as the "(a 2) component"). The ratio (a1)/(a2) of the mass of the component (a1) to the mass of the component (a2) is preferably 30/70 to 90/10, more preferably 40/60 to 85/15, still more preferably 50/50 to 80/20, and particularly preferably 60/40 to 80/20. When (a1)/(a2) is within the above range, the water repellency and water impermeability imparted to the fibrous base material can be easily improved.

In the case where the water repellent composition of the present embodiment includes an acrylic resin as the component (α), the total composition ratio of the monomers (a) in the acrylic resin may be 50 to 100% by mass, and from the viewpoint of improving the water repellency and water repellency imparted to the fiber base material, the total amount of the monomer components constituting the acrylic resin is preferably 50 to 99% by mass, more preferably 60 to 99% by mass, and still more preferably 70 to 99% by mass.

The weight average molecular weight of the acrylic resin is preferably 10 ten thousand or more. If the weight average molecular weight is 10 ten thousand or more, the water repellency of the obtained water-repellent fiber product tends to be easily improved. In addition, from the viewpoint of further improving the water repellency of the water-repellent fiber product obtained, the weight average molecular weight of the acrylic resin is more preferably 50 ten thousand or more. The upper limit of the weight average molecular weight of the acrylic resin is preferably about 500 ten thousand. In the present specification, the weight average molecular weight refers to a value obtained by measuring by GPC (Gel Permeation chromatography) and converting into standard polystyrene.

In the present embodiment, the melt viscosity of the acrylic resin at 105 ℃ is preferably 1000 pas or less. When the melt viscosity at 105 ℃ is 1000 pas or less, a water-repellent fiber product having excellent texture tends to be easily obtained. Further, when the melt viscosity at 105 ℃ is 1000Pa · s or less, precipitation or precipitation of the acrylic resin when the acrylic resin is emulsified or dispersed to prepare the water repellent composition can be suppressed, and the storage stability of the water repellent composition tends to be improved. The melt viscosity of the acrylic resin at 105 ℃ is more preferably 500 pas or less. In this case, the obtained water-repellent fiber product or the like has sufficient water repellency and is also excellent in texture.

The acrylic resin preferably contains, as a monomer component, at least 1 kind of reactive emulsifier (B) (hereinafter, also referred to as "reactive emulsifier (B)") selected from the group consisting of (B1) a compound represented by the following general formula (B-1) having an HLB of 7 to 18, (B2) a compound represented by the following general formula (B-2) having an HLB of 7 to 18, and (B3) a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a fat or oil having a hydroxyl group and a polymerizable unsaturated group, the compounds having an HLB of 7 to 18, in addition to the monomer (a), from the viewpoint of improving water repellency and water permeation resistance, and emulsion stability in the composition during and after emulsion polymerization of the acrylic resin.

[ solution 5]

[ in the formula (B-1), R³Hydrogen or methyl, X represents a C1-6 linear or branched alkylene group, Y¹Represents a 2-valent group containing C2-4 alkyleneoxy groups.]

[ solution 6]

[ in the formula (B-2), R⁴Y represents a C13-17 unsaturated 1-valent hydrocarbon group having a polymerizable unsaturated group²Represents a 2-valent group containing C2-4 alkyleneoxy groups.]

The "reactive emulsifier" is an emulsifying dispersant having radical reactivity, that is, a surfactant having 1 or more polymerizable unsaturated groups in the molecule, and is copolymerizable with a monomer such as (meth) acrylate.

In the present specification, the term "HLB" refers to an HLB value calculated by the Griffin Method (Griffin Method) with an ethyleneoxy group as a hydrophilic group and all other groups as lipophilic groups unless otherwise specified.

The HLB of the compounds (B1) to (B3) is 7 to 18, and preferably 9 to 15 in terms of emulsion stability during and after emulsion polymerization or dispersion polymerization of the acrylic resin (hereinafter referred to simply as emulsion stability). Further, in terms of storage stability of the water repellent composition, it is more preferable to use 2 or more kinds of reactive emulsifiers (B) having different HLBs within the above range in combination.

In the reactive emulsifier (B1) represented by the above general formula (B-1), R³Hydrogen or methyl, and methyl is more preferable in terms of copolymerizability with the monomer (a). X is a C1-6 linear or branched alkylene group, and more preferably a C2-3 linear alkylene group in terms of emulsion stability of the acrylic resin. Y is¹Is a 2-valent group containing C2-4 alkyleneoxy groups. With respect to Y¹The kind, combination and addition number of the alkyleneoxy groups in (4) can be appropriately selected so as to fall within the above-mentioned HLB range. Further, in the case where the alkylene oxide group is 2 or more, they may have a block addition structure or a random addition structure.

The compound represented by the general formula (B-1) is preferably a compound represented by the following general formula (B-1).

[ solution 7]

[ in the formula (b-1), R³Represents hydrogen or methyl, X represents a C1-6 linear or branched alkylene group, A¹O represents an alkyleneoxy group having 2 to 4 carbon atoms, m can be appropriately selected so as to fall within the above HLB range, specifically, an integer of 1 to 80 is preferable, and when m is 2 or more, m A' s¹O may be the same or different.]

In the compound represented by the above general formula (b-1), R³Hydrogen or methyl, and methyl is more preferable in terms of copolymerizability with the monomer (a). X is a C1-6 linear or branched alkylene group, and more preferably a C2-3 linear alkylene group in terms of emulsion stability of the acrylic resin. A. the¹O is an alkyleneoxy group having 2 to 4 carbon atoms. With respect to A¹The kind and combination of O and the number of m can be appropriately selected so as to fall within the above-mentioned HLB range. In terms of emulsion stability of the acrylic resin, m is preferably an integer of 1 to 80, and more preferablyPreferably an integer of 1 to 60. When m is 2 or more, m are A¹O may be the same or different. In addition, in A¹When O is 2 or more, they may have a block addition structure or a random addition structure.

The reactive emulsifier (B1) represented by the above general formula (B-1) can be obtained by a conventionally known method, and is not particularly limited. Further, the compounds can be easily obtained from commercially available products, and examples thereof include "Latemul PD-420", "Latemul PD-430" and "Latemul PD-450" manufactured by Kao corporation.

In the reactive emulsifier (B2) represented by the above general formula (B-2), R⁴The 1-valent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group includes: tridecenyl, tridecadienyl, tetradecenyl, tetradienyl, pentadecenyl, heptadecenyl, and the like. In terms of emulsion stability of the acrylic resin, R⁴More preferably a C14-16 unsaturated hydrocarbon group having a valence of 1.

Y²Is a 2-valent group containing C2-4 alkyleneoxy groups. With respect to Y²The kind, combination and addition number of the alkyleneoxy groups in (4) can be appropriately selected so as to fall within the above-mentioned HLB range. Further, in the case where the alkylene oxide group is 2 or more, they may have a block addition structure or a random addition structure. The alkyleneoxy group is more preferably an ethyleneoxy group in terms of emulsion stability of the acrylic resin.

The compound represented by the general formula (B-2) is preferably a compound represented by the following general formula (B-2).

[ solution 8]

[ in the formula (b-2), R⁴Represents a C13-17 unsaturated 1-valent hydrocarbon group having a polymerizable unsaturated group, A²O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n may be in the above-mentioned HLB rangeThe number of A is appropriately selected, specifically, an integer of 1 to 50 is preferable, and when n is 2 or more, n A are preferable²O may be the same or different.]

R in the compound represented by the above general formula (b-2)⁴Examples thereof include R in the above-mentioned general formula (B-2)⁴The same groups.

A²O is an alkyleneoxy group having 2 to 4 carbon atoms. In terms of emulsion stability of the acrylic resin, A is²The kind and combination of O and the number of n can be appropriately selected so as to fall within the above HLB range. In terms of emulsion stability of the acrylic resin, A²O is more preferably an ethyleneoxy group, and n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, and further preferably an integer of 8 to 14. When n is 2 or more, n A²O may be the same or different. In addition, in A²When O is 2 or more, they may have a block addition structure or a random addition structure.

The reactive emulsifier (B2) represented by the above general formula (B-2) can be synthesized by adding an alkylene oxide to a phenol having a corresponding unsaturated hydrocarbon group by a conventionally known method, and is not particularly limited. For example, the alkylene oxide can be synthesized by adding a specific amount of alkylene oxide to an alkali catalyst such as caustic soda or caustic potash under pressure at 120 to 170 ℃.

The phenol having a corresponding unsaturated hydrocarbon group includes a pure product or a mixture extracted and purified from a plant or the like, in addition to a pure product or a mixture industrially produced. Examples thereof include 3- [8(Z),11(Z), 14-pentadecenyl ] phenol, 3- [8(Z),11(Z) -pentadecenyl ] phenol, 3- [8(Z) -pentadecenyl ] phenol, and 3- [11(Z) -pentadecenyl ] phenol, which are extracted from the shell of cashew nuts and are collectively called Cardanol (Cardanol).

The reactive emulsifier (B3) is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an oil or fat having a hydroxyl group and a polymerizable unsaturated group, and has an HLB of 7 to 18. Examples of the fat or oil having a hydroxyl group and a polymerizable unsaturated group include: and mono-or diglycerides of fatty acids which may have unsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α -linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.), triglycerides of fatty acids which contain at least 1 kind of hydroxyl unsaturated fatty acids (ricinoleic acid, 2-hydroxyeicosatetraenoic acid, etc.), and the like. In terms of emulsion stability of the acrylic resin, the alkylene oxide adduct of a triglyceride of a fatty acid containing at least 1 kind of hydroxyl unsaturated fatty acid is preferable, the alkylene oxide adduct of castor oil (triglyceride of a fatty acid containing ricinoleic acid) having 2 to 4 carbon atoms is more preferable, and the ethylene oxide adduct of castor oil is even more preferable. The number of moles of alkylene oxide added may be appropriately selected so as to fall within the above HLB range, and is more preferably 20 to 50 moles, and still more preferably 25 to 45 moles, from the viewpoint of emulsion stability of the acrylic resin. Further, in the case where the alkylene oxide is 2 or more, they may have a block addition structure or a random addition structure.

The reactive emulsifier (B3) can be synthesized by adding an alkylene oxide to an oil or fat having a hydroxyl group and a polymerizable unsaturated group by a conventionally known method, and is not particularly limited. For example, castor oil, which is a triglyceride of fatty acids including ricinoleic acid, can be synthesized by adding a specific amount of alkylene oxide to castor oil under pressure at 120 to 170 ℃ using an alkaline catalyst such as caustic soda or caustic potash.

The proportion of the reactive emulsifier (B) in the acrylic resin is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 3 to 10% by mass, based on the total amount of the monomer components constituting the acrylic resin, from the viewpoint of improving water repellency and emulsion stability of the acrylic resin.

When the water repellent composition contains an acrylic resin as the (α) component, the acrylic resin preferably contains, as a monomer component, in addition to the monomer (a), at least 1 type of 2 (meth) acrylate monomer (C) (hereinafter, also referred to as "monomer (C)") selected from the group consisting of (C1), (C2), (C3), (C4) and (C5) described below.

(C1) Is a (meth) acrylate monomer represented by the following general formula (C-1) except (C5).

[ solution 9]

[ formula (C-1) wherein R⁵Represents hydrogen or methyl, R⁶A 1-valent chain hydrocarbon group having 1 to 11 carbon atoms and having at least 1 functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group and a (meth) acryloyloxy group; wherein the number of (meth) acryloyloxy groups in the molecule is 2 or less.]

(C2) Is a (meth) acrylate monomer represented by the following general formula (C-2).

[ solution 10]

[ formula (C-2) wherein R⁷Represents hydrogen or methyl, R⁸Represents a C1-11 cyclic hydrocarbon group which may have a substituent.]

(C3) Is a methacrylate monomer represented by the following general formula (C-3).

[ solution 11]

[ formula (C-3) wherein R⁹Represents an unsubstituted C1-4 chain hydrocarbon group having a valence of 1.]

(C4) Is a (meth) acrylate monomer represented by the following general formula (C-4).

[ solution 12]

[ formula (C-4) wherein R¹⁰Represents hydrogen or methyl, p represents an integer of 2 or more, S represents a (p +1) -valent organic group, and T represents a 1-valent organic group having a polymerizable unsaturated groupAn organic group.]

(C5) Is a (meth) acrylate monomer represented by the following general formula (C-5).

[ solution 13]

[ formula (C-5) wherein R¹⁵Represents hydrogen or methyl, R¹⁶Represents a C3-6 1-valent chain-like saturated hydrocarbon group having at least 1 functional group selected from the group consisting of a chlorine group and a bromine group and a hydroxyl group.]

The monomer (C1) is a (meth) acrylate monomer having a 1-valent chain hydrocarbon group having 1 to 11 carbon atoms and at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group and a (meth) acryloyloxy group in an ester portion, and is a (meth) acrylate monomer other than the (C5). The 1-valent chain hydrocarbon group having 1 to 11 carbon atoms preferably has at least 1 functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group, in terms of being reactive with a crosslinking agent. When the fiber base material is treated with the composition containing the crosslinking agent and the acrylic resin containing the monomer of (C1) having the group reactive with the crosslinking agent, the water repellency can be improved while maintaining the texture of the fiber base material. The isocyanate group may also be a blocked isocyanate group protected by a blocking agent.

The chain hydrocarbon group may be straight or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The chain hydrocarbon group may further have a substituent in addition to the functional group. Among them, from the viewpoint of water repellency and texture, a linear and/or saturated hydrocarbon group is preferable.

Specific examples of the monomer (C1) include 2-hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, and 1, 1-bis (acryloyloxymethyl) ethyl isocyanate. These monomers may be used alone in 1 kind, or 2 or more kinds may be used in combination. Among them, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and 1, 1-bis (acryloyloxymethyl) ethyl isocyanate are preferable from the viewpoint of water repellency. From the viewpoint of water repellency, dimethylaminoethyl (meth) acrylate is preferable.

The proportion of the monomer of (C1) in the acrylic resin is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass, relative to the total amount of the monomer components constituting the acrylic resin, from the viewpoint of water repellency.

The monomer (C2) is a (meth) acrylate monomer having a 1-valent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester moiety, and examples of the cyclic hydrocarbon group include isobornyl, cyclohexyl, and dicyclopentyl. These cyclic hydrocarbon groups may have a substituent such as an alkyl group. When the substituent is a hydrocarbon group, the total number of carbon atoms of the substituent and the cyclic hydrocarbon group is selected to be 11 or less. In addition, these cyclic hydrocarbon groups are preferably directly bonded to an ester bond from the viewpoint of water repellency. The cyclic hydrocarbon group may be an alicyclic group or an aromatic group, and in the case of an alicyclic group, it may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Specific examples of the monomer include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. These monomers may be used alone in 1 kind, or 2 or more kinds may be used in combination. Among them, isobornyl (meth) acrylate and cyclohexyl methacrylate are preferable, and isobornyl methacrylate is more preferable, from the viewpoint of water repellency.

The proportion of the monomer of (C2) in the acrylic resin is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass, based on the total amount of the monomer components constituting the acrylic resin, from the viewpoint of water repellency.

The monomer (C3) is a methacrylate monomer in which an unsubstituted C1-4 chain hydrocarbon group is directly bonded to an ester bond in the ester moiety. The chain hydrocarbon group having 1 to 4 carbon atoms is preferably a straight-chain hydrocarbon group having 1 to 2 carbon atoms or a branched-chain hydrocarbon group having 3 to 4 carbon atoms. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl and the like. Specific examples of the compounds include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, and the like. These monomers may be used alone in 1 kind, or 2 or more kinds may be used in combination. Among these, methyl methacrylate, isopropyl methacrylate, and tert-butyl methacrylate are preferable, and methyl methacrylate is more preferable, from the viewpoint of water repellency.

The proportion of the monomer of (C3) in the acrylic resin is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass, based on the total amount of the monomer components constituting the acrylic resin, from the viewpoint of water repellency.

The monomer (C4) is a (meth) acrylate monomer having 3 or more polymerizable unsaturated groups in 1 molecule. In the present embodiment, a polyfunctional (meth) acrylate monomer having 3 or more (meth) acryloyloxy groups in 1 molecule, in which T in the general formula (C-4) is a (meth) acryloyloxy group, is preferable. In the formula (C-4), p T's may be the same or different. Specific examples of the compounds include: ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. These monomers may be used alone in 1 kind, or 2 or more kinds may be used in combination. Among these, tetramethylolmethane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferable from the viewpoint of water repellency.

The proportion of the monomer of (C4) in the acrylic resin is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass, based on the total amount of the monomer components constituting the acrylic resin, from the viewpoint of water repellency.

The monomer (C5) has a 1-valent chain saturated hydrocarbon group having 3 to 6 carbon atoms, and the chain saturated hydrocarbon group has at least 1 functional group selected from the group consisting of a chlorine group and a bromine group, and a hydroxyl group. In the monomer of (C5), R¹⁵Is hydrogen or methyl. From the viewpoint of water repellency, R¹⁵Preferably methyl.

R¹⁶Is a C3-6 1-valent chain-like saturated hydrocarbon group having at least 1 functional group selected from the group consisting of a chlorine group and a bromine group and a hydroxyl group. The chain saturated hydrocarbon group may be linear or branched. From the viewpoint of water repellency, the chain saturated hydrocarbon group is preferably linear. The number of carbon atoms in the chain-like saturated hydrocarbon group is preferably 3 to 4, more preferably 3, from the viewpoint of water repellency.

The chain saturated hydrocarbon group preferably has one or two chlorine groups and one hydroxyl group, and more preferably has one chlorine group and one hydroxyl group, from the viewpoint of water repellency. In addition, from the viewpoint of water repellency, the chain-like saturated hydrocarbon group is more preferably in the β -position (bonded to CH)₂＝CR¹⁵Carbon atoms adjacent to the carbon atom of (CO) O-) have a hydroxyl group. Specific examples of the chain saturated hydrocarbon group include: 3-chloro-2-hydroxypropyl, 3-chloro-2-hydroxybutyl, 5-chloro-2-hydroxypentyl, 3-chloro-2-hydroxy-2-methylpropyl, and 3-bromo-2-hydroxypropyl, and the like.

Specific examples of the monomer (C5) include: 3-chloro-2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxybutyl (meth) acrylate, 5-chloro-2-hydroxypentyl (meth) acrylate, and 3-bromo-2-hydroxypropyl (meth) acrylate, and the like. Among these, 3-chloro-2-hydroxypropyl (meth) acrylate and 3-chloro-2-hydroxypropyl methacrylate are preferable, and 3-chloro-2-hydroxypropyl methacrylate is more preferable, from the viewpoint of water repellency.

The proportion of the monomer of (C5) in the acrylic resin is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass, based on the total amount of the monomer components constituting the acrylic resin, from the viewpoint of water repellency.

The total composition ratio of the monomers (C) in the acrylic resin is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass, based on the total amount of the monomer components constituting the acrylic resin, from the viewpoint of water repellency.

When the water repellent composition contains an acrylic resin as the component (α), the acrylic resin may contain a monofunctional monomer (D) (hereinafter, also referred to as "monomer (D)") copolymerizable therewith in addition to the monomer (a), the reactive emulsifier (B) and the monomer (C) within a range not to impair the effects of the present invention.

Examples of the monomer (D) include: and (C) a vinyl monomer other than the monomer (E) described below, which does not contain fluorine, such as (meth) acryloylmorpholine, (meth) acrylate having a hydrocarbon group other than the monomer (a) and the monomer (C), (meth) acrylic acid, a fumarate ester, a maleate ester, fumaric acid, maleic acid, (meth) acrylamide, N-methylolacrylamide, a vinyl ether, a vinyl ester, ethylene, and styrene. The (meth) acrylate having a hydrocarbon group other than the monomer (a) and the monomer (C) may have a substituent such as a vinyl group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, or a blocked isocyanate group in the hydrocarbon group, may have a substituent other than a group reactive with the crosslinking agent such as a quaternary ammonium group, and may have an ether bond, an ester bond, an amide bond, or a urethane bond. Examples of the (meth) acrylic acid ester other than the monomer (a) and the monomer (C) include: methyl acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, and ethylene glycol di (meth) acrylate.

The proportion of the monomer (D) in the acrylic resin is preferably 10 mass% or less with respect to the total amount of monomer components constituting the acrylic resin, from the viewpoint of water repellency.

When the water repellent composition contains an acrylic resin as the (α) component, the acrylic resin preferably has at least 1 functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group, which is reactive with the crosslinking agent, from the viewpoint of water repellency. The isocyanate groups may also form blocked isocyanate groups which are protected by blocking agents. The acrylic resin preferably has an amino group from the viewpoint of water repellency.

When the water repellent composition contains an acrylic resin, the acrylic resin preferably contains at least 1 monomer (E) of vinyl chloride and vinylidene chloride (hereinafter also referred to as "monomer (E)") as a monomer component in addition to the monomer (a) from the viewpoint of peel strength.

In the present embodiment, at least any 1 kind of monomer (E) of vinyl chloride and vinylidene chloride used is preferably vinyl chloride from the viewpoint of maintaining the texture of the fiber base material.

The proportion of the monomer (E) in the acrylic resin may be 1 to 50% by mass, and from the viewpoint of water repellency and peel strength, the proportion is preferably 1 to 45% by mass, more preferably 3 to 40% by mass, and still more preferably 5 to 35% by mass, based on the total amount of the monomer components constituting the acrylic resin.

The acrylic resin can be synthesized by a conventionally known method, and is not particularly limited, and can be synthesized by, for example, a radical polymerization method. In the radical polymerization method, polymerization is preferably carried out by emulsion polymerization or dispersion polymerization in terms of the performance of the obtained water repellent and the environment.

For example, the acrylic resin can be obtained by emulsion polymerization or dispersion polymerization of the (meth) acrylate monomer (a) represented by the above general formula (a-1) in a medium. More specifically, for example, the monomer (a) and, if necessary, the reactive emulsifier (B), the monomer (C), the monomer (D), and the monomer (E), and an emulsification aid or a dispersion aid are added to a medium, and the mixture is emulsified or dispersed to obtain an emulsion or a dispersion. The monomers and the reactive emulsifier can be polymerized by adding a polymerization initiator to the obtained emulsion or dispersion to start the polymerization reaction. Further, as means for emulsifying or dispersing the mixed solution, a homomixer, a high-pressure emulsifier, ultrasonic waves, or the like can be mentioned.

As the emulsification aid, dispersion aid, or the like (hereinafter, also referred to as "emulsification aid or the like"), 1 or more kinds selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants other than the reactive emulsifier (B) can be used. From the viewpoint of storage stability, nonionic surfactants are preferred, such as emulsification aids.

Examples of the nonionic surfactant include: alcohols, polycyclic phenols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, oils and fats, alkylene oxide adducts of polypropylene glycol, and the like.

Examples of alcohols include: straight-chain or branched C8-24 alcohol or enol (alkenol), alkynol represented by the following general formula (AL-1) or (AL-2), and the like.

[ solution 14]

[ in the formula (AL-1), R²¹And R²²Each independently represents a C1-C8 linear or branched alkyl group or a C2-C8 linear or branched alkenyl group.]

[ solution 15]

[ in the formula (AL-2), R²³Represents a C1-8 linear or branched alkyl group or a C2-8 linear or branched alkenyl group.]

Examples of the polycyclic phenols include 1-valent phenols such as phenol and naphthol having a hydrocarbon group of 1 to 12 carbon atoms, styrene (styrene,. alpha. -methylstyrene, vinyltoluene) adducts thereof, benzyl chloride reaction products thereof, and the like. Examples of the amine include linear or branched aliphatic amines having 8 to 44 carbon atoms.

Examples of the amide include a linear or branched aliphatic amide having 8 to 44 carbon atoms.

Examples of the fatty acids include linear or branched fatty acids having 8 to 24 carbon atoms.

Examples of the polyol fatty acid esters include condensation products of a polyol and a linear or branched fatty acid having 8 to 24 carbon atoms.

Examples of the oils and fats include: vegetable oil and fat, animal oil and fat, vegetable wax, animal wax, mineral wax, hardened oil, etc.

Among these, from the viewpoints of less influence on water repellency and water repellency durability, less influence on light resistance, good emulsifiability of the acrylic resin, and the like, a linear or branched C8-24 alcohol or enol, and an alkynol represented by the general formula (AL-1) are preferable, and a linear or branched C8-24 alcohol, and an alkynol represented by the general formula (AL-1) are more preferable.

Examples of alkylene oxides include: ethylene oxide, 1, 2-propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, 1, 4-butylene oxide, styrene oxide, epichlorohydrin, and the like. The alkylene oxide is preferably ethylene oxide and 1, 2-propylene oxide, and more preferably ethylene oxide, from the viewpoints of reducing the influence on water resistance and improving emulsifiability of the copolymer.

The number of moles of alkylene oxide added is preferably 1 to 200, more preferably 3 to 100, and still more preferably 5 to 50. When the molar number of addition of the alkylene oxide is within the above range, water repellency and emulsifiability of the copolymer tend to be further improved.

In the copolymer of the present embodiment, when a nonionic surfactant having HLB defined by the following formula (H) of 4 to 17 is used as the nonionic surfactant, a more favorable aqueous dispersion can be obtained. Here, the HLB defined by the following formula (H) is an HLB by Griffin (Griffin), and the Griffin formula is changed to the following formula (H). Here, the hydrophilic group means an ethylene oxide group.

HLB (hydrophilic group. times.20)/molecular weight (H)

The HLB of the nonionic surfactant defined by the formula (H) is preferably 5 to 15 in terms of emulsion stability (hereinafter, simply referred to as emulsion stability) in the composition during and after emulsion polymerization or dispersion polymerization of the component (a). Further, from the viewpoint of storage stability of the water repellent composition, it is more preferable to use 2 or more nonionic surfactants having different HLBs within the above range in combination. In addition, from the viewpoint of emulsion stability and water resistance, it is preferable to use a cationic surfactant in combination with a nonionic surfactant.

The content of the emulsification aid and the like is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total monomers constituting the acrylic resin. If the content of the emulsification aid or the like is 0.5 parts by mass or more, the dispersion stability of the mixed liquid tends to be further improved as compared with the case where the content of the emulsification aid or the like is less than 0.5 parts by mass, and if the content of the emulsification aid or the like is 30 parts by mass or less, the water repellency of the obtained water repellent composition tends to be improved as compared with the case where the content of the emulsification aid or the like exceeds 30 parts by mass.

The medium for the emulsion polymerization or dispersion polymerization is preferably water, and water may be mixed with an organic solvent as required. Examples of the organic solvent include: alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether, and glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol. In order to further improve the water repellency and water impermeability imparted to the fiber base material, it is preferable to use a glycol. The ratio of water to the organic solvent is not particularly limited.

As the polymerization initiator, a known polymerization initiator such as azo type, peroxide type, or redox type can be suitably used. The content of the polymerization initiator is preferably 0.01 to 2 parts by mass relative to 100 parts by mass of the total monomers constituting the acrylic resin. When the content of the polymerization initiator is in the above range, an acrylic resin having a weight average molecular weight of 10 ten thousand or more can be efficiently produced.

In the polymerization reaction, a chain transfer agent such as dodecyl mercaptan or tert-butyl alcohol may be used for adjusting the molecular weight.

Further, a polymerization inhibitor may be used for the adjustment of the molecular weight. By adding the polymerization inhibitor, an acrylic resin having a desired weight average molecular weight can be easily obtained.

The polymerization temperature is preferably from 20 ℃ to 150 ℃. If the temperature is less than 20 ℃, polymerization tends to be insufficient as compared with the case where the temperature is in the above range, and if the temperature exceeds 150 ℃, control of the reaction heat may be difficult.

In the polymerization reaction, the weight average molecular weight of the obtained acrylic resin can be adjusted by increasing or decreasing the contents of the above-mentioned polymerization initiator, chain transfer agent and polymerization inhibitor, and the melt viscosity at 105 ℃ can be adjusted by increasing or decreasing the contents of the polyfunctional monomer and the polymerization initiator. When the melt viscosity at 105 ℃ is to be decreased, the content of the monomer having 2 or more polymerizable functional groups may be decreased or the content of the polymerization initiator may be increased.

The content of the acrylic resin in the emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, based on the total amount of the emulsion or dispersion, from the viewpoint of storage stability and handling properties of the composition.

In the polymerization reaction, for example, polymerization reaction may be carried out by photopolymerization such as irradiation with ultraviolet rays, electron beams, or ionizing radiation such as γ rays, instead of carrying out polymerization reaction by a polymerization initiator.

Next, the urethane resin will be described.

The urethane resin as the component (. alpha.) can be obtained by reacting at least the polyfunctional compound represented by the above general formula (I-1) with the isocyanate compound represented by the above general formula (II-1).

The polyfunctional compound represented by the above general formula (I-1) will be described.

In the above general formula (I-1), when d is 2 or more, a plurality of W's are present¹May be the same or different. There are a plurality of R³²May be the same or different. There are a plurality of V¹May be the same or different.

R³¹An organic group having a valence of (d + e). From the viewpoint of water repellency and water permeation resistance, R³¹The carbon number of (b) is preferably 2 to 40, more preferably 4 to 12. As R³¹The group represented by the following chemical formula (1), the group represented by the following chemical formula (2), and the group represented by the following chemical formula (3) are preferable. The (d + e) is preferably 3 to 4 from the viewpoint of ease of handling of the urethane resin.

[ solution 16]

[ solution 17]

[ solution 18]

In the formula (3), r represents an integer of 1 or more. ]

r represents an integer of 1 or more, preferably 1 to 3.

R³¹The residue may be a residue obtained by removing (d + e) functional groups from a polyfunctional compound having (d + e) functional groups of at least 1 kind selected from the group consisting of hydroxyl groups, amino groups, and carboxyl groups (hereinafter, also referred to as "polyfunctional compound a"). Wherein 2 or more of the (d + e) functional groups are hydroxyl and/or amino.

Examples of the polyfunctional compound a include: trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, glycerol, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, aminoethylethanolamine, diethanolamine, triethanolamine, and the like. Among these, trimethylolpropane, ditrimethylolpropane, diethanolamine and diethylenetriamine are preferable from the viewpoint of water repellency and water impermeability and emulsion dispersion stability of the obtained urethane resin.

W¹2-valent groups which are represented as ester groups, amide groups, urethane groups or urea groups. W¹From the viewpoint of water repellency and water permeation resistance, an ester group or a urethane group is preferable.

R³²Represents a linear or branched 1-valent hydrocarbon group having 10 to 24 carbon atoms. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may further have an alicyclic or aromatic cyclic structure. The hydrocarbon group is preferably a linear alkyl group, and more preferably a linear alkyl group, from the viewpoint of water repellency and water permeation resistance. The number of carbon atoms of the hydrocarbon group is preferably 10 to 24, more preferably 12 to 22, and particularly preferably 12 to 18. When the carbon number is in this range, it is easy to sufficiently maintain the texture of the fiber base material and to improve the water repellency and water impermeability imparted to the fiber base material. The hydrocarbon group is particularly preferably a linear alkyl group having 12 to 18 carbon atoms.

As R³²Examples thereof include: nonyl, decyl, undecyl, dodecyl (lauryl), tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, and behenyl groups.

R³²May be a residue obtained by removing a reactive group from a reactive hydrocarbon compound having a reactive group capable of reacting with the functional group of the polyfunctional compound a. Examples of the reactive hydrocarbon compound include: a higher fatty acid having 8 to 24 carbon atoms (the carbon atoms include a carbonyl group), a higher aliphatic alcohol, a higher aliphatic monoisocyanate, and a higher aliphatic amine.

Examples of the higher fatty acid include: lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, eicosanoic acid, behenic acid, and the like.

Examples of the higher aliphatic alcohol include: lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, arachidyl alcohol, heneicosanol, behenyl alcohol and the like.

Examples of the higher aliphatic monoisocyanate include: decyl isocyanate, undecyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, pentadecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, eicosyl isocyanate, and behenyl isocyanate.

Examples of the higher aliphatic amine include: decylamine, laurylamine, tetradecylamine, stearylamine, and behenylamine, and the like.

V¹Represents a hydroxyl group, an amino group or a carboxyl group. V¹From the viewpoint of water repellency, a hydroxyl group or an amino group is preferable.

The polyfunctional compound represented by the above general formula (I-1) can be produced, for example, by introducing d [ -W ] s into a polyfunctional compound (polyfunctional compound A) having (d + e) at least 1 functional group selected from the group consisting of the above hydroxyl groups, amino groups and carboxyl groups¹-R³²]The hydrophobic group shown.

[-W¹-R³²]The hydrophobic group represented by the formula (i) can be introduced, for example, by reacting 1 mole or more of the reactive hydrocarbon compound with 1 mole of the polyfunctional compound (a) by an esterification reaction, an amidation reaction or a urethane reaction, which is a conventionally known synthesis method, so that the number e of unreacted functional groups of the polyfunctional compound (a) is 2 or more.

The polyfunctional compound represented by the above general formula (I-1) is not particularly limited, and is preferably at least 1 selected from the group consisting of a polyfunctional compound represented by the following general formula (I-2), a polyfunctional compound represented by the following general formula (I-3), and a polyfunctional compound represented by the following general formula (I-4).

C[-R⁴¹]_g[-R⁴²-V²]_h[-R⁴³-W²-R⁴⁴]_i (I-2)

[ in the formula (I-2)G is an integer of 0 or 1, h is an integer of 2 or 3, i is an integer of 1 or 2, (g + h + i) is 4, R⁴¹Represents a C1-4 linear or branched hydrocarbon group, R⁴²Represents C1-2 alkylene, R⁴³Represents C1-4 alkylene 2, R⁴⁴W represents a linear or branched 1-valent hydrocarbon group having 8 to 24 carbon atoms²A 2-valent radical which is an ester, amide, carbamate or urea group, V²Represents a hydroxyl group, an amino group or a carboxyl group. Wherein, more than 2V²Hydroxyl and/or amino.]

[ solution 19]

[ in the formula (I-3), R⁵¹And R⁵²Each independently represents a C1-4 linear or branched hydrocarbon group, R⁵⁴And R⁵⁵Each independently represents a C1-4 alkylene group having a valence of 2, R⁵³、R⁵⁶、R⁵⁷And R⁵⁸Each independently represents a 1-valent group represented by the following general formula (4) or the following general formula (5);

-R⁵⁹-V³(4)

{R⁵⁹represents a C1-4 alkylene group having a valence of 2, V³Represents a hydroxyl group, an amino group or a carboxyl group. }

-R⁶⁰-W³-R⁶¹(5)

{R⁶⁰Represents C1-4 alkylene 2, R⁶¹W represents a linear or branched 1-valent hydrocarbon group having 8 to 24 carbon atoms³2-valent groups which are represented as ester groups, amide groups, urethane groups or urea groups. },

wherein R is⁵³、R⁵⁶、R⁵⁷And R⁵⁸At least 2 of which are V³A group represented by the above general formula (4) which is a hydroxyl group or an amino group.]

[ solution 20]

[ formula (I-4) wherein j represents an integer of 1 to 4, R⁷¹And R⁷³Each independently represents a C1-4 alkylene group having a valence of 2, R⁷²And R⁷⁴Each independently represents a hydroxyl group, an amino group or a 1-valent group represented by the following general formula (6)⁷⁵Represents hydrogen, a 1-valent group represented by the following general formula (7), the following general formula (8) or the following general formula (9);

-W⁴-R⁷⁶ (6)

{ formula (6) { W⁴A 2-valent radical which is an ester, amide, carbamate or urea group, R⁷⁶Represents a C8-24 linear or branched 1-valent hydrocarbon group. }

-R⁷⁷-OH (7)

{ formula (7) { wherein R is⁷⁷Represents an alkylene group having 2 to 3 carbon atoms. }

-R⁷⁸-W⁵-R⁷⁹ (8)

{ formula (8) { wherein R⁷⁸R represents a C2-3 alkylene group⁷⁹W represents a linear or branched 1-valent hydrocarbon group having 8 to 24 carbon atoms⁵2-valent groups which are represented as ester groups, amide groups, urethane groups or urea groups. }

-W⁶-R⁸⁰ (9)

{ formula (9) } W⁶Represents a carbonyl or amide group, R⁸⁰Represents a C8-24 linear or branched 1-valent hydrocarbon group. },

wherein R is⁷²、R⁷⁴And j R⁷⁵At least 2 of the above groups are hydroxyl, amino, hydrogen, a 1-valent group represented by the above general formula (7), R⁷²And R⁷⁴Is hydroxy or amino, R⁷⁵Is hydrogen or a 1-valent group represented by the above general formula (7).]

In the polyfunctional compound represented by the above general formula (I-2), when I is 2, a plurality of W's are present²May be the same or different. In the case where i is 2, there are a plurality of R⁴³May be the same or different. In the case where i is 2, there are a plurality of R⁴⁴May be the same or different. R⁴⁴And R in the above general formula (I-1)³²Correspond to. There are a plurality of R⁴²May be the same or different. There are a plurality of V²May be the same or different.

In the polyfunctional compound represented by the above general formula (I-2), W²Is a 2-valent radical which is an ester group, amide group, urethane group or urea group. W²From the viewpoint of water repellency and water permeation resistance, an ester group or a urethane group is preferable.

In the polyfunctional compound represented by the above general formula (I-2), V²Is hydroxyl, amino or carboxyl. V²From the viewpoint of water repellency, a hydroxyl group or an amino group is preferable.

In the group represented by the above general formula (4), V³Is hydroxyl, amino or carboxyl. V³From the viewpoint of water repellency, a hydroxyl group or an amino group is preferable.

In the group represented by the above general formula (5), R⁶¹Is a C8-24 linear or branched 1-valent hydrocarbon group. R⁶¹And R in the above general formula (I-1)³²And (7) corresponding.

In the group represented by the above general formula (5), W³Is a 2-valent radical which is an ester group, amide group, urethane group or urea group. W³From the viewpoint of water repellency and water permeation resistance, an ester group or a urethane group is preferable.

In the group represented by the above general formula (6), R⁷⁶Is a C8-24 linear or branched 1-valent hydrocarbon group. R⁷⁶And R in the above general formula (I-1)³²And (7) corresponding.

In the group represented by the above general formula (6), W⁴Is a 2-valent radical which is an ester group, amide group, urethane group or urea group. W⁴From the viewpoint of water repellency and water permeation resistance, an ester group, an amide group, or a urethane group is preferable.

In the group represented by the above general formula (8), R⁷⁹Is a C8-24 linear or branched 1-valent hydrocarbon group. R⁷⁹And R in the above general formula (I-1)³²And (7) corresponding.

In the group represented by the above general formula (8), W⁵Is an ester group, an amide group, a carbamateRadical or 2-valent radical of a ureido group. W⁵From the viewpoint of water repellency and water permeation resistance, an ester group, an amide group, or a urethane group is preferable.

In the group represented by the above general formula (9), R⁸⁰Is a C8-24 linear or branched 1-valent hydrocarbon group. R⁸⁰And R in the above general formula (I-1)³²And (7) corresponding.

Next, the isocyanate compound represented by the above general formula (II-1) will be described.

R³³Represents an f-valent organic group. R³³The carbon number of (b) is preferably 4 to 40, more preferably 6 to 18, from the viewpoint of water repellency and water impermeability. As R³³Preferably, it is hexylene. f may be an integer of 2 to 7, and is preferably 2 to 3 from the viewpoint of water repellency and water permeation resistance.

The isocyanate compound represented by the above general formula (II-1) may be a polyisocyanate compound. Examples of the polyisocyanate compound include: diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate (MDI), liquid MDI represented by polyphenyl polymethylene polyisocyanate, crude MDI, hexamethylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and isophorone diisocyanate, and trimers thereof, which are isocyanurate rings. Among these, hexamethylene diisocyanate is preferable from the viewpoint of water repellency and water impermeability.

Examples of the urethane resin obtained by reacting the polyfunctional compound represented by the general formula (I-1) with the isocyanate compound represented by the general formula (II-1) include urethane resins having partial structures represented by the following general formula (III-1), general formula (III-2) and general formula (III-3).

[ solution 21]

[ in the formula (III-1), k1 represents an integer of 2 or more, R¹¹¹And R¹¹²Each independently represents a linear or branched 1-valent hydrocarbon group having 10 to 24 carbon atoms.]

k1 is an integer of 2 or more, and is preferably 2 to 100, more preferably 2 to 50, from the viewpoint of water repellency and water impermeability, further improvement in emulsion dispersion stability of the urethane resin, and further easier handling of the urethane resin.

[ solution 22]

[ in the formula (III-2), k2 represents an integer of 2 or more, k3 represents an integer of 1 or more, and R¹¹³Each independently represents a linear or branched 1-valent hydrocarbon group having 10 to 24 carbon atoms.]

k2 is an integer of 2 or more, and is preferably 2 to 200, more preferably 2 to 100, from the viewpoint of water repellency and water impermeability, further improvement in emulsion dispersion stability of the urethane resin, and further easier handling of the urethane resin.

k3 represents an integer of 1 or more, and is preferably 1 to 3, more preferably 1, from the viewpoint of water repellency and water impermeability, and further improvement in emulsion dispersion stability of the urethane resin.

[ solution 23]

[ in the formula (III-3), k4 represents an integer of 2 or more, R¹¹⁴Each independently represents a linear or branched 1-valent hydrocarbon group having 10 to 24 carbon atoms.]

k4 is an integer of 2 or more, and is preferably 2 to 200, more preferably 2 to 100, from the viewpoint of water repellency and water impermeability, further improvement in emulsion dispersion stability of the urethane resin, and further easier handling of the urethane resin.

Examples of the urethane resin having a partial structure represented by the above general formula (III-1) include compounds represented by the following general formula (III-4).

[ solution 24]

[ in the formula (III-4), k5 represents an integer of 2 or more, R_XRepresents a monovalent organic group represented by the following formula (R-1).]

k5 is an integer of 2 or more, and is preferably 2 to 100, more preferably 2 to 50, from the viewpoint of water repellency and water impermeability, further improvement in emulsion dispersion stability of the urethane resin, and further easier handling of the urethane resin.

[ solution 25]

Examples of the urethane resin having a partial structure represented by the above general formula (III-2) include compounds represented by the following general formula (III-5).

[ solution 26]

[ in the formula (III-5), k6 represents an integer of 2 or more, and k7 represents an integer of 1 or more; r_XRepresents a monovalent organic group represented by the formula (R-1).]

k6 is an integer of 2 or more, and is preferably 2 to 200, more preferably 2 to 100, from the viewpoint of water repellency and water impermeability, further improvement in emulsion dispersion stability of the urethane resin, and further easier handling of the urethane resin.

k7 represents an integer of 1 or more, and is preferably 1 to 3, more preferably 1, from the viewpoint of water repellency and water impermeability, from the viewpoint of further improving the emulsion dispersion stability of the urethane resin, and from the viewpoint of further facilitating the handling of the urethane resin.

Examples of the urethane resin having a partial structure represented by the above general formula (III-3) include compounds represented by the following general formula (III-6).

[ solution 27]

[ in the formula (III-6), k8 represents an integer of 2 or more, R_XRepresents a monovalent organic group represented by the formula (R-1).]

k8 is an integer of 2 or more, and is preferably 2 to 200, more preferably 2 to 100, from the viewpoint of water repellency and water impermeability, further improvement in emulsion dispersion stability of the urethane resin, and further easier handling of the urethane resin.

The urethane resin preferably has a blocked isocyanate group protected with a blocking agent in terms of further improvement in chemical resistance. The ratio of the blocked isocyanate group to the total number of the isocyanate group and the blocked isocyanate group contained in the urethane resin is preferably 80% or more, more preferably 90% or more, and further preferably 100% from the viewpoint of chemical resistance.

Examples of the blocked isocyanate group protected with a blocking agent include a group represented by the following general formula (10).

(-NH-CO-B) (10)

[ in formula (10), B is a group derived from a capping agent. ]

Examples of the blocking agent include: pyrazoles such as 3, 5-dimethylpyrazole, 3-methylpyrazole, 3, 5-dimethyl-4-nitropyrazole, 3, 5-dimethyl-4-bromopyrazole and pyrazole; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and t-butanol; phenols such as phenol, methylphenol, chlorophenol, p-isobutylphenol, p-tert-butylphenol, p-isopentylphenol, p-octylphenol, and p-nonylphenol; active methylene compounds such as dimethyl malonate, diethyl malonate, acetylacetone, methyl acetoacetate, and ethyl acetoacetate; oximes such as formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; lactams such as epsilon-caprolactam, delta-valerolactam and gamma-butyrolactam; n-substituted amides such as N-methylacetamide and acetanilide; imide compounds such as succinimide and phthalimide; imidazole compounds such as imidazole and 2-methylimidazole. The blocking agent can be used alone in 1 kind, also can be used in more than 2 kinds combination. Among these, from the viewpoint of general versatility, reactivity of blocked isocyanate groups, and easiness of blocking, it is preferable to use at least 1 compound selected from the group consisting of pyrazoles, oximes, and lactams, and more preferably at least 1 compound selected from the group consisting of dimethylpyrazole, methyl ethyl ketoxime, and caprolactam.

The weight average molecular weight of the urethane resin is preferably 2,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 2,000 to 20,000, from the viewpoint of water repellency and water impermeability, and from the viewpoint of further improving the emulsion dispersion stability of the urethane resin.

About making have e¹The amount of the compound represented by the general formula (II-1) added when the polyfunctional compound represented by the general formula (I-1) having a hydroxyl group and/or an amino group reacts with the compound represented by the general formula (II-1) is preferably (0.8 to 1.20). times.2/e per 1 mol of the polyfunctional compound represented by the general formula (I-1)¹More preferably (0.80 to 0.99). times.2/e¹The molar ratio is more preferably (0.85 to 0.95). times.2/e¹And (3) mol. Or more preferably (1.01 to 1.20). times.2/e¹The molar ratio is more preferably (1.05 to 1.15). times.2/e¹。

The urethane resin of the present embodiment is preferably emulsified or dispersed with an emulsification aid or a dispersion aid in terms of water-repellent performance and environment. The emulsion or dispersion containing the urethane resin of the present embodiment can be produced, for example, as follows.

An emulsion or dispersion can be obtained by: the urethane resin of the present embodiment is added with a surfactant as an emulsification aid or a dispersion aid to be uniform, and water is slowly added thereto while stirring.

As the surfactant, 1 or more conventionally known surfactants selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants can be used. The content of the emulsification aid and the like is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, and still more preferably 20 to 30 parts by mass with respect to 100 parts by mass of the urethane resin of the present embodiment. If the content of the emulsification aid or the like is in the above range, the emulsion dispersion stability of the urethane resin can be improved while the water repellency is easily maintained.

The medium for emulsification or dispersion is preferably water, and water may be mixed with an organic solvent as needed. Examples of the organic solvent include: alcohols such as methanol and ethanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether; glycols such as propylene glycol, dipropylene glycol, tripropylene glycol, and the like. The ratio of mixing water and the organic solvent is not particularly limited. The organic solvent may be distilled off under reduced pressure during or after the preparation of the aqueous dispersion, or may be left as it is.

The obtained aqueous dispersion of the urethane resin can be made into uniform particles by a homogenizer (manufactured by Primix), a homogenizer (manufactured by nirosavi or APVGAULIN), a nanotimizer (manufactured by yoda mechanical co., ltd.), an altizer (アルチマイザー, manufactured by Sugino Machine corporation), a high-pressure emulsifier or an ultrasonic emulsifier such as Starburst (manufactured by Sugino Machine co., ltd.).

The component (β) contained in the water repellent composition of the present embodiment will be described in detail below.

In the above general formula (L-1), each structural unit may be a block, may be random, or may be arranged alternately.

In the component (. beta.) of the present embodiment, the alkoxy group having 1 to 4 carbon atoms may be linear or branched. MakingThe alkoxy group having 1 to 4 carbon atoms includes, for example: methoxy, ethoxy, propoxy, butoxy, and the like. R is easy to industrially produce and purchase²²⁰、R²²¹And R²²²Each independently is preferably a hydrogen atom or a methyl group, more preferably a methyl group.

Examples of the C8-40 hydrocarbon group having an aromatic ring include C8-40 aralkyl groups, groups represented by the following general formula (L-2) or (L-3), and the like.

[ solution 28]

[ in the formula (L-2), R²⁴⁰R represents a C2-6 alkylene group²⁴¹Represents a single bond or an alkylene group having 1 to 4 carbon atoms, and a3 represents an integer of 0 to 3. In the case where a3 is 2 or 3, there are a plurality of R²⁴¹May be the same or different.]

The alkylene group may be linear or branched.

[ solution 29]

[ formula (L-3) wherein R²⁴²R represents a C2-6 alkylene group²⁴³Represents a single bond or an alkylene group having 1 to 4 carbon atoms, and a4 represents an integer of 0 to 3. In the case where a4 is 2 or 3, there are a plurality of R²⁴³May be the same or different.]

The alkylene group may be linear or branched.

Examples of the aralkyl group having 8 to 40 carbon atoms include: phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, naphthylethyl, and the like. Among them, phenylethyl and phenylpropyl are preferable in terms of easy industrial production and easy purchase.

Among the groups represented by the above general formula (L-2), R is easy to produce industrially and to purchase²⁴⁰Preferably an alkylene group having 2 to 4 carbon atoms, and a3 is preferably 0 or 1, more preferably 0.

Among the groups represented by the above general formula (L-3), R is easily industrially produced and easily purchased²⁴²Preferably an alkylene group having 2 to 4 carbon atoms, and a4 is preferably 0 or 1, more preferably 0.

The C8-40 hydrocarbon group having an aromatic ring is preferably the C8-40 aralkyl group or the group represented by the general formula (L-2), and more preferably the C8-40 aralkyl group, from the viewpoint of imparting water repellency and water impermeability to the fibrous base material, in view of easy industrial production and easy purchase.

The alkyl group having 3 to 22 carbon atoms may be straight or branched. Examples of the alkyl group having 3 to 22 carbon atoms include: hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, and octadecyl, and the like. The alkyl group having 3 to 22 carbon atoms is preferably an alkyl group having 8 to 20 carbon atoms, more preferably an alkyl group having 12 to 18 carbon atoms, from the viewpoint of imparting water repellency and water repellency to the fiber base material.

In the component (. beta.) of the present embodiment, R²³⁰、R²³¹、R²³²、R²³³、R²³⁴And R²³⁵Each independently represents a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms. R is preferably R in view of easy industrial production and easy purchase²³⁰、R²³¹、R²³²、R²³³、R²³⁴And R²³⁵Each independently represents a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms, and more preferably a methyl group.

In the component (β) of the present embodiment, a1 is an integer of 0 or more. From the viewpoint of easy industrial production and easy purchase, and imparting water repellency and water-proof property to the fiber base material, a1 is preferably 40 or less, more preferably 30 or less.

In the component (β) of the present embodiment, (a1+ a2) is 10 to 200. In terms of easy industrial production and easy purchase, (a1+ a2) is preferably 20 to 100, more preferably 40 to 60. If (a1+ a2) is within the above range, the silicone itself tends to be easily produced or handled.

The component (β) of the present embodiment can be synthesized by a conventionally known method. The component (β) of the present embodiment can be obtained, for example, by subjecting an aromatic compound having a vinyl group and/or an α -olefin to a hydrosilylation reaction with an organosilicon having an SiH group.

Examples of the silicone having an SiH group include methylhydrogensilicone having a polymerization degree of 10 to 200, and a copolymer of dimethylsiloxane and methylhydrogensiloxane. Among these, methyl hydrogen silicone is preferable in terms of easy industrial production and easy purchase.

The aromatic compound having a vinyl group is R in the general formula (L-1)²²³Wherein the aromatic ring is a compound derived from a C8-40 hydrocarbon group. Examples of the aromatic compound having a vinyl group include: styrene, α -methylstyrene, vinylnaphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-cumyl phenyl ether, allyl-o-phenyl ether, allyl-tris (phenylethyl) -phenyl ether, and allyl-tris (2-phenylpropyl) phenyl ether.

The alpha-olefin is R in the general formula (L-1)²²³A compound derived from an alkyl group having 3 to 22 carbon atoms. As the α -olefin, for example, there can be mentioned: and alpha-olefins having 3 to 22 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene.

The hydrosilylation reaction may be carried out by reacting the aromatic compound having a vinyl group and the α -olefin with the organosilicon having an SiH group in stages or at a time in the presence of a catalyst as necessary.

The amounts of the SiH group-containing silicone, the vinyl group-containing aromatic compound, and the α -olefin used in the hydrosilylation reaction can be appropriately selected according to the SiH group equivalent weight, the number average molecular weight, and the like of the SiH group-containing silicone.

Examples of the catalyst used for the hydrosilylation reaction include compounds such as platinum and palladium, and among them, a platinum compound is preferable. Examples of the platinum compound include platinum (IV) chloride.

The reaction conditions of the hydrosilylation reaction are not particularly limited and may be appropriately adjusted. The reaction temperature is, for example, 10 to 200 ℃ and preferably 50 to 150 ℃. The reaction time can be set to 3 to 12 hours at a reaction temperature of 50 to 150 ℃.

Further, the hydrosilylation reaction is preferably performed in an inert gas atmosphere. Examples of the inert gas include nitrogen gas and argon gas. The reaction can be carried out even without a solvent, but a solvent can also be used. Examples of the solvent include: dioxane, methyl isobutyl ketone, toluene, xylene, butyl acetate, and the like.

The content ratio of the (α) component to the (β) component in the present embodiment is preferably 95: 5-50: 50, more preferably 90: 10-60: 40, more preferably 80: 20-70: 30.

the component (γ) contained in the water repellent composition of the present embodiment will be described in detail below.

The component (γ) in the present embodiment is not particularly limited, and examples thereof include: paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, animal and vegetable waxes, mineral waxes, and the like. The component (γ) is preferably paraffin from the viewpoint of water resistance and texture.

The compound constituting the component (γ) of the present embodiment is not particularly limited, and examples thereof include n-alkanes and n-alkenes. The component (γ) is preferably n-alkane from the viewpoint of water repellency and texture.

Examples of the n-alkane include: tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, triacontane, tetratriacontane, pentadecane and hexadecane. From the viewpoint of water repellency and texture, n-alkane is preferably triacontane, hentriacontane, and dotriacontane.

Examples of the normal olefins include: 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosene, triacontene, undecene, dotriacontone, dotetradecene, dotriacontane, and dotriacontane. The n-olefin is preferably triacontene, triundecene, and triacontene from the viewpoint of water resistance and texture.

The carbon number of the component (γ) in the present embodiment is not particularly limited, and may be 20 to 60, and is preferably 25 to 45 from the viewpoint of water repellency and texture.

The weight average molecular weight of the component (γ) in the present embodiment is not particularly limited, and may be 300 to 850, and is preferably 300 to 700 from the viewpoint of water repellency and texture.

The melting point of the component (γ) in the present embodiment is not particularly limited, and may be, for example, 40 to 90 ℃, and is preferably 55 to 85 ℃, more preferably 60 to 80 ℃, even more preferably 65 to 78 ℃, and particularly preferably 70 to 78 ℃ from the viewpoint of water repellency and texture. The melting point of the (. gamma.) component means a value measured in accordance with JIS K2235-1991.

The penetration degree of the component (γ) in the present embodiment is not particularly limited, and may be, for example, 30 or less, and from the viewpoint of water repellency, preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. The penetration degree of the component (γ) in the present embodiment is not particularly limited, and may be, for example, 0.1 or more, and may be 1 or more. The penetration of the component (. gamma.) is a value measured by the same method as JIS K2235-1991.

The content ratio of the (α) component to the (γ) component in the present embodiment is preferably 90: 10-40: 60, more preferably 80: 20-50: 50, more preferably 70: 30-60: 40. when the content ratio of the component (α) to the component (γ) is in the above range, the texture of the fiber base material can be sufficiently maintained and excellent water repellency and water impermeability can be provided.

The component (γ) of the present embodiment is preferably emulsified or dispersed with an emulsification aid or a dispersion aid in terms of water-repellent performance and environment. The aqueous dispersion of the component (γ) of the present embodiment can be produced by dispersing the component (γ) in water in the presence of an emulsifier for wax. The aqueous dispersion of the component (γ) is preferably produced by mixing the component (γ), water, and wax with an emulsifier. The temperature during mixing is not particularly limited, and may be, for example, 60 to 90 ℃. The time for mixing is not particularly limited, and may be, for example, 10 seconds to 10 hours. The mixing is preferably carried out by using a homomixer.

The water repellent composition of the present embodiment may further contain a crosslinking agent (hereinafter, also referred to as "(δ)" component) from the viewpoint of water repellency. The component (δ) will be described in detail below.

The component (δ) in the present embodiment is not particularly limited, and examples thereof include: melamine resins, glyoxal resins, and compounds having 1 or more isocyanate groups or blocked isocyanate groups. Further, the compound having 1 or more isocyanate groups or blocked isocyanate groups as the component (δ) does not contain a urethane resin having a structural unit derived from the polyfunctional compound represented by the above general formula (I-1) and a structural unit derived from the isocyanate compound represented by the above general formula (II-1). The component (δ) may be used alone in 1 kind or in combination of 2 or more kinds.

As the melamine resin, a compound having a melamine skeleton can be used, and examples thereof include: polyhydroxylmethylmelamines such as trimethylol melamine and hexamethylolmelamine; an alkoxymethyl melamine in which a part or all of the methylol groups of the polymethylol melamine are alkoxymethyl groups having an alkyl group having 1 to 6 carbon atoms; and acyloxymethylmelamine in which a part or all of the methylol groups of the polymethylolmelamine are acyloxymethyl groups having acyl groups having 2 to 6 carbon atoms. These melamine resins may be monomers or polymers of two or more dimers, or a mixture thereof may be used. Further, a product obtained by co-condensing urea or the like on a part of melamine may be used. Examples of such melamine resins include: beckamine APM, Beckamine M-3(60), Beckamine MA-S, Beckamine J-101LF, Unica Resin (ユニカレジン)380K from Union chemical industries, Riken Resin (リケンレジン) MM series from Sanko industries, Ltd.

As the glyoxal resin, conventionally known glyoxal resins can be used. Examples of the glyoxal resin include: 1, 3-dimethylglyoxalurea resin, dimethylol dihydroxy ethylene urea resin, dimethylol dihydroxy propylene urea resin, and the like. The functional groups of these resins may also be substituted with other functional groups. Examples of the glyoxal resin include: beckamine N-80, Beckamine NS-11, Beckamine LF-K, Beckamine NS-19, Beckamine LF-55P Conc, Beckamine NS-210L, Beckamine NS-200, Beckamine NF-3, Union Resin (ユニレジン) GS-20E, produced by Union chemical industries, Riken Resin RG series, and Riken Resin MS series, produced by Sanko industries, all of which are available from DIC corporation.

When a melamine resin and a glyoxal resin are used as the (δ) component, the water repellent composition of the present embodiment preferably further contains a catalyst from the viewpoint of promoting the reaction. Such a catalyst is not particularly limited as long as it is a catalyst that is generally used, and examples thereof include: boron-fluorine compounds such as ammonium borofluoride and zinc borofluoride (in salt form); neutral metal salt catalysts such as magnesium chloride and magnesium sulfate; inorganic acids such as phosphoric acid, hydrochloric acid, and boric acid. Among these catalysts, an organic acid such as citric acid, tartaric acid, malic acid, maleic acid, or lactic acid may be used as a co-catalyst as necessary. Examples of such a catalyst include: (iii) Catalyst ACX, Catalyst 376, Catalyst O, Catalyst M, Catalyst G (GT), Catalyst X-110, Catalyst GT-3, and Catalyst NFC-1 manufactured by DIC, Unica Catalyst (ユニカキャタリスト)3-P manufactured by Union chemical Co., Ltd, and Unica Catalyst MC-109, Riken Fixer (リケンフィクサー) RC series, Riken Fixer series, and Riken Fixer RZ-5 manufactured by Sanko Industrial Co., Ltd.

As the compound having 1 or more isocyanate groups or blocked isocyanate groups, a monofunctional (mono) isocyanate compound such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate, or naphthalene isocyanate, a polyfunctional isocyanate compound, or the like can be used.

The polyfunctional isocyanate compound is not particularly limited as long as it has 2 or more isocyanate groups in the molecule, and a known polyisocyanate compound can be used. Examples of the polyfunctional isocyanate compound include: and diisocyanate compounds such as alkylene diisocyanate, aryl diisocyanate and cycloalkyl diisocyanate, and modified polyisocyanate compounds such as dimers and trimers of these diisocyanate compounds. The number of carbon atoms of the alkylene diisocyanate is preferably 1 to 12.

Examples of the diisocyanate compound include: 2, 4-or 2, 6-tolylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, 4, 4-diphenylmethane diisocyanate, p-phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,4, 4-trimethylhexamethylene-1, 6-diisocyanate, phenylene diisocyanate, toluene or naphthalene diisocyanate, 4,4' -methylene-bis (phenylisocyanate), 2,4' -methylene-bis (phenylisocyanate), 3,4' -methylene-bis (phenylisocyanate), 4,4' -ethylene-bis (phenylisocyanate), ω ' -diisocyanato-1, 3-dimethylbenzene, omega ' -diisocyanate-1, 4-dimethylcyclohexane, omega ' -diisocyanate-1, 4-dimethylbenzene, omega ' -diisocyanate-1, 3-dimethylcyclohexane, 1-methyl-2, 4-diisocyanatocyclohexane, 4' -methylene-bis (cyclohexyl isocyanate), 3-isocyanato-methyl-3, 5, 5-trimethylcyclohexyl isocyanate, acid-diisocyanate dimer, omega ' -diisocyanatodiethylbenzene, omega ' -diisocyanatodimethyltoluene, omega ' -diisocyanatodiethyltoluene, fumaric acid bis (2-isocyanatoethyl) ester, maleic acid, 1, 4-bis (2-isocyanato-propan-2-yl) benzene, and 1, 3-bis (2-isocyanato-propan-2-yl) benzene.

Examples of triisocyanate compound include: triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, tris (isocyanatophenyl) -thiophosphate, and the like.

The modified polyisocyanate compound derived from a diisocyanate compound is not particularly limited as long as it has 2 or more isocyanate groups, and examples thereof include: polyisocyanates having a biuret structure, an isocyanurate structure, a urethane structure, an uretdione structure, an allophanate structure, a trimer structure, etc., and adducts of aliphatic isocyanates of trimethylolpropane. Further, polymeric MDI (MDI ═ diphenylmethane diisocyanate) may also be used as the polyfunctional isocyanate compound.

As for the polyfunctional isocyanate compound, 1 kind may be used alone or 2 or more kinds may be used in combination.

The isocyanate group of the polyfunctional isocyanate compound may be either a blocked isocyanate group blocked with a blocking agent or the like as it is. Examples of the blocking agent include: pyrazoles such as 3, 5-dimethylpyrazole, 3-methylpyrazole, 3, 5-dimethyl-4-nitropyrazole, 3, 5-dimethyl-4-bromopyrazole and pyrazole; phenols such as phenol, methylphenol, chlorophenol, isobutylphenol, tert-butylphenol, isopentylphenol, octylphenol, and nonylphenol; lactams such as epsilon-caprolactam, delta-valerolactam and gamma-butyrolactam; active methylene compounds such as dimethyl malonate, diethyl malonate, acetylacetone, methyl acetoacetate, and ethyl acetoacetate; oximes such as formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; imidazole compounds such as imidazole and 2-methylimidazole; sodium bisulfite and the like. Of these, pyrazoles and oximes are preferable from the viewpoint of water repellency.

As the polyfunctional isocyanate compound, a water-dispersible isocyanate which imparts water dispersibility to the polyisocyanate by introducing a hydrophilic group into the polyisocyanate structure to give a surface active effect can also be used. In addition, a known catalyst such as organotin or organozinc may be used in combination to accelerate the reaction.

The content ratio of the (α) component to the (δ) component in the present embodiment is preferably 95: 5-60: 40, more preferably 95: 5-70: 30, more preferably 90: 10-80: 20. when the content ratio of the component (α) to the component (δ) is in the above range, a fiber base material which can provide excellent water repellency and water impermeability and has sufficient peel strength while maintaining the texture of the fiber base material sufficiently can be easily obtained.

The water repellent composition of the present embodiment may also contain additives and the like as necessary. Examples of additives include: other water-proofing agents, surfactants, antifoaming agents, pH adjusting agents, antibacterial agents, antifungal agents, coloring agents, antioxidants, deodorants, various organic solvents, chelating agents, antistatic agents, antibacterial and deodorant agents, flame retardants, softeners, wrinkle proofing agents, and the like.

As the surfactant, known nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used. The surfactants may be used alone in 1 kind or in combination of 2 or more kinds.

Examples of the defoaming agent include: grease-based antifoaming agents such as castor oil, sesame oil, linseed oil, animal and vegetable oils, and the like; fatty acid defoaming agents such as stearic acid, oleic acid and palmitic acid; fatty acid ester-based antifoaming agents such as isoamyl stearate, distearyl succinate, ethylene glycol distearate and butyl stearate; alcohol defoaming agents such as polyoxyalkylene monohydroxy alcohol di-t-pentylphenoxyethanol, 3-heptanol, and 2-ethylhexanol; ether-based antifoaming agents such as di-t-pentylphenoxyethanol 3-heptyl cellosolve, nonyl cellosolve, 3-heptyl carbitol and the like; phosphate ester-based antifoaming agents such as tributyl phosphate (トリブチルオスフェート) and tributoxyethyl phosphate; amine defoaming agents such as dipentylamine; amide-based antifoaming agents such as polyalkylene amides and acylated polyamines; sulfate-based antifoaming agents such as sodium lauryl sulfate; mineral oil, etc. The defoaming agents may be used alone in 1 kind or in combination of 2 or more kinds.

Examples of the pH adjuster include: organic acids such as lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, citric acid, malic acid, sulfonic acid, methanesulfonic acid, and toluenesulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, and the like; bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonia, alkanolamines, pyridine, morpholine, and the like. The pH adjusting agent may be used alone in 1 kind or in combination of 2 or more kinds.

Examples of the organic solvent include: aliphatic alcohols having 1 to 8 carbon atoms such as methanol, ethanol, isopropanol, isobutanol, hexanol, and 2-ethylhexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol and the like; esters such as ethyl acetate, methyl acetate, butyl acetate, methyl lactate, and ethyl lactate; ethers such as diethyl ether, diisopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, dioxane, methyl tert-butyl ether, and butyl carbitol; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol; glycol ethers such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, and 3-methoxy-3-methyl-1-butanol; glycol esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc.; amides such as formamide, acetamide, benzamide, N-dimethylformamide, and acetanilide. The organic solvent may be used alone in 1 kind or in combination of 2 or more kinds.

As the antistatic agent, an antistatic agent having a property of hardly hindering water repellency can be used. Examples of antistatic agents include: examples of the surfactant include cationic surfactants such as higher alcohol sulfate, sulfated oils, sulfonates, quaternary ammonium salts and imidazoline type quaternary salts, nonionic surfactants such as polyethylene glycol type and polyol ester type surfactants, amphoteric surfactants such as imidazoline type quaternary salts, alanine type and betaine type surfactants, antistatic (antistatic) polymers of high molecular compound type, and polyalkylamines. The antistatic agent may be used alone in 1 kind or in combination of 2 or more kinds.

The waterproof fiber product of the present embodiment will be described.

The waterproof fiber product of the present embodiment includes a fiber base material, and the waterproof agent composition of the present embodiment attached to the fiber base material.

The fibrous base material may be a fibrous product or a fibrous raw material constituting the fibrous product.

The raw material of the fiber base material is not particularly limited, and examples thereof include: natural fibers such as cotton, hemp, silk and wool, semisynthetic fibers such as rayon and acetate, synthetic fibers such as nylon, polyester, polyurethane and polypropylene, and composite fibers and blend fibers thereof.

The form of the fiber base material is not particularly limited, and may be any form such as fiber, thread, cloth, nonwoven fabric, and paper.

The water-repellent fiber product of the present embodiment may further include a coating film. The coating film may, for example, contain at least 1 resin selected from urethane resins, acrylic resins, and polyester resins other than those contained in the water repellent composition of the present invention.

A method for producing a water-repellent fiber product according to the present embodiment will be described.

The method for producing a water repellent fiber product of the present embodiment includes a step of bringing a treatment liquid containing the water repellent composition of the present embodiment into contact with a fiber base material.

Examples of the method for treating the fiber base material with the treatment liquid include processing methods such as dipping, spraying, and coating. In addition, when the water repellent composition contains water, it is preferable to remove the water by drying after attaching it to the fiber base material.

The water-repellent fiber product of the present embodiment can be coated on a specific portion. Examples of the coating process include moisture-permeable waterproofing and windproof processes for sports use and outdoor use. As a processing method, for example, in the case of moisture-permeable waterproofing processing, processing can be performed as follows: a coating liquid containing a urethane resin, an acrylic resin, or the like other than those contained in the water repellent composition of the present invention and a medium is applied to one surface of the water repellent-treated textile product and dried.

The amount of the water repellent composition attached to the fiber base material can be appropriately adjusted depending on the degree of water repellency required, and from the viewpoint of sufficiently maintaining the texture of the fiber base material, imparting water repellency and water repellency, and sufficiently ensuring peel strength, the amount of the water repellent composition attached to the total of the component (α), the component (β), and the component (γ) is preferably adjusted so as to be 0.01 to 10g, more preferably 0.05 to 5g, per 100g of the fiber base material.

After the water repellent composition of the present embodiment is attached to the fiber base material, it is preferable to perform heat treatment as appropriate. The temperature condition is not particularly limited, and if the water repellent composition of the present embodiment is used, the fiber base material can exhibit sufficiently good water repellency under mild conditions of 100 to 130 ℃. The temperature condition may be a high temperature treatment of 130 ℃ or more (preferably 200 ℃ or less), and in this case, the treatment time can be shortened as compared with the conventional case of using a fluorine-based water repellent. Therefore, according to the method for producing a water repellent fiber product of the present embodiment, it is possible to suppress the deterioration of the fiber base material due to heat, to soften the texture of the fiber base material at the time of water repellent treatment, and to impart sufficient water repellency to the fiber base material under mild heat treatment conditions, i.e., low-temperature curing conditions.

In the case where the water repellent composition of the present embodiment contains the (δ) component, from the viewpoint of sufficiently advancing the reaction of the crosslinking agent to more effectively impart water repellency and water repellency, and from the viewpoint of effectively improving the peel strength, it is preferable to heat the fiber base to which the (δ) component has been adhered at 110 to 180 ℃ for 1 to 5 minutes. The amount of the (δ) component adhering to the fiber base material is preferably 0.1 to 50% by mass, and more preferably 0.1 to 10% by mass, based on the weight of the fiber base material.

The components contained in the water repellent composition of the present embodiment can be contained in a plurality of treatment liquids. For example, the treatment liquid may be classified into a treatment liquid containing a component (α), a component (β), and a component (γ), and a treatment liquid containing a component (δ).

The water-repellent fiber product obtained by the production method of the present embodiment can exhibit sufficient water repellency even when used outdoors for a long time, and is excellent in texture, and the water-repellent fiber product can be an environmentally friendly product because it does not use a fluorine-based compound.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

[ examples ]

The present invention is further illustrated by the following examples, but the present invention is not limited to these examples.

< adjustment of acrylic resin Dispersion >

Using the materials shown in Table 1 and Table 2{ in the tables, the numerical values (g) }, polymerization was carried out in the order shown below to obtain an acrylic resin dispersion.

(Synthesis example 1)

Into a 0.5L autoclave were charged 15g of stearyl acrylate, 5g of stearyl methacrylate, 0.5g of Surfynol465 (HLB 13, manufactured by Nikken chemical Co., Ltd.), 1g of Surfynol440 (HLB 8, manufactured by Nikken chemical Co., Ltd.), 0.5g of Noigen XL-40 (polyoxyalkylene branched decyl ether, HLB 10.5, manufactured by first Industrial pharmaceutical Co., Ltd.), 1g of stearyl trimethylammonium sulfate, 15g of tripropylene glycol, and 54.9g of water, and the mixture was mixed and stirred at 45 ℃. The mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.15g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution, and 7g of vinyl chloride was continuously pressed under a nitrogen atmosphere while maintaining the internal pressure of the autoclave at 0.3MPa and the temperature at 61 ℃ to react for 6 hours, to obtain an acrylic resin dispersion containing 27 mass% of an acrylic resin.

(Synthesis examples 2 to 13)

An acrylic resin dispersion was obtained in the same manner as in synthesis example 1, except that the materials shown in tables 1 and 2 were used.

< adjustment of urethane resin Dispersion >

(Synthesis example 14)

A1000 ml flask was charged with 206.74g of ditrimethylolpropane, 469.87g of stearic acid, and 3.4g of p-toluenesulfonic acid. Then, the temperature is raised to 140 ℃ under nitrogen atmosphere, and then dehydration reaction is carried out for 5 hours at a temperature raising rate of about 0.4 ℃/min under nitrogen flow at 140-190 ℃. The nitrogen flow was 5ml per minute. After the reaction was completed, the acid value of the resultant was measured. The acid value was 2.0 mgKOH/g.

Next, 101.12g to 300ml of the above reaction product was taken in a flask, and 23.78g of hexamethylene diisocyanate, 25g of methyl ethyl ketone, and 0.125g of a bismuth-based catalyst (NEOSTANN U-600: manufactured by NITTON CHEMICAL CO., LTD.) were added thereto to conduct a reaction at 80 ℃ for 7 hours. The reaction was carried out until the NCO% became 0.64%. After the reaction, the temperature was reduced to 40 ℃, and then 2.36g of 3, 5-dimethylpyrazole was added thereto to carry out a reaction at 40 ℃ for 1 hour, thereby obtaining a urethane resin dispersion containing 83 mass% of urethane resin. The weight average molecular weight of the obtained urethane resin was measured using gel permeation chromatography (HLC-8320gpc (tosoh corporation)), and the weight average molecular weight was 11700.

The urethane resin contained in the urethane resin dispersion liquid obtained is a compound obtained by reacting R in the general formula (I-1)³¹A residue obtained by removing 4 hydroxyl groups from di-trimethylolpropane, d is 2, e is 2, W¹Is an ester group, R³²Is heptadecyl, V¹A polyfunctional compound having a hydroxyl group, and R in the above general formula (II-1)³³An isocyanate compound having a hexamethylene group and f is 2, and then the remaining unreacted isocyanate group is blocked with 3, 5-dimethylpyrazole.

40g of the urethane resin (isolate) obtained as described above, 50g of methyl ethyl ketone, 5g of Decaglyn (デカグリン)1-L (nonionic surfactant, first Industrial pharmaceutical manufacture), 5g of Decaglyn 1-SV (nonionic surfactant, first Industrial pharmaceutical manufacture), and 5g of ARQUAD T-28 (cationic surfactant, manufactured by LION SPECIALTY CHEMICALS) were placed in a 500mL stainless steel container and dissolved by heating to 50 ℃. Next, 295g of hot water at 80 ℃ was added thereto, and emulsification was carried out for 20 minutes while maintaining the temperature at 80 ℃ by using an ultrasonic emulsifier US-600E (manufactured by Nippon Seiko Co., Ltd.). Thereafter, cooling was performed to obtain a dispersion containing 10 mass% of the urethane resin.

(Synthesis example 15)

A1000 ml flask was charged with 255.88g of trimethylolpropane, 542.51g of stearic acid, and 1.6g of p-toluenesulfonic acid. Then, the temperature is raised to 140 ℃ under nitrogen atmosphere, and then dehydration reaction is carried out at 140 to 190 ℃ for 5 hours under nitrogen flow at a temperature raising rate of about 0.4 ℃/min. The nitrogen flow was 5ml per minute. After the reaction was completed, the acid value of the resultant was measured. The acid value was 2.0 mgKOH/g.

Next, 87.83g to 300ml of the above reaction product was taken out, 37.11g of hexamethylene diisocyanate, 25g of methyl ethyl ketone and 0.125g of bismuth catalyst were added thereto, and the reaction was carried out at 80 ℃ for 7 hours. The reaction was carried out until the NCO% became 0.69%. After the reaction, the temperature was decreased to 40 ℃, and then 2.37g of 3, 5-dimethylpyrazole was added and the reaction was carried out at 40 ℃ for 1 hour to obtain a urethane resin dispersion containing 83 mass% of urethane resin. The weight average molecular weight of the obtained urethane resin was measured by gel permeation chromatography, and the weight average molecular weight was 17500.

The urethane resin contained in the urethane resin dispersion liquid obtained is a compound obtained by reacting R in the general formula (I-1)³¹A residue obtained by removing 3 hydroxyl groups from trimethylolpropane, d is 1, e is 2, W¹Is an ester group, R³²Is heptadecyl, V¹A polyfunctional compound having a hydroxyl group, and R in the above general formula (II-1)³³An isocyanate compound having a hexamethylene group and f is 2, and then the remaining unreacted isocyanate group is blocked with 3, 5-dimethylpyrazole.

40g of the urethane resin (isolate) obtained as described above, 50g of methyl ethyl ketone, 5g of Decaglyn 1-L (nonionic surfactant, manufactured by first Industrial pharmaceutical Co., Ltd.), 5g of Decaglyn 1-SV (nonionic surfactant, manufactured by first Industrial pharmaceutical Co., Ltd.), and 5g of ARQUAD T-28 (cationic surfactant, manufactured by LION SPECIALTY CHEMICALS) were placed in a 500mL stainless steel container and heated to 50 ℃ to dissolve them. Next, 295g of hot water at 80 ℃ was added thereto, and emulsification was performed for 20 minutes while maintaining 80 ℃ by using an ultrasonic emulsifier US-600E (manufactured by Nippon Seiko Co., Ltd.). Thereafter, cooling was performed to obtain a dispersion containing 10 mass% of the urethane resin.

< adjustment of organically modified Silicone emulsion >

(Synthesis example 16)

63.2g of methylhydrogensilicone having an SiH equivalent of 63.2g/mol and a polymerization degree of 50 was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel, and was heated to 65 ℃ while introducing nitrogen gas, and mixed until uniform. A mixed solution of ethylene glycol monobutyl ether and toluene of platinum (IV) chloride as a hydrosilylation catalyst was added so that the platinum concentration became 5ppm with respect to the reactants in the system. 168.3g of 1 mol of 1-dodecene was added dropwise at a temperature of 120 ℃ and the reaction mixture was allowed to react at 120 ℃ for 6 hours. Confirmation of completion of the addition reaction can be carried out by: FT-IR analysis of the obtained organomodified silicone was performed to confirm that the absorption spectrum of the SiH groups derived from the methylhydrogenosilicones disappeared. In this way, a1 of 0, a2 of 50, R in the above general formula (L-1) are obtained²²²Is methyl, R²²³Is dodecyl, R²³⁰、R²³¹、R²³²、R²³³、R²³⁴And R²³⁵An organically modified silicone which is a methyl group. Further, 20 parts by mass of the obtained organic modified silicone is mixed with 3 parts by mass of an ethylene oxide 9 mol adduct of a branched higher alcohol having 12 to 14 carbon atoms. Then, 77 parts by mass of water was added to the mixture in small amounts and the mixture was emulsified in water to obtain an organically modified silicone emulsion containing 20 mass% of organically modified silicone.

(Synthesis example 17)

An organically modified silicone and an organically modified silicone emulsion were obtained in the same manner as in synthetic example 16, except that 84.2g of 1 mol of 1-hexene was used instead of 168.3g of 1 mol of 1-dodecene. Further, the organically modified silicone is obtained by obtaining a number a1 of 0, a2 of 50, R in the above general formula (L-1)²²²Is methyl, R²²³Is hexyl, R²³⁰、R²³¹、R²³²、R²³³、R²³⁴And R²³⁵An organically modified silicone which is a methyl group.

(Synthesis example 18)

An organically modified silicone and an organically modified silicone emulsion were obtained in the same manner as in synthetic example 16, except that 252.5g of 1 mol of 1-octadecene was used instead of 168.3g of 1 mol of 1-dodecene. Further, the organically modified silicone is one in which a1 is 0, a2 is 50, R is obtained in the above general formula (L-1)²²²Is methyl, R²²³Is octadecyl, R²³⁰、R²³¹、R²³²、R²³³、R²³⁴And R²³⁵An organically modified silicone which is a methyl group.

(Synthesis example 19)

An organically modified silicone and an organically modified silicone emulsion were obtained in the same manner as in synthesis example 16, except that 84.2g of 1-dodecene was used in an amount of 0.5 mol, and 126.2g of 1-octadecene was used in an amount of 0.5 mol, instead of 168.3g of 1-dodecene. Further, the organically modified silicone is one in which a1 is 0, a2 is 50, R is obtained in the above general formula (L-1)²²²Is methyl, R²²³Is dodecyl or octadecyl, R²³⁰、R²³¹、R²³²、R²³³、R²³⁴And R²³⁵An organically modified silicone which is a methyl group.

(Synthesis example 20)

An organically modified silicone and an organically modified silicone emulsion were obtained in the same manner as in synthetic example 17, except that 140.5g of a copolymer of dimethylsiloxane and methylhydrogensiloxane was used in place of 63.2g of methylhydrogensiloxane and that 252.5g of 1 mol of 1-octadecene was used in place of 168.3g of 1 mol of 1-dodecene. The copolymer of dimethylsiloxane and methylhydrogensiloxane had an SiH group equivalent of 140.5g/mol and a degree of polymerization of 50. Further, the organically modified silicone is one in which a1 is 25, a2 is 25, R is 25, and the above general formula (L-1)²²⁰And R²²¹Is methyl, R²²²Is methyl, R²²³Is octadecyl, R²³⁰、R²³¹、R²³²、R²³³、R²³⁴And R²³⁵Organically modified silicones as methyl groups。

< preparation example of emulsifying wax >

Production example 1

Into a high-pressure reaction vessel were charged paraffin { melting point 69 ℃, penetration 12(25 ℃) }150g, pure water 350g, polyoxyethylene stearyl ether (HLB ═ 10.7)8.5g, and polyoxyalkylene branched decyl ether (HLB ═ 14.7)6.5g, and the vessel was sealed. And then, stirring and heating to 110-120 ℃ in the container. Thereafter, the inside of the vessel was emulsified under high pressure for 30 minutes while maintaining the high pressure, to obtain an aqueous dispersion of paraffin wax. Further, the wax content was adjusted to 30 mass% with pure water to obtain an emulsified wax.

Production example 2

An aqueous dispersion of paraffin wax and an emulsified wax were obtained in the same manner as in production example 1, except that paraffin wax { melting point 77 ℃, penetration 4(25 ℃) }150g was used in place of paraffin wax { melting point 69 ℃, penetration 12(25 ℃) }150 g.

(production example 3)

An aqueous dispersion of paraffin and an emulsifying wax were obtained in the same manner as in production example 1, except that paraffin { melting point 50 ℃, penetration 22(25 ℃) }150g was used instead of paraffin { melting point 69 ℃, penetration 12(25 ℃).

< preparation of test solution >

(example 1)

The acrylic resin dispersion obtained in synthesis example 1, the organically modified silicone emulsion obtained in synthesis example 18, the emulsifying wax obtained in production example 2, diethylene glycol butyl ether (ブチルジグリコール) as a medium, and niceole (ナイスポール) FE-26 (manufactured by hitachi chemical corporation) as an antistatic agent were mixed so as to have the composition (parts by mass) shown in table 3, to obtain a test liquid. The amounts of the acrylic resin, the organic modified silicone, and the wax to be blended in the test solution of example 1 were calculated to be 20 parts by mass × 27 parts by mass to 5.4 parts by mass, 10 parts by mass × 20 parts by mass to 2 parts by mass, and 10 parts by mass × 30 parts by mass to 3 parts by mass, respectively.

The details of the materials shown in tables 3 to 6 are shown below.

IE-7045 (trade name, manufactured by Tollido Kangning Co., Ltd., Dimethicone)

NICEPOLE FE-26 (trade name, manufactured by Rihua chemical Co., Ltd.)

(examples 2 to 23 and comparative examples 1 to 8)

Test solutions were obtained in the same manner as in example 1 except that the materials shown in tables 3 to 6 were used.

I. Evaluation of initial Water repellency by spraying method for Water-repellent fiber product

The test was carried out by setting the water temperature for spraying to 20 ℃ in the same manner as in the spraying method of JIS L1092 (2009). In this test, the test solutions prepared in examples and comparative examples were diluted with water so that the total content of the acrylic resin, other acrylic resin, urethane resin, organic modified silicone, dimethyl silicone, wax, and other wax was 1 mass% to obtain treatment solutions. Next, the dyed 100% polyester cloth or 100% nylon cloth was subjected to an impregnation treatment (mangle ratio (ピックアップ rate) 60 mass%) in the obtained treatment liquid. Next, the cloth subjected to the impregnation treatment was dried at 130 ℃ for 2 minutes, and further subjected to a heat treatment at 170 ℃ for 1 minute, to obtain a water-repellent fiber product. The water repellency of the water-repellent fiber product was evaluated. The results were evaluated visually on the following scale. The evaluation results are shown in tables 3 to 6.

Water resistance: status of state

5: no adhesion wetting on the surface

4: slightly show adhesive wetting on the surface

3: exhibit localized wetting at the surface

2: exhibit wetting at the surface

1: exhibit wetting over the entire surface

0: completely wet on both front and back sides

Evaluation of durable Water repellency by spraying method of Water repellent fiber product

NK ASSIST NY-30 (manufactured by Rihua chemical Co., Ltd.) as a crosslinking agent was added to the test solutions prepared in the compositions of examples and comparative examples so that the amount of the crosslinking agent was 3 g/L. Next, the test solution was diluted with water so that the total content of the acrylic resin, the other acrylic resin, the urethane resin, the organically modified silicone, the dimethyl silicone, the wax, the other wax, and the crosslinking agent became 1 mass%, and the treatment solution was adjusted. The dyed 100% polyester cloth or 100% nylon cloth was subjected to an impregnation treatment using a treatment solution (mangle yield 60 mass%). Next, the cloth subjected to the impregnation treatment was dried at 130 ℃ for 2 minutes, and further heat-treated at 170 ℃ for 1 minute, to obtain a water-repellent fiber product. The obtained water-repellent fiber product was washed 10 times (L-10) by method 103 of JIS L0217 (1995), and the water repellency after air-drying was evaluated in the same manner as in the above-mentioned water-repellent evaluation method. The evaluation results are shown in tables 3 to 6.

Measurement of contact Angle of Water-repellent fiber product

The water-repellent fiber product was obtained in the same manner as in ii. To the obtained water-repellent fiber product, 20. mu.l of ion-exchanged water was added dropwise, and the contact angle of the formed water droplet was measured. For measuring the contact angle, an automatic contact angle meter DSA25 manufactured by KRUSS was used. The evaluation results are shown in tables 3 to 6.

Evaluation of Water repellency of Water-repellent fiber product

The water-repellent fiber product was obtained in the same manner as in ii. The obtained water-repellent fiber product was placed in a horizontal and flat place, and 200. mu.l of water droplets were dropped 3 drops at a time onto the water-repellent fiber product and placed at room temperature. The number of droplets remaining on the water-repellent fiber product in the state of water droplets having a contact angle of 90 ° or more after 10 minutes, 30 minutes, 60 minutes, and 120 minutes was used as the evaluation result. The evaluation results are shown in tables 3 to 6.

V. evaluation of texture of Water-repellent fiber product

The polyester 100% water-repellent fiber product described in II was evaluated by hand at 5 grades shown below. The evaluation criteria were defined as the texture of the water-repellent fiber product of comparative example 1 being 2 and the texture of the water-repellent fiber product of comparative example 2 being 5. The evaluation results are shown in tables 3 to 6.

1: hard-5: softness

Evaluation of peel Strength of Water-repellent fiber product

The test was carried out in accordance with JIS K6404-5 (1999). First, NK ASSIST NY-30 (manufactured by Rihua chemical Co., Ltd.) as a crosslinking agent was added to the test solutions prepared in examples and comparative examples so that the amount of the crosslinking agent was 3 g/L. Next, the test solution was diluted with water so that the total content of the acrylic resin, the other acrylic resin, the urethane resin, the organically modified silicone, the dimethyl silicone, the wax, the other wax, and the crosslinking agent became 3 mass%, and the treatment solution was adjusted. Next, the dyed 100% nylon cloth was subjected to an impregnation treatment using the obtained treatment liquid (mangle ratio 60 mass%). Next, the cloth subjected to the impregnation treatment was dried at 130 ℃ for 2 minutes, and further heat-treated at 160 ℃ for 30 seconds to obtain a base cloth. The obtained base fabric was thermally bonded to a Seam Tape (seatape) ("MELCO Tape" manufactured by サン chemical company) at 150 ℃ for 1 minute using a thermal bonding apparatus, and the peel strength between the base fabric and the Seam Tape was measured by Autograph (AG-IS, manufactured by shimadzu corporation). The moving speed of the holder was set to 100mm/min, and the average value of the stress was defined as the peel strength [ N/inch ]. The results are shown in tables 3 to 6.