TW202018058A - Water-repellent agent composition for fibers, water-repellent textile product, and production method for water-repellent textile product - Google Patents

Abstract

This water-repellent agent composition contains: an acrylic resin having a constituent unit derived from a (meth)acrylic acid ester monomer (A) represented by general formula (A-1) and/or a urethane resin having a structural unit derived from a polyfunctional compound represented by general formula (I-1) and a structural unit derived from an isocyanate compound represented by general formula (II-1); an organo-modified silicone represented by general formula (L-1); and a wax. [In formula (A-1), R1 represents hydrogen or a methyl group, R2 represents an optionally substituted monovalent hydrocarbon group having 12 or more carbon atoms.] (I-1): R31[-W1-R32]d[-V1]e [In formula (I-1), d represents an integer of one or more, e represents an integer of two or more, (d+e) is 3-6, R31 represents a (d+e)-valent organic group, W1 represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group, R32 represents a straight-chain or branched monovalent hydrocarbon group having 8-24 carbon atoms, and V1 represents a hydroxyl group, an amino group, or a carboxy group. Note that two or more among the e-number of V1's are a hydroxyl group and/or an amino group.] (II-1): R33[-NCO]f [In formula (II-1), R33 represents an f-valent organic group, and f represents an integer of 2-7.] [In formula (L-1), R220, R221, and R222 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1-4 carbon atoms, R223 represents a hydrocarbon group having an aromatic ring and having 8-40 carbon atoms, or an alkyl group having 3-22 carbon atoms, R230, R231, R232, R233, R234, and R235 each independently represent a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1-4 carbon atoms, a hydrocarbon group having an aromatic ring and having 8-40 carbon atoms, or an alkyl group having 3-22 carbon atoms, a1 represents an integer of zero or more, a2 represents an integer of one or more, (a1 + a2) is 10-200, in the case where a1 is two or more, respective R220's and respective R221's may be the same or different from each other, and in the case where a2 is two or more, respective R222's and respective R223's may be the same or different from each other.].

Description

Water-repellent composition for fiber, water-repellent fiber product and method for manufacturing water-repellent fiber product

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

Conventionally, as a water-repellent agent used for water-repellent processing and the like, a fluorine-based water-repellent agent having a fluoroalkyl group is known, and by treating the surface of the fiber with the fluorine-based water-repellent agent, water repellency can be obtained Fiber products. However, although fiber products treated with a fluorine-based water repellent will exhibit excellent water repellency, concerns about the environmental load of the long-chain fluoroalkyl compounds used have become clear, so international requirements are made to be completely free of fluorine-based compounds In the case of non-fluorine-based water repellent that exhibits high-performance water-repellent properties comparable to those of fluorine-based ones.

Therefore, in recent years, research has been conducted on non-fluorine-based water repellent agents that do not contain fluorine. For example, the following Patent Document 1 discloses a fiber processing agent containing at least one kind of silicon-based compound, wax-based compound, and wax-zirconium-based compound. In addition, Patent Document 2 below proposes a soft water repellent containing an amine-modified polysiloxane and a polyfunctional isocyanate. Furthermore, in the following Patent Document 3, a water repellent containing a specific non-fluorine-based polymer is proposed. The specific non-fluorine-based polymer includes a (meth)acrylate having at least 12 carbon atoms in the ester portion as Monomer unit. [Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2006-124866 Patent Document 2: Japanese Patent Laid-Open No. 2004-59609 Patent Document 3: Japanese Patent Laid-Open No. 2006-328624

[Problems to be solved by the invention]

However, the previous non-fluorine-based water repellent agent can confirm the initial water repellent effect in the spray method of JIS L 1092 (2009), one of the usual water repellent evaluation tests, but it is assumed that the practical and actual wearing of fiber products Sometimes sufficient results cannot be obtained in evaluation tests. For practical use, a durable water repellent that is difficult to reduce water repellency even after repeated washing is required. For actual wearing, it is required to prevent water seepage for a long time. If the water-impermeability is not sufficient, there may be a case where part of the water droplet penetrates into the fiber as time passes, causing the wetting of the opposite surface. The practical and actual wearing performance of the previous non-fluorine-based water repellent agent is not sufficient compared with the fluorine-based water-repellent agent.

However, water-repellent processed fiber products, etc., may sometimes be coated with urethane resin or acrylic resin. In this case, the fiber product has sufficient water repellency, but it is required that the coating part is not easy to peel off. The degree of peeling of the coating is not easy to be evaluated by measuring the stress (peel strength) required to peel the coating film from the water-repellent fiber substrate, but the previous non-fluorine-based water repellent agent is not sufficient The research on such peel strength has been conducted, and there is room for further improvement in order to balance the above-mentioned practical and actual wearing performance and peel strength to a higher level.

The present invention has been completed in view of the above circumstances, and an object thereof is to provide a fiber substrate that can impart excellent initial water repellency, durable water repellency, and water repellency to a fiber substrate and impart such characteristics to a fiber substrate having sufficient peel strength Water repellent composition for fibers, and water-repellent fiber products using the same and methods for producing water-repellent fiber products. [Technical means to solve the problem]

In order to solve the above-mentioned problems, the present inventors conducted intensive research, and as a result, it was found that the cloth used for water-repellent processing by using a water-repellent composition prepared by combining a specific resin with a specific polysiloxane and wax not only exhibits It showed excellent initial water repellency, and also showed good results in the evaluation of durable water repellency after washing, the evaluation of water permeability resistance, and the evaluation of peel strength. Based on this knowledge, the present invention was completed.

An aspect of the present invention relates to a water repellent composition for fibers, which contains: a structural unit derived from a (meth)acrylate monomer (A) represented by the following general formula (A-1) Acrylic resin and/or an amine group 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) Formate resin, organically modified polysiloxane represented by the following general formula (L-1), and wax.

[式(A-1)中，R¹ 表示氫或甲基，R² 表示可具有取代基之碳數12以上之1價烴基][Chemical 1]

[In formula (A-1), R ¹ represents hydrogen or methyl, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent]

R ³¹ [-W ¹ -R ³² ] _d [-V ¹ ] _e (I-1) [In formula (I-1), d represents an integer of 1 or more, e represents an integer of 2 or more, and (d+e) is 3 ～6, R ³¹ represents a (d+e) valent organic group, W ¹ represents a divalent group of an ester group, an amide group, a carbamate group or a urea group, and R ³² represents a linear chain having 8 to 24 carbon atoms Or a branched monovalent hydrocarbon group, V ¹ represents a hydroxyl group, an amine group, or a carboxyl group; wherein, 2 or more of e V ¹ are hydroxyl and/or amine groups]

R ³³ [-NCO] _f (II-1) [In formula (II-1), R ³³ represents an organic group with a valence of f, and f represents an integer of 2 to 7]

[式(L-1)中，R²²⁰ 、R²²¹ 及R²²² 分別獨立，表示氫原子、甲基、乙基或碳數1～4之烷氧基，R²²³ 表示具有芳香族環之碳數8～40之烴基、或碳數3～22之烷基，R²³⁰ 、R²³¹ 、R²³² 、R²³³ 、R²³⁴ 及R²³⁵ 分別獨立，表示氫原子、甲基、乙基、碳數1～4之烷氧基、具有芳香族環之碳數8～40之烴基、或碳數3～22之烷基，a1表示0以上之整數，a2表示1以上之整數，(a1＋a2)為10～200，於a1為2以上之情形時，存在複數個之R²²⁰ 及R²²¹ 分別可相同亦可不同，於a2為2以上之情形時，存在複數個之R²²² 及R²²³ 分別可相同亦可不同][Chem 2]

[In formula (L-1), R ²²⁰ , R ²²¹ and R ²²² are each independently and represent a hydrogen atom, a methyl group, an ethyl group or a C 1-4 alkoxy group, and R ²²³ represents a carbon number having an aromatic ring Hydrocarbon groups of 8 to 40, or alkyl groups of 3 to 22 carbon atoms, R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ^234, and R ²³⁵ are independent of each other and represent a hydrogen atom, a methyl group, an ethyl group, and a carbon number of 1 to 4 alkoxy groups, hydrocarbon groups having 8 to 40 carbon atoms with aromatic rings, or alkyl groups 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 , When a1 is 2 or more, there are a plurality of R ²²⁰ and R ^{221 that} can be the same or different, and when a2 is 2 or more, there are a plurality of R ²²² and R ^{223 that} can be the same or different ]

According to the water repellent composition for fibers of the present invention, it is possible to impart excellent initial water repellency, durable water repellency and water permeability resistance to the fiber substrate, and to obtain a fiber substrate having sufficient peel strength in spite of this characteristic . Thereby, water-repellent fiber products with practical and practical wearing performance can be realized.

Moreover, although the water repellent composition for fibers of the present invention is a water repellent composition that does not contain a compound having a fluoroalkyl group or fluorine, it can impart excellent water repellency (the effect of increasing the contact angle with water), therefore It can be used as a substitute for fluorine-based water repellent, and it can eliminate the worry about the impact on the environment. Furthermore, according to the water repellent composition for fibers of the present invention, it is possible to obtain a fiber substrate having sufficient peel strength while maintaining the texture of the fiber substrate and imparting the above-mentioned excellent initial water repellency, durable water repellency and water permeability resistance.

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

The water repellent composition for fibers 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 above-mentioned water repellent composition for fibers adhered to the fiber base material.

The water-repellent fiber product of the present invention is provided with excellent initial water-repellent, durable water-repellent and water-impermeable water by the fiber water-repellent composition of the present invention. Furthermore, when coating processing is performed, it can have sufficient Peel strength. Therefore, the water-repellent fiber product of the present invention can become suitable for practical and practical wear.

Still another aspect of the present invention relates to a method for producing a water-repellent fiber product, the method comprising the step of bringing a treatment liquid containing the water-repellent composition of the present invention into contact with a fiber substrate.

According to the method for manufacturing a water-repellent fiber product of the present invention, a water-repellent fiber product having excellent initial water-repellent property, durable water-repellent property and water-impermeability and having sufficient peel strength can be obtained. [Effect of invention]

According to the present invention, it is possible to provide a water-repellent agent combination for fibers that can impart excellent initial water repellency, durable water repellency and water-impermeability to fiber substrates, and that the fiber substrates imparted with such characteristics can have sufficient peel strength Materials, and water-repellent fiber products using the same, and methods for manufacturing water-repellent fiber products.

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

In this specification, the term "(meth)acrylate" means "acrylate" or its corresponding "methacrylate". In "(meth)acrylic acid" and "(meth)acrylamide" Synonymous with.

In this specification, the ester group means a group represented by -O-CO-. Acylamino means the group represented by -NH-CO-. The carbamate group means a group represented by -O-CO-NH-. Urea group means the group represented by -NH-CO-NH-. The isocyanate group means the group represented by -N=C=O. Carbonyl means the group represented by -CO-.

In this specification, the so-called fiber base material is an object to be subjected to water repellent processing by the water repellent composition, and may be a fiber product or a fiber material constituting a fiber product.

The water repellent composition for fibers of this 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 has a structural unit derived from a polyfunctional compound represented by the following general formula (I-1), and an isocyanate compound derived from the following general formula (II-1) The structural unit of the urethane resin (hereinafter, also referred to as "urethane resin"), the organically modified polysiloxane represented by the following general formula (L-1) (hereinafter, also referred to as "Organic modified polysiloxane"), and wax.

[式(A-1)中，R¹ 表示氫或甲基，R² 表示可具有取代基之碳數12以上之1價烴基][Chemical 3]

[In formula (A-1), R ¹ represents hydrogen or methyl, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent]

R ³¹ [-W ¹ -R ³² ] _d [-V ¹ ] _e (I-1) [In formula (I-1), d represents an integer of 1 or more, e represents an integer of 2 or more, and (d+e) is 3 ～6, R ³¹ represents a (d+e) valent organic group, W ¹ represents a divalent group of an ester group, an amide group, a carbamate group or a urea group, and R ³² represents a linear chain having 8 to 24 carbon atoms Or a branched monovalent hydrocarbon group, V ¹ represents a hydroxyl group, an amine group, or a carboxyl group; wherein, 2 or more of e V ¹ are hydroxyl and/or amine groups]

R ³³ [-NCO] _f (II-1) [In formula (II-1), R ³³ represents an organic group with a valence of f, and f represents an integer of 2 to 7]

[式(L-1)中，R²²⁰ 、R²²¹ 及R²²² 分別獨立，表示氫原子、甲基、乙基或碳數1～4之烷氧基，R²²³ 表示具有芳香族環之碳數8～40之烴基、或碳數3～22之烷基，R²³⁰ 、R²³¹ 、R²³² 、R²³³ 、R²³⁴ 及R²³⁵ 分別獨立，表示氫原子、甲基、乙基、碳數1～4之烷氧基、具有芳香族環之碳數8～40之烴基、或碳數3～22之烷基，a1表示0以上之整數，a2表示1以上之整數，(a1＋a2)為10～200，於a1為2以上之情形時，存在複數個之R²²⁰ 及R²²¹ 分別可相同亦可不同，於a2為2以上之情形時，存在複數個之R²²² 及R²²³ 分別可相同亦可不同][Chemical 4]

[In formula (L-1), R ²²⁰ , R ²²¹ and R ²²² are each independently and represent a hydrogen atom, a methyl group, an ethyl group or a C 1-4 alkoxy group, and R ²²³ represents a carbon number having an aromatic ring Hydrocarbon groups of 8 to 40, or alkyl groups of 3 to 22 carbon atoms, R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ^234, and R ²³⁵ are independent of each other and represent a hydrogen atom, a methyl group, an ethyl group, and a carbon number of 1 to 4 alkoxy groups, hydrocarbon groups having 8 to 40 carbon atoms with aromatic rings, or alkyl groups 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 , When a1 is 2 or more, there are a plurality of R ²²⁰ and R ^{221 that} can be the same or different, and when a2 is 2 or more, there are a plurality of R ²²² and R ^{223 that} can be the same or different ]

Hereinafter, the acrylic resin and the urethane resin will be referred to as "(α) component", the organically modified polysiloxane will be referred to as "(β) component", and the wax will be referred to as "(γ)" Ingredients".

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

The component (α) is preferably an acrylic resin. When the (α) component is an acrylic resin, it is easy to improve the initial water repellency, durable water repellency, or both (hereinafter, also simply referred to as “water repellency”), and water permeability resistance.

Hereinafter, the acrylic resin will be described.

The (meth)acrylate monomer (A) represented by the general formula (A-1) used in this embodiment (hereinafter, also referred to as "monomer (A)") has a carbon which may have a substituent The number is a monovalent hydrocarbon group of 12 or more. The hydrocarbon group may be linear or branched, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may further have an alicyclic or aromatic ring. Among these, from the viewpoint of water repellency and water repellency, linear ones are preferred, and linear alkyl groups are more preferred. When the monovalent hydrocarbon group having 12 or more carbon atoms has a substituent, examples of the substituent include a hydroxyl group, an amine group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, and (methyl) One or more of propylene acetyloxy and the like. In the present embodiment, in the above general formula (A-1), R ^{2 is} preferably an unsubstituted hydrocarbon group.

The carbon number of the hydrocarbon group is preferably 12-24, and more preferably 12-22. If the carbon number of the hydrocarbon group is within this range, it is easy to sufficiently maintain the texture of the fiber substrate and improve the water repellency and water permeability resistance imparted to the fiber substrate. 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, and (methyl) ) Pentadecyl acrylate, heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, arachidyl (meth) acrylate Base ester, behenate (meth)acrylate, wax (meth)acrylate, beeswax (meth)acrylate, etc.

The above monomer (A) may have at least one functional group selected from the group consisting of a hydroxyl group, an amine group, a carboxyl group, an epoxy group, and an isocyanate group that can react with a crosslinking agent described below. In this case, it is easy to increase the water repellency and water permeability resistance imparted to the fiber substrate. The isocyanate group can form a blocked isocyanate group protected by a blocking agent. In addition, when the monomer (A) has an amine group, the texture of the obtained fiber product can be further improved.

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

One type of the monomer (A) may be used alone, or two or more types may be used in combination.

Regarding the above-mentioned monomer (A), from the viewpoint of improving the water repellency and water permeability resistance imparted to the fiber base material, it is preferable to use the acrylate monomer (a1) (hereinafter, also referred to as "(a1) component" ) Is used in combination with the methacrylate monomer (a2) (hereinafter, also referred to as "(a2) component"). The ratio of the mass of the (a1) component to the mass of the (a2) component (a1)/(a2) is preferably 30/70 to 90/10, more preferably 40/60 to 85/15, and further preferably 50/50～80/20, especially 60/40～80/20. In the case where (a1)/(a2) is within the above range, it is easy to increase the water repellency and water permeability resistance imparted to the fiber base material.

When the water repellent composition of the present embodiment contains an acrylic resin as the (α) component, the total composition ratio of the above-mentioned monomers (A) in the acrylic resin can be 50 to 100% by mass, which improves the fiber From the viewpoint of water repellency and water permeability resistance imparted by the substrate, it is preferably 50 to 99% by mass, more preferably 60 to 99% by mass, and still more preferably the total amount of monomer components constituting the acrylic resin. 70 to 99% by mass.

The weight average molecular weight of the acrylic resin is preferably 100,000 or more. If the weight average molecular weight is 100,000 or more, the water repellency of the obtained water repellent fiber product tends to be easily increased. Furthermore, from the viewpoint of further improving the water repellency of the obtained water repellent fiber product, the weight average molecular weight of the acrylic resin is more preferably 500,000 or more. The upper limit of the weight average molecular weight of the acrylic resin is preferably about 5 million. In the specification of this case, the weight average molecular weight refers to a value measured by GPC (Gel Permeation Chromatograph, gel permeation chromatography) and converted to standard polystyrene.

In the present embodiment, the melt viscosity of the acrylic resin at 105° C. is preferably 1000 Pa·s or less. When the melt viscosity at 105°C is 1000 Pa·s or less, there is a tendency to easily obtain a water-repellent fiber product with excellent texture. In addition, when the melt viscosity at 105°C is 1000 Pa·s or less, precipitation or precipitation of the acrylic resin can be suppressed when the acrylic resin is emulsified or dispersed to form a water repellent composition, and the water repellent agent combination is present The tendency of the storage stability of objects to improve. Furthermore, the melt viscosity of the acrylic resin at 105°C is more preferably 500 Pa·s or less. In this case, the obtained water-repellent fiber products and the like have sufficient water-repellent properties and are more excellent in texture.

Regarding the acrylic resin, from the viewpoint of improving the emulsion stability of the water-repellent and water-impermeable water, and the emulsion polymerization or dispersion polymerization of the acrylic resin and after polymerization, it is preferable to remove the monomer (A ) Contains (B1) a compound represented by the following general formula (B-1) with an HLB of 7 to 18, (B2) a compound represented by the following general formula (B-2) with an HLB of 7 to 18 And (B3) at least one reactive emulsifier (B) in a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an oil and fat having a hydroxyl group and a polymerizable unsaturated group with an HLB of 7 to 18 (B) ( Hereinafter, it is also called "reactive emulsifier (B)") as a monomer component.

[式(B-1)中，R³ 表示氫或甲基，X表示碳數1～6之直鏈或支鏈之伸烷基，Y¹ 表示包含碳數2～4之伸烷氧基之2價基][Chem 5]

[In formula (B-1), R ³ represents hydrogen or methyl, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y ¹ represents an alkylene group containing 2 to 4 carbon atoms. 2 price base]

[式(B-2)中，R⁴ 表示具有聚合性不飽和基之碳數13～17之1價不飽和烴基，Y² 表示包含碳數2～4之伸烷氧基之2價基][化6]

[In formula (B-2), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms with a polymerizable unsaturated group, and Y ² represents a divalent group including an alkoxy group having 2 to 4 carbon atoms]

The so-called "reactive emulsifier" is an emulsifying and dispersing agent with radical reactivity, that is, a surfactant having at least one polymerizable unsaturated group in the molecule, and can be used with monomers such as (meth)acrylate Copolymerize.

In the description of this case, the so-called "HLB", unless otherwise stated, refers to the treatment of ethoxylated groups as hydrophilic groups and all other groups as lipophilic groups, calculated by the Griffin Method HLB value.

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

In the reactive emulsifier (B1) represented by the general formula (B-1), R ³ is hydrogen or methyl, and in terms of copolymerization with the monomer (A), it is more preferably methyl. X is a linear or branched alkylene group having 1 to 6 carbon atoms. In terms of the emulsion stability of the acrylic resin, it is more preferably a linear alkylene group having 2 to 3 carbon atoms. Y ¹ is a divalent group containing an alkoxy group having 2 to 4 carbon atoms. The kind, combination, and addition number of the alkoxy group in Y ¹ can be appropriately selected so as to fall within the range of the above HLB. In addition, when there are two or more alkoxy groups, these may have a block addition structure or a random addition structure.

As the compound represented by the general formula (B-1), the compound represented by the following general formula (b-1) is preferred.

[式(b-1)中，R³ 表示氫或甲基，X表示碳數1～6之直鏈或支鏈之伸烷基，A¹ O表示碳數2～4之伸烷氧基，m能夠以成為上述HLB之範圍內之方式適當選擇，具體而言，較佳為1～80之整數，於m為2以上時，m個A¹ O可相同亦可不同][化7]

[In formula (b-1), R ³ represents hydrogen or methyl, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and A ¹ O represents an alkoxy group having 2 to 4 carbon atoms, m can be appropriately selected so as to be within the range of the above HLB, specifically, it is preferably an integer of 1 to 80, and when m is 2 or more, m A ¹ O may be the same or different]

In the compound represented by the general formula (b-1), R ³ is hydrogen or methyl, and in terms of copolymerization with the monomer (A), it is more preferably methyl. X is a linear or branched alkylene group having 1 to 6 carbon atoms. In terms of the emulsion stability of the acrylic resin, it is more preferably a linear alkylene group having 2 to 3 carbon atoms. A ¹ O is an alkoxy group having 2 to 4 carbon atoms. The type and combination of A ¹ O and the number of m can be appropriately selected so as to fall within the range of the above HLB. Regarding the emulsification stability of the acrylic resin, m is preferably an integer of 1 to 80, more preferably an integer of 1 to 60. When m is 2 or more, m A ¹ O may be the same or different. Moreover, when A ¹ O is 2 or more types, these may have a block addition structure or a random addition structure.

The reactive emulsifier (B1) represented by the general formula (b-1) can be obtained by a previously known method, and is not particularly limited. In addition, it can be easily obtained from commercially available products, and examples 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), R ⁴ is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and examples include tridecene Group, tridecadienyl, tetradecenyl, tetradienyl, tetradienyl, pentadecenyl, pentadecadienyl, pentadecenyl, heptadecenyl, ten Seven carbon dienyl and seventeen carbon trienyl. In terms of the emulsion stability of the acrylic resin, R ^{4 is more} preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

Y ² is a divalent group containing an alkoxy group having 2 to 4 carbon atoms. The kind, combination, and addition number of the alkoxy group in Y ² can be appropriately selected so as to fall within the range of the above HLB. In addition, when there are two or more alkoxy groups, these may have a block addition structure or a random addition structure. In terms of the emulsion stability of the acrylic resin, the alkoxy group is more preferably an ethoxy group.

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

[式(b-2)中，R⁴ 表示具有聚合性不飽和基之碳數13～17之1價不飽和烴基，A² O表示碳數2～4之伸烷氧基，n能夠以成為上述HLB之範圍內之方式適當選擇，具體而言，較佳為1～50之整數，於n為2以上時，n個A² O可相同亦可不同][Chem 8]

[In formula (b-2), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, A ² O represents an alkoxy group having 2 to 4 carbon atoms, and n can be The method within the range of the above HLB is appropriately selected, specifically, it is preferably an integer of 1 to 50, and when n is 2 or more, n A ² O may be the same or different]

Compound of the formula (b-2) represented by the R ⁴ in the above general formula include R (B-2) are the same as those of ^4.

A ² O is an alkoxy group having 2 to 4 carbon atoms. Regarding the emulsification stability of the acrylic resin, the type and combination of A ² O and the number of n can be appropriately selected so as to fall within the range of the above HLB. In terms of the emulsification stability of the acrylic resin, A ² O is more preferably an ethoxy group, n is preferably an integer of 1-50, more preferably an integer of 5-20, and further preferably 8-14 An integer. When n is 2 or more, n A ² O may be the same or different. Moreover, when A ² O is 2 or more types, these 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 a alkylene oxide of phenol having a corresponding unsaturated hydrocarbon group by a previously known method, and is not particularly limited. For example, it can be synthesized by adding a specific amount of alkylene oxide at 120 to 170°C under pressure using alkaline catalysts such as caustic soda and caustic potash.

The above-mentioned phenol having a corresponding unsaturated hydrocarbon group includes, in addition to industrially produced pure products or mixtures, those extracted and refined from plants and the like in the form of pure products or mixtures. For example, 3-[8(Z), 11(Z), 14-pentadecatrienyl]phenol, 3-[8(Z), which are extracted from the shells of cashew nuts and are collectively called Cardanol 11(Z)-Pentadecadienyl]phenol, 3-[8(Z)-Pentadecenyl]phenol and 3-[11(Z)-Pentadecenyl]phenol, etc.

The reactive emulsifier (B3) is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an oil and fat having a hydroxyl group and a polymerizable unsaturated group with an HLB of 7 to 18. Examples of oils and fats having a hydroxyl group and a polymerizable unsaturated group include unsaturated fatty acids (palmitoleic acid, oleic acid, linolenic acid, α-linolenic acid, arachidonic acid, and eicosapentaenoic acid). , Docosapentenoic acid, etc.) fatty acid mono- or diglycerides, fatty acids containing at least one hydroxy unsaturated fatty acid (ricinoleic acid, trans ricinoleic acid, 2-hydroxytetracosenoic acid, etc.) Triglycerides, etc. In terms of emulsification stability of acrylic resins, alkylene oxide adducts of triglycerides of fatty acids containing at least one hydroxy unsaturated fatty acid are preferred, and castor oil (including ricinoleic acid-containing fatty acids) is more preferred Alkylene oxide adduct of carbon number 2 to 4 of triglyceride), more preferably ethylene oxide adduct of castor oil. Furthermore, the addition mole number of the alkylene oxide can be appropriately selected so as to fall within the range of the above HLB, and in terms of the emulsion stability of the acrylic resin, it is more preferably 20 to 50 moles, and even more preferably 25 to 45 moles. In addition, when there are two or more types of alkylene oxides, these may have a block addition structure or a random addition structure.

The reactive emulsifier (B3) can be synthesized by the addition of alkylene oxide to a fat and oil having a hydroxyl group and a polymerizable unsaturated group by a previously known method, and is not particularly limited. For example, it can be synthesized by adding caustic soda, caustic potash and other alkaline catalysts to a certain amount of alkylene oxide at 120-170°C under pressure using castor oil, which is a triglyceride containing ricinoleic acid fatty acid.

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

When the water repellent composition contains an acrylic resin as the (α) component, from the viewpoint of water repellency, the acrylic resin preferably contains, in addition to the monomer (A), a resin selected from the following (C1), ( At least one second (meth)acrylate monomer (C) in the group consisting of C2), (C3), (C4) and (C5) (hereinafter also referred to as "monomer (C)") As a monomer component.

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

[式(C-1)中，R⁵ 表示氫或甲基，R⁶ 表示具有選自由羥基、胺基、羧基、環氧基、異氰酸基及(甲基)丙烯醯氧基所組成之群中之至少1種官能基之碳數1～11之1價鏈狀烴基；其中，分子內中之(甲基)丙烯醯氧基之數為2以下][化9]

[In formula (C-1), R ⁵ represents hydrogen or methyl, and R ⁶ represents a compound selected from the group consisting of hydroxy, amine, carboxy, epoxy, isocyanate, and (meth)acryloyloxy At least one functional group in the group has a monovalent chain hydrocarbon group having a carbon number of 1 to 11; 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).

[式(C-2)中，R⁷ 表示氫或甲基，R⁸ 表示可具有取代基之碳數1～11之1價環狀烴基][化10]

[In formula (C-2), R ⁷ represents hydrogen or methyl, and R ⁸ represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent]

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

[式(C-3)中，R⁹ 表示未經取代之碳數1～4之1價鏈狀烴基][Chem 11]

[In formula (C-3), R ⁹ represents an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms]

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

[式(C-4)中，R¹⁰ 表示氫或甲基，p表示2以上之整數，S表示(p＋1)價之有機基，T表示具有聚合性不飽和基之1價有機基][化12]

[In formula (C-4), R ¹⁰ represents hydrogen or methyl, p represents an integer of 2 or more, S represents an (p+1)-valent organic group, and T represents a monovalent organic group having a polymerizable unsaturated group]

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

[式(C-5)中，R¹⁵ 表示氫或甲基，R¹⁶ 表示具有選自由氯基及溴基所組成之群中之至少1種官能基及羥基之碳數3～6之1價鏈狀飽和烴基][Chem 13]

[In formula (C-5), R ¹⁵ represents hydrogen or methyl, and R ¹⁶ represents a monovalent carbon number of 3 to 6 having at least one functional group selected from the group consisting of a chloro group and a bromo group and a hydroxyl group. Chain saturated hydrocarbon group]

The monomer of (C1) above has at least one functional group selected from the group consisting of hydroxyl group, amine group, carboxyl group, epoxy group, isocyanate group and (meth)acryloyloxy group in the ester part A (meth)acrylate monomer having a monovalent chain hydrocarbon group having 1 to 11 carbon atoms, and is a (meth)acrylate monomer other than the above (C5). In terms of being reactive with a crosslinking agent, the above-mentioned monovalent chain hydrocarbon group having 1 to 11 carbon atoms preferably has a group selected from the group consisting of a hydroxyl group, an amine group, a carboxyl group, an epoxy group and an isocyanate group At least one functional group. When the fiber base material is treated with a composition containing a cross-linking agent and an acrylic resin containing monomers (C1) capable of reacting with the cross-linking agent, the fiber base material can be maintained Improve water repellency without changing texture. The isocyanate group may also be a blocked isocyanate group protected by a blocking agent.

The chain hydrocarbon group may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, the chain hydrocarbon group may have a substituent in addition to the above functional group. Among them, from the viewpoints of water repellency and texture, linear and/or saturated hydrocarbon groups are preferred.

Specific monomers of (C1) include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and isocyanate 1,1 -Bis (acryloyloxymethyl) ethyl ester, etc. One type of these monomers may be used alone, or two or more types may be used in combination. Among them, from the viewpoint of water repellency, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are preferred ester. Furthermore, from the viewpoint of water repellency, dimethylaminoethyl (meth)acrylate is preferred.

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

The above-mentioned (C2) monomer is a (meth)acrylate monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester portion. Examples of the cyclic hydrocarbon group include isobutyl, cyclohexyl, and dicyclopentane. Base etc. The cyclic hydrocarbon group may have a substituent such as an alkyl group. However, 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 a hydrocarbon group of 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 alicyclic or aromatic. In the case of alicyclic, it may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of specific monomers include isomethacrylate (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentyl (meth)acrylate. One type of these monomers may be used alone, or two or more types may be used in combination. Among them, from the viewpoint of water repellency, isocyanate (meth)acrylate and cyclohexyl methacrylate are preferred, and isocyanate methacrylate is more preferred.

The composition ratio of the above-mentioned (C2) monomer in the acrylic resin is preferably 1 to 30% by mass relative to the total amount of monomer components constituting the acrylic resin from the viewpoint of water repellency, and more preferably It is 3 to 25% by mass, and more preferably 5 to 20% by mass.

The above-mentioned (C3) monomer is a methacrylate monomer having an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms directly bonded to the ester bond of the ester portion. The linear hydrocarbon group having 1 to 4 carbon atoms is preferably a linear hydrocarbon group having 1 to 2 carbon atoms and a branched 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, and tertiary butyl groups. Specific compounds include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and methyl methacrylate Third butyl acrylate and so on. One type of these monomers may be used alone, or two or more types may be used in combination. Among them, from the viewpoint of water repellency, methyl methacrylate, isopropyl methacrylate, and third butyl methacrylate are preferred, and methyl methacrylate is more preferred.

The composition ratio of the above-mentioned (C3) monomer in the acrylic resin is preferably from 1 to 30% by mass relative to the total amount of monomer components constituting the acrylic resin from the viewpoint of water repellency, and more preferably It is 3 to 25% by mass, and more preferably 5 to 20% by mass.

The above-mentioned (C4) monomer is a (meth)acrylate monomer having three or more polymerizable unsaturated groups in one molecule. In this embodiment, it is preferable that T in the above general formula (C-4) is a (meth)acryloyloxy group having more than three (meth)acryloyloxy groups in one molecule. (Meth) acrylate monomer. In formula (C-4), p Ts may be the same or different. Specific compounds include, for example, ethoxylated isocyanurate triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethacrylate Hydroxymethylpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. One type of these monomers may be used alone, or two or more types may be used in combination. Among them, from the viewpoint of water repellency, tetramethylolmethane tetraacrylate and ethoxylated isocyanurate triacrylate are more preferred.

The composition ratio of the above-mentioned (C4) monomer in the acrylic resin is preferably from 1 to 30% by mass relative to the total amount of monomer components constituting the acrylic resin from the viewpoint of water repellency, and more preferably It is 3 to 25% by mass, and more preferably 5 to 20% by mass.

The monomer of (C5) has a monovalent chain saturated hydrocarbon group having 3 to 6 carbon atoms, and the chain saturated hydrocarbon group has at least one functional group and a hydroxyl group selected from the group consisting of a chlorine group and a bromine group. In the above monomer (C5), R ¹⁵ is hydrogen or methyl. From the viewpoint of water repellency, R ^{15 is} preferably a methyl group.

R ¹⁶ is a C 3-6 monovalent chain saturated hydrocarbon group having at least one functional group selected from the group consisting of a chlorine group and a bromine group and a hydroxyl group. The chain-shaped saturated hydrocarbon group may be linear or branched. From the viewpoint of water repellency, the chain saturated hydrocarbon group is preferably linear. The carbon number of the chain saturated hydrocarbon group is preferably 3 to 4, and more preferably 3 from the viewpoint of water repellency.

From the viewpoint of water repellency, the above-mentioned chain-like 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. In addition, from the viewpoint of water repellency, the chain-like saturated hydrocarbon group preferably further has a hydroxyl group at the β position (the carbon atom adjacent to the carbon atom bonded to CH ₂ =CR ¹⁵ (CO)O-). Specific examples of the chain saturated hydrocarbon group include, for example, 3-chloro-2-hydroxypropyl, 3-chloro-2-hydroxybutyl, 5-chloro-2-hydroxypentyl, and 3-chloro-2-hydroxy -2-methylpropyl and 3-bromo-2-hydroxypropyl, etc.

Specific monomers of (C5) include, for example, 3-chloro-2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxybutyl (meth)acrylate, and (meth)acrylic acid 5 -Chloro-2-hydroxypentyl ester and 3-bromo-2-hydroxypropyl (meth)acrylate, etc. Among them, from the viewpoint of water repellency, 3-chloro-2-hydroxypropyl (meth)acrylate and 3-chloro-2-hydroxypropyl methacrylate are preferred, and 3-chloromethacrylate is more preferred. -2-hydroxypropyl ester.

The composition ratio of the above-mentioned (C5) monomer in the acrylic resin is preferably from 1 to 30% by mass relative to the total amount of monomer components constituting the acrylic resin from the viewpoint of water repellency, and more preferably It is 3 to 25% by mass, and more preferably 5 to 20% by mass.

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

In the case where the water repellent composition contains an acrylic resin as the (α) component, the acrylic resin, in addition to the monomer (A), the reactive emulsifier (B) and the monomer (C), can be used without prejudice to the present invention. The monofunctional monomer (D) copolymerizable with these (hereinafter, also referred to as "monomer (D)") is included in the range of effects.

Examples of the monomer (D) include (meth)acrylonitrile, (meth)acrylic acid esters having a hydrocarbon group other than monomer (A) and monomer (C), (meth)acrylic acid , Fumaric acid ester, maleic acid ester, fumaric acid, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ether, vinyl ester Vinyl monomers other than monomers (E) described below which do not contain fluorine such as ethylene, styrene, etc. In addition, the (meth)acrylate having a hydrocarbon group other than the monomer (A) and the monomer (C) may have a vinyl group, a hydroxyl group, an amine group, an epoxy group and an isocyanate group in the hydrocarbon group. Substituents such as cyano groups may also have quaternary ammonium groups and other substituents other than the groups that can react with the crosslinking agent, and may also have ether bonds, ester bonds, amide bonds, or carbamate bonds, etc. . Examples of (meth)acrylates other than monomer (A) and monomer (C) include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and Ethylene glycol di(meth)acrylate, etc.

The composition ratio of the monomer (D) in the acrylic resin is preferably 10% by mass or less relative 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, from the viewpoint of water repellency, the acrylic resin preferably has a reaction group selected from the group consisting of a hydroxyl group, an amine group, and a carboxyl group. At least one functional group in the group consisting of epoxy groups and isocyanate groups. The isocyanate group can also form a blocked isocyanate group protected by a blocking agent. In addition, the acrylic resin preferably has an amine group from the viewpoint of water repellency.

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

From the viewpoint of maintaining the texture of the fiber base material, at least one monomer (E) of vinyl chloride and vinylidene chloride used in the present embodiment is preferably vinyl chloride.

The composition ratio of the monomer of the above-mentioned monomer (E) in the acrylic resin may be 1 to 50% by mass. From the viewpoint of water repellency and peel strength, relative to the total amount of monomer components constituting the acrylic resin The amount is preferably 1 to 45% by mass, more preferably 3 to 40% by mass, and still more preferably 5 to 35% by mass.

The acrylic resin can be synthesized by a conventionally known method, and is not particularly limited. For example, it can be synthesized by a radical polymerization method. In addition, in this radical polymerization method, in terms of the performance and environment of the water repellent agent obtained, it is preferable to carry out polymerization by an emulsion polymerization method or a dispersion polymerization method.

For example, an acrylic resin can be obtained by subjecting the (meth)acrylate monomer (A) represented by the general formula (A-1) to emulsion polymerization or dispersion polymerization in a medium. More specifically, for example, the monomer (A) and the above-mentioned reactive emulsifier (B), the above-mentioned monomer (C), the above-mentioned monomer (D) and the above-mentioned monomer (E) are added to the medium, and An emulsification auxiliary agent or dispersion auxiliary agent emulsifies or disperses the mixed liquid to obtain an emulsified product or a dispersed product. The monomer and the reactive emulsifier can be polymerized by adding a polymerization initiator to the obtained emulsion or dispersion to start the polymerization reaction. In addition, examples of the mechanism for emulsifying or dispersing the mixed liquid include a homomixer, a high-pressure emulsifier, and ultrasonic waves.

As the above-mentioned emulsification aid or dispersion aid, etc. (hereinafter, also referred to as "emulsification aid, etc."), other than the reactive emulsifier (B), selected from nonionic surfactants, cationic surfactants, At least one of anionic surfactants and amphoteric surfactants. From the viewpoint of storage stability, an emulsification aid or the like is preferably a nonionic surfactant.

Examples of nonionic surfactants include alcohols, polycyclic phenols, amines, amides, fatty acids, polyol fatty acid esters, oils and fats, and alkylene oxide adducts of polypropylene glycol.

Examples of the alcohols include linear or branched alcohols having 8 to 24 carbon atoms or alkenols, or represented by the following general formula (AL-1) or the following general formula (AL-2) The acetylene alcohol and so on.

[式(AL-1)中，R²¹ 及R²² 分別獨立，表示碳數1～8之具有直鏈或者支鏈之烷基或碳數2～8之具有直鏈或者支鏈之烯基][化14]

[In formula (AL-1), R ²¹ and R ²² are each independently, and represent a C1-C8 linear or branched alkyl group or a C2-C8 linear or branched alkenyl group]

[式(AL-2)中，R²³ 表示碳數1～8之具有直鏈或者支鏈之烷基或碳數2～8之具有直鏈或者支鏈之烯基][化15]

[In formula (AL-2), R ²³ represents a linear or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkenyl group having 2 to 8 carbon atoms]

Examples of the polycyclic phenols include monovalent phenols such as phenol and naphthol having a hydrocarbon group of 1 to 12 carbons or styrenes (styrene, α-methylstyrene, vinyltoluene) Adducts or such benzyl chloride reactants, etc. Examples of the amines include linear or branched aliphatic amines having 8 to 44 carbon atoms.

Examples of the amides include straight-chain or branched aliphatic amides having 8 to 44 carbon atoms.

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

Examples of the polyhydric alcohol fatty acid esters include condensation products of polyhydric alcohols and linear or branched fatty acids having 8 to 24 carbon atoms.

Examples of oils and fats include vegetable oils, animal oils, vegetable waxes, animal waxes, mineral waxes, and hydrogenated oils.

Among these, from the viewpoint of less influence on water repellency and water repellency durability, less influence on light resistance, and better emulsification of acrylic resin, linear or branched chain is preferred The alcohol or alkenol having 8 to 24 carbon atoms and the acetylene alcohol represented by the above general formula (AL-1) are more preferably linear or branched alcohols having 8 to 24 carbon atoms and the above general formula (AL-1) ) Represents acetylene alcohol.

Examples of the alkylene oxide include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,4-butylene oxide, and cyclic Oxybenzene and epichlorohydrin. From the viewpoint of less influence on water repellency and better emulsification of the copolymer, the alkylene oxide is preferably ethylene oxide and 1,2-propylene oxide, more preferably ethylene oxide .

The addition mole number of alkylene oxide is preferably 1 to 200, more preferably 3 to 100, and still more preferably 5 to 50. If the addition mole number of the alkylene oxide is within the above range, the water repellency and the emulsification of the copolymer tend to be further improved.

In the copolymer of the present embodiment, when a nonionic surfactant having an HLB of 4 to 17 defined by the following formula (H) is used as the nonionic surfactant, a better aqueous dispersion can be obtained. Here, the HLB defined by the following formula (H) is based on Griffin's HLB, and the Griffin's formula is changed to the following formula (H). Here, the hydrophilic group refers to an ethylene oxide group. HLB = (hydrophilic group × 20) / molecular weight (H)

Regarding the HLB specified in the above formula (H) of the above nonionic surfactant, regarding the emulsification stability of the component (A) at the time of emulsion polymerization or dispersion polymerization and after polymerization (hereinafter, referred to as emulsion stability) In this respect, it is preferably 5 to 15. Furthermore, in terms of storage stability of the water repellent composition, it is more preferable to use two or more nonionic surfactants having different HLBs within the above range. In addition, from the viewpoint of emulsification stability and water repellency, 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 relative to 100 parts by mass of the total monomer constituting the acrylic resin. If the content of the above-mentioned emulsification auxiliary agent is 0.5 parts by mass or more, there is a tendency to further improve the dispersion stability of the mixed liquid compared with the case where the content of the emulsification auxiliary agent is less than 0.5 parts by mass. When the content is 30 parts by mass or less, compared with the case where the content of the emulsification auxiliary agent exceeds 30 parts by mass, there is a tendency for the water repellent composition of the obtained water repellent composition to increase.

As a medium for emulsification polymerization or dispersion polymerization, water is preferable, and water and an organic solvent may be mixed as needed. Examples of the organic solvent at this time include alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, ethers such as diethyl ether, and the like, propylene glycol, dipropylene glycol, and tripropylene glycol. Other glycols. In terms of further improving the water repellency and water permeability resistance imparted to the fiber base material, it is preferable to use glycols. Furthermore, the ratio of water to organic solvent is not particularly limited.

As the polymerization initiator, a known polymerization initiator such as azo-based, peroxide-based, or redox-based can be used as appropriate. The content of the polymerization initiator is preferably 0.01 to 2 parts by mass relative to 100 parts by mass of the total monomer constituting the acrylic resin. If the content of the polymerization initiator is within the above range, an acrylic resin having a weight average molecular weight of 100,000 or more can be efficiently produced.

In addition, in the polymerization reaction, a chain transfer agent such as dodecyl mercaptan and third butanol may be used for molecular weight adjustment.

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

The temperature of the polymerization reaction is preferably 20°C to 150°C. If the temperature does not reach 20°C, the polymerization tends to be insufficient compared to when the temperature is within the above range, and if the temperature exceeds 150°C, the control of the reaction heat may become difficult.

In the polymerization reaction, the weight average molecular weight of the acrylic resin obtained can be adjusted by the increase or decrease of the content of the above polymerization initiator, chain transfer agent, polymerization inhibitor, and the melt viscosity at 105°C can be multifunctional Adjust the increase and decrease of the monomer content and the polymerization initiator content. Furthermore, when the melt viscosity at 105° C. is to be reduced, it is only necessary to reduce the content of monomers having two or more polymerizable functional groups or increase the content of the polymerization initiator.

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

In the polymerization reaction, for example, the polymerization reaction may be performed by photopolymerization by irradiation of ultraviolet radiation, electron beams, free radiation such as γ rays, etc., instead of the polymerization reaction by the polymerization initiator.

Next, the urethane resin will be described.

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

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

In the above general formula (I-1), when d is 2 or more, a plurality of W ¹ may be the same or different. A plurality of R ³² may be the same or different. There are multiple V ^{1s that} may be the same or different.

R ³¹ represents a (d+e)-valent organic group. From the viewpoint of water repellency and water permeability resistance, the carbon number of R ³¹ is preferably 2 to 40, more preferably 4 to 12. R ^{31 is} preferably a group represented by the following chemical formula (1), a group represented by the following chemical formula (2), and a group represented by the following chemical formula (3). From the viewpoint of ease of handling of the urethane resin, (d+e) is preferably 3 to 4.

[Chem 16]

[化17]

[式(3)中，r表示1以上之整數][Chemical 18]

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

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

R ³¹ may be removed from a polyfunctional compound having (d+e) at least one functional group selected from the group consisting of a hydroxyl group, an amine group, and a carboxyl group (hereinafter, also referred to as "polyfunctional compound A") (d+e ) Residues derived from a functional group. Among them, two or more of the (d+e) functional groups are hydroxyl groups and/or amine groups.

Examples of the polyfunctional compound A include trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, glycerin, diethylenetriamine, triethylenetetramine, and tetrakis Ethylene pentamine, pentaethyl hexaamine, aminoethyl ethanolamine, diethanolamine, triethanolamine, etc. Among these, from the viewpoints of water repellency and water permeability resistance, and the emulsion dispersion stability of the obtained urethane resin, trimethylolpropane, di-trimethylolpropane, Diethanolamine and diethylenetriamine.

W ¹ represents a divalent group of an ester group, an amide group, a carbamate group or a urea group. W ¹ is preferably an ester group or a urethane group from the viewpoint of water repellency and water permeability resistance.

R ³² represents a linear or branched monovalent 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 ring. As the hydrocarbon group, from the viewpoint of water repellency and water permeability resistance, those having a straight chain shape are preferred, and a straight chain alkyl group is more preferred. The carbon number of the hydrocarbon group is preferably 10-24, more preferably 12-22, and particularly preferably 12-18. When the carbon number is within this range, it is easy to sufficiently maintain the texture of the fiber substrate and improve the water repellency and water permeability resistance imparted to the fiber substrate. As the hydrocarbon group, a linear alkyl group having 12 to 18 carbon atoms is particularly preferred.

Examples of R ³² include nonyl, decyl, undecyl, dodecyl (lauryl), tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. Alkyl, nonadecyl, eicosyl, behenyl and behenyl etc.

R ³² may be a residue obtained by removing a reactive group from a reactive hydrocarbon compound having a reactive group that can react with the functional group possessed by the polyfunctional compound A. Examples of the reactive hydrocarbon compound include higher fatty acids having 8 to 24 carbon atoms (in addition, the carbon number includes carbon of a carbonyl group), higher aliphatic alcohols, higher aliphatic monoisocyanates, and higher aliphatic amines.

Examples of higher fatty acids include lauric acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, oleic acid, eicosanoic acid, and behenic acid.

Examples of higher aliphatic alcohols include lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, eicosyl alcohol, behenyl alcohol, and behenyl alcohol.

Examples of the higher aliphatic monoisocyanate include decyl isocyanate, undecyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, and pentadecyl isocyanate. Esters, cetyl isocyanate, octadecyl isocyanate, eicosyl isocyanate and behenate isocyanate.

Examples of higher aliphatic amines include decylamine, laurylamine, myristylamine, stearylamine, and behenamine.

V ¹ represents a hydroxyl group, an amine group or a carboxyl group. From the viewpoint of water repellency, V ¹ is preferably a hydroxyl group or an amine group.

The polyfunctional compound represented by the above general formula (I-1) can be, for example, a polyfunctional compound having (d+e) at least one functional group selected from the group consisting of the above hydroxyl group, amine group and carboxyl group (multiple The functional compound A) is produced by introducing d hydrophobic groups represented by [-W ¹ -R ³² ].

The hydrophobic group represented by [-W ¹ -R ³² ] can be, for example, the unreacted function of the polyfunctional compound A by making the reactive hydrocarbon compound of 1 mole or more with respect to 1 mole of the polyfunctional compound A. The method in which the number of groups e becomes 2 or more is introduced by a reaction by a previously known synthesis method, that is, an esterification reaction, an amidation reaction, or a carbamate reaction.

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

C[-R ⁴¹ ] _g [-R ⁴² -V ² ] _h [-R ⁴³ -W ² -R ⁴⁴ ] _i (I-2) [In 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, R ⁴¹ represents a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ⁴² represents a divalent value of 1 to 2 carbon atoms Alkyl extension, R ⁴³ represents a bivalent alkylene group having 1 to 4 carbon atoms, R ⁴⁴ represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms, and W ² represents an ester group, an amide group, an amine Divalent group of carbamate group or urea group, V ² represents a hydroxyl group, an amine group or a carboxyl group; wherein, more than ^two V ² are a hydroxyl group and/or an amine group]

[式(I-3)中，R⁵¹ 及R⁵² 分別獨立地表示碳數1～4之直鏈或支鏈之烴基，R⁵⁴ 及R⁵⁵ 分別獨立地表示碳數1～4之2價伸烷基，R⁵³ 、R⁵⁶ 、R⁵⁷ 及R⁵⁸ 分別獨立地表示下述通式(4)或下述通式(5)所表示之1價基； -R⁵⁹ -V³ (4) {R⁵⁹ 表示碳數1～4之2價伸烷基，V³ 表示羥基、胺基或羧基} -R⁶⁰ -W³ -R⁶¹ (5) {R⁶⁰ 表示碳數1～4之2價伸烷基，R⁶¹ 表示碳數8～24之直鏈或支鏈之1價烴基，W³ 表示為酯基、醯胺基、胺基甲酸酯基或脲基之2價基}， 其中，R⁵³ 、R⁵⁶ 、R⁵⁷ 及R⁵⁸ 中之至少2個為V³ 為羥基或胺基之上述通式(4)所表示之基][Chem 19]

[In formula (I-3), R ⁵¹ and R ⁵² each independently represent a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ⁵⁴ and R ⁵⁵ each independently represent a divalent extension of 1 to 4 carbon atoms. Alkyl, R ⁵³ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent group represented by the following general formula (4) or the following general formula (5); -R ⁵⁹ -V ³ (4) { R ⁵⁹ represents a bivalent alkylene group having 1 to 4 carbon atoms, and V ³ represents a hydroxyl group, an amine group or a carboxyl group. -R ⁶⁰ -W ³ -R ⁶¹ (5) {R ⁶⁰ represents a divalent alkylene group having 1 to 4 carbon atoms Alkyl group, R ⁶¹ represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms, and W ³ represents a divalent group of an ester group, an amido group, a carbamate group or a urea group}, where, At least two of R ⁵³ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ are groups represented by the above general formula (4) in which V ³ is a hydroxyl group or an amine group]

[式(I-4)中，j表示1～4之整數，R⁷¹ 及R⁷³ 分別獨立地表示碳數1～4之2價伸烷基，R⁷² 及R⁷⁴ 分別獨立地表示羥基、胺基或下述通式(6)所表示之1價基，R⁷⁵ 表示氫、下述通式(7)、下述通式(8)或下述通式(9)所表示之1價基； -W⁴ -R⁷⁶ (6) {式(6)中，W⁴ 表示為酯基、醯胺基、胺基甲酸酯基或脲基之2價基，R⁷⁶ 表示碳數8～24之直鏈或支鏈之1價烴基} -R⁷⁷ -OH      (7) {式(7)中，R⁷⁷ 表示碳數2～3之伸烷基} -R⁷⁸ -W⁵ -R⁷⁹ (8) {式(8)中，R⁷⁸ 表示碳數2～3之伸烷基，R⁷⁹ 表示碳數8～24之直鏈或支鏈之1價烴基，W⁵ 表示為酯基、醯胺基、胺基甲酸酯基或脲基之2價基} -W⁶ -R⁸⁰ (9) {式(9)中，W⁶ 表示羰基或醯胺基，R⁸⁰ 表示碳數8～24之直鏈或支鏈之1價烴基}， 其中，R⁷² 、R⁷⁴ 及j個R⁷⁵ 中之至少2個為羥基、胺基、氫、上述通式(7)所表示之1價基，R⁷² 及R⁷⁴ 為羥基或胺基，R⁷⁵ 為氫或上述通式(7)所表示之1價基][化20]

[In formula (I-4), j represents an integer of 1 to 4, R ⁷¹ and R ⁷³ each independently represent a divalent alkylene group having 1 to 4 carbon atoms, and R ⁷² and R ⁷⁴ each independently represent a hydroxyl group and an amine Group or a monovalent group represented by the following general formula (6), R ⁷⁵ represents hydrogen, a monovalent group represented by the following general formula (7), the following general formula (8) or the following general formula (9) ; -W ⁴ -R ⁷⁶ (6) {In formula (6), W ⁴ represents a divalent group of an ester group, an amide group, a carbamate group or a urea group, and R ⁷⁶ represents a carbon number of 8-24 Straight-chain or branched monovalent hydrocarbon group} -R ⁷⁷ -OH (7) {In formula (7), R ⁷⁷ represents an alkylene group having 2 to 3 carbon atoms} -R ⁷⁸ -W ⁵ -R ⁷⁹ (8 ) {In formula (8), R ⁷⁸ represents an alkylene group having 2 to 3 carbon atoms, R ⁷⁹ represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms, and W ⁵ represents an ester group or an amide group , Divalent group of carbamate group or urea group) -W ⁶ -R ⁸⁰ (9) {In formula (9), W ⁶ represents a carbonyl group or an amide group, R ⁸⁰ represents a straight number of carbon numbers 8 to 24 Chain or branched monovalent hydrocarbon group}, wherein at least two of R ⁷² , R ⁷⁴ and j R ⁷⁵ are hydroxyl, amine group, hydrogen, monovalent group represented by the above general formula (7), R ⁷² And R ⁷⁴ is a hydroxyl group or an amine group, R ⁷⁵ is hydrogen or a monovalent group represented by the above general formula (7)]

In the multifunctional compound represented by the above general formula (I-2), when i is 2, there are plural W ² which may be the same or different. When i is 2, there are a plurality of R ⁴³ which may be the same or different. When i is 2, there are a plurality of R ⁴⁴ which may be the same or different. R ⁴⁴ corresponds to R ³² in the above general formula (I-1). A plurality of R ⁴² may be the same or different. There are a plurality of V ² which may be the same or different.

In the multifunctional compound represented by the above general formula (I-2), W ² is a divalent group of an ester group, an amide group, a carbamate group or a urea group. W ² is preferably an ester group or a urethane group from the viewpoint of water repellency and water permeability resistance.

In the polyfunctional compound represented by the above general formula (I-2), V ² is a hydroxyl group, an amine group or a carboxyl group. From the viewpoint of water repellency, V ² is preferably a hydroxyl group or an amine group.

In the group represented by the above general formula (4), V ³ is a hydroxyl group, an amine group or a carboxyl group. From the viewpoint of water repellency, V ³ is preferably a hydroxyl group or an amine group.

In the group represented by the above general formula (5), R ⁶¹ is a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms. R ⁶¹ corresponds to R ³² in the above general formula (I-1).

Among the groups represented by the above general formula (5), W ³ is a divalent group of an ester group, an amide group, a carbamate group or a urea group. W ³ is preferably an ester group or a urethane group from the viewpoint of water repellency and water permeability resistance.

In the group represented by the above general formula (6), R ⁷⁶ is a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms. R ⁷⁶ corresponds to R ³² in the above general formula (I-1).

Among the groups represented by the above general formula (6), W ⁴ is a divalent group of an ester group, an amide group, a carbamate group or a urea group. W ⁴ is preferably an ester group, an amide group or a carbamate group from the viewpoint of water repellency and water permeability resistance.

In the group represented by the general formula (8), R ⁷⁹ is a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms. R ⁷⁹ corresponds to R ³² in the above general formula (I-1).

Among the groups represented by the above general formula (8), W ⁵ is a divalent group of an ester group, an amide group, a carbamate group or a urea group. W ⁵ is preferably an ester group, an amide group or a carbamate group from the viewpoint of water repellency and water permeability resistance.

In the group represented by the general formula (9), R ⁸⁰ is a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms. R ⁸⁰ corresponds to R ³² in the above general formula (I-1).

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

R ³³ represents an f-valent organic group. The carbon number of R ³³ is preferably from 4 to 40, and more preferably from 6 to 18 from the viewpoint of water repellency and water permeability resistance. R ^{33 is} preferably hexanyl. f may be an integer of 2 to 7, and from the viewpoint of water repellency and water permeability resistance, preferably 2 to 3.

The isocyanate compound represented by the above general formula (II-1) may be a polyisocyanate compound. Examples of the polyisocyanate compound include toluene diisocyanate, diphenylmethane diisocyanate (MDI), liquid MDI represented by polyphenyl polymethyl polyisocyanate, crude MDI, hexamethylene diisocyanate, and xylylene Diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate and other diisocyanates, and the isocyanurate ring or ternary body of these. Among these, from the viewpoint of water repellency and water permeability resistance, hexamethylene diisocyanate is preferred.

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 the following general formula ( III-1), partly structured urethane resins represented by general formula (III-2) and general formula (III-3), etc.

[式(III-1)中，k1表示2以上之整數，R¹¹¹ 及R¹¹² 分別獨立地表示碳數10～24之直鏈或支鏈之1價烴基][化21]

[In formula (III-1), k1 represents an integer of 2 or more, and R ¹¹¹ and R ¹¹² each independently represent a linear or branched monovalent hydrocarbon group having 10 to 24 carbon atoms]

k1 represents an integer of 2 or more, and it is preferable from the viewpoint of water repellency and water permeability resistance, and the further improvement of the emulsion dispersion stability of the urethane resin and the easier operation of the urethane resin It is 2 to 100, more preferably 2 to 50.

[式(III-2)中，k2表示2以上之整數，k3表示1以上之整數，R¹¹³ 分別獨立地表示碳數10～24之直鏈或支鏈之1價烴基][化22]

[In formula (III-2), k2 represents an integer of 2 or more, k3 represents an integer of 1 or more, and R ¹¹³ each independently represents a linear or branched monovalent hydrocarbon group having 10 to 24 carbon atoms]

k2 represents an integer of 2 or more, and it is preferable from the viewpoints of water repellency and water permeability resistance, and the emulsion dispersion stability of the urethane resin is further improved, and the operation of the urethane resin is easier. It is 2 to 200, more preferably 2 to 100.

k3 represents an integer of 1 or more, and from the viewpoint of water repellency and water permeability resistance, and from the viewpoint of further improving the emulsion dispersion stability of the urethane resin, it is preferably 1 to 3, and more preferably 1.

[式(III-3)中，k4表示2以上之整數，R¹¹⁴ 分別獨立地表示碳數10～24之直鏈或支鏈之1價烴基][化23]

[In formula (III-3), k4 represents an integer of 2 or more, and R ¹¹⁴ each independently represents a linear or branched monovalent hydrocarbon group having 10 to 24 carbon atoms]

k4 represents an integer of 2 or more, and it is preferable from the viewpoint of water repellency and water permeability resistance, and the further improvement of the emulsion dispersion stability of the urethane resin and the easier operation of the urethane resin It is 2 to 200, more preferably 2 to 100.

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

[式(III-4)中，k5表示2以上之整數，R_X 表示下述式(R-1)所表示之一價有機基][化24]

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

k5 represents an integer of 2 or more, and it is preferable from the viewpoint of water repellency and water permeability resistance, and the emulsion dispersion stability of the urethane resin is further improved, and the operation of the urethane resin is easier. It is 2 to 100, more preferably 2 to 50.

[化25]

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

[式(III-5)中，k6表示2以上之整數，k7表示1以上之整數；R_X 表示上述式(R-1)所表示之一價有機基][化26]

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

k6 represents an integer of 2 or more, and it is preferable from the viewpoint of water repellency and water permeability resistance, and the further improvement of the emulsification and dispersion stability of the urethane resin, and the easier operation of the urethane resin. It is 2 to 200, more preferably 2 to 100.

k7 represents an integer of 1 or more, and it is preferable from the viewpoints of water repellency and water permeability resistance, and the emulsion dispersion stability of the urethane resin is further improved, and the operation of the urethane resin is easier. 1 to 3, more preferably 1.

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

[式(III-6)中，k8表示2以上之整數，R_X 表示上述式(R-1)所表示之一價有機基][化27]

[In formula (III-6), k8 represents an integer of 2 or more, and R _X represents a monovalent organic group represented by the above formula (R-1)]

k8 represents an integer of 2 or more, and it is preferable from the viewpoint of water repellency and water permeability resistance, and the further improvement of the emulsion dispersion stability of the urethane resin, and the easier operation of the urethane resin It is 2 to 200, more preferably 2 to 100.

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

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

(-NH-CO-B) (10) [In formula (10), B is a group derived from a blocking agent]

Examples of the blocking agent include 3,5-dimethylpyrazole, 3-methylpyrazole, 3,5-dimethyl-4-nitropyrazole, and 3,5-dimethyl-4. -Pyrazoles such as bromopyrazole and pyrazole; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and third butanol; phenol, methylphenol, chlorophenol, Isobutylphenol, p-third butylphenol, p-isoamylphenol, p-octylphenol, p-nonylphenol and other phenols; dimethyl malonate, diethyl malonate, acetone, ethyl acetate Methyl acetate, ethyl acetate and other active methylene compounds; formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime Other oximes; ε-caprolactam, δ-valerolactam, γ-butyramamide and other lactams; N-methylacetamide, acetanilide and other N-substituted amides; amber Acetylimide compounds such as imidate, phthalimide, etc.; imidazole compounds such as imidazole, 2-methylimidazole, etc. The blocking agent may be used alone or in combination of two or more. Among these, from the viewpoints of versatility, reactivity of blocked isocyanate groups, and ease of blocking, it is preferably used selected from the group consisting of pyrazoles, oximes, and lactams Of the at least one compound, it is more preferable to use at least one compound selected from the group consisting of dimethylpyrazole, methyl ethyl ketoxime, and caprolactam.

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

The above general formula (II-1) when reacting the polyfunctional compound represented by the above general formula (I-1) having e ¹ hydroxyl group and/or amine group with the compound represented by the above general formula (II-1) The compounding amount of the compound represented by) is preferably (0.8 to 1.20)×2/e ¹ mole, and more preferably (0.80) relative to 1 mole of the multifunctional compound represented by the general formula (I-1). -0.99)×2/e ¹ mole, more preferably (0.85-0.95)×2/e ¹ mole. It is more preferably (1.01 to 1.20)×2/e ¹ mole, and further preferably (1.05 to 1.15)×2/e ¹ .

The urethane resin of the present embodiment is preferably used for emulsification or dispersion 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 this embodiment can be produced as follows, for example.

The emulsification or dispersion liquid can be obtained by adding a surfactant as an emulsification aid or dispersion aid to the urethane resin of this embodiment and making it uniform, and slowly adding it while stirring it while facing it water.

As the surfactant, one or more conventionally known ones 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 relative to 100 parts by mass of the urethane resin of the present embodiment. Copies. If the content of the emulsification aid or the like is within the above range, it is easy to maintain water repellency and improve the emulsion dispersion stability of the urethane resin.

As the emulsifying or dispersing medium, water is preferable, and water and an organic solvent can be mixed as needed. Examples of organic solvents 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, and tripropylene glycol. class. In addition, the ratio of mixing water with an organic solvent is not particularly limited. In addition, the organic solvent can be distilled off under reduced pressure during or after the preparation of the aqueous dispersion, or it can be left directly.

The obtained aqueous dispersion of the urethane resin can also use a homomixer (manufactured by Primix), a homogenizer (manufactured by NIROSOAVI, or manufactured by APVGAULIN), Nanomizer (manufactured by Yoshida Machinery Co., Ltd.), Altimizer ( Sugino Machine Co., Ltd.), Starburst (Sugino Machine Co., Ltd.) and other high-pressure emulsifiers or ultrasonic emulsifiers, etc. to homogenize the particles.

The (β) component contained in the water repellent composition of this 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 (β) component of the present embodiment, the alkoxy group having 1 to 4 carbon atoms may be linear or branched. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy. In terms of ease of industrial manufacture and ease of purchase, R ²²⁰ , R ^221, and R ²²² are each independent, preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

Examples of the hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring include aralkyl groups having 8 to 40 carbon atoms, groups represented by the following general formula (L-2) or (L-3), and the like.

[式(L-2)中，R²⁴⁰ 表示碳數2～6之伸烷基，R²⁴¹ 表示單鍵或碳數1～4之伸烷基，a3表示0～3之整數；於a3為2或3之情形時，存在複數個之R²⁴¹ 可相同亦可不同][Chem 28]

[In formula (L-2), R ²⁴⁰ represents an alkylene group having 2 to 6 carbon atoms, R ²⁴¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, a3 represents an integer of 0 to 3; in a3 is 2 Or 3, there are multiple R ²⁴¹ which may be the same or different]

The alkylene group may be linear or branched.

[式(L-3)中，R²⁴² 表示碳數2～6之伸烷基，R²⁴³ 表示單鍵或碳數1～4之伸烷基，a4表示0～3之整數；於a4為2或3之情形時，存在複數個之R²⁴³ 可相同亦可不同][Chem 29]

[In formula (L-3), R ²⁴² represents an alkylene group having 2 to 6 carbon atoms, R ²⁴³ represents a single bond or an alkylene group having 1 to 4 carbon atoms, a4 represents an integer of 0 to 3; in a4 is 2 Or 3, there are multiple R ²⁴³ which may 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, and naphthylethyl. Among them, phenylethyl and phenylpropyl are preferred in terms of ease of industrial production and ease of purchase.

Among the groups represented by the above general formula (L-2), R ^{240 is} preferably an alkylene group having 2 to 4 carbon atoms, and a3 is preferably 0 or 1 in terms of ease of industrial manufacture and ease of purchase. , More preferably 0.

Among the groups represented by the above general formula (L-3), R ^{242 is} preferably an alkylene group having 2 to 4 carbon atoms, and a4 is preferably 0 or 1 in terms of ease of industrial manufacture and ease of purchase. , More preferably 0.

As the above-mentioned hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, it is preferably the above-mentioned aralkyl group having 8 to 40 carbon atoms and the above-mentioned general formula (L-2) in terms of ease of industrial manufacture and easy purchase. The group represented by) is more preferably the aralkyl group having 8 to 40 carbon atoms from the viewpoint of imparting water repellency and water permeability resistance to the fiber base material.

The alkyl group having 3 to 22 carbon atoms may be linear 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. Alkyl and so on. As the alkyl group having 3 to 22 carbon atoms, from the viewpoint of imparting water repellency and water permeability resistance to the fiber substrate, the alkyl group having 8 to 20 carbon atoms is preferred, and the alkyl group having 12 to 18 carbon atoms is more preferred. .

In the (β) component of this embodiment, R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ^234, and R ²³⁵ are each independently, and are a hydrogen atom, a methyl group, an ethyl group, and a C 1-4 alkoxy group , A hydrocarbon group having 8 to 40 carbon atoms with an aromatic ring, or an alkyl group having 3 to 22 carbon atoms. In terms of ease of industrial manufacture and ease of purchase, R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ and R ²³⁵ are each independently a hydrogen atom, a methyl group, an ethyl group or a carbon number of 1 to 4 The alkoxy group is more preferably a methyl group.

In the (β) component of this embodiment, a1 is an integer of 0 or more. From the viewpoints of industrial ease of manufacture, ease of purchase, and the provision of water repellency and water permeability resistance to the fiber substrate, a1 is preferably 40 or less, and more preferably 30 or less.

In the (β) component of this embodiment, (a1+a2) is 10 to 200. In terms of ease of industrial manufacture and ease of purchase, (a1+a2) is preferably 20 to 100, and more preferably 40 to 60. If (a1+a2) is within the above range, there is a tendency that the production or operation of polysiloxane itself becomes easy.

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

Examples of the polysiloxane having SiH groups include methylhydropolysiloxane having a degree of polymerization of 10 to 200, or a copolymer of dimethylsiloxane and methylhydrogensiloxane. Among these, in terms of industrial ease of manufacture and ease of purchase, methylhydrogen polysiloxane is preferred.

The aromatic compound having a vinyl group is a compound that is a source of a hydrocarbon group having 8 to 40 carbon atoms and having an aromatic ring in R ²²³ in the general formula (L-1). Examples of aromatic compounds having a vinyl group include styrene, α-methylstyrene, vinyl naphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-cumyl Phenyl ether, allyl-o-phenylphenyl ether, allyl-tri(phenylethyl)-phenyl ether and allyl-tri(2-phenylpropyl) phenyl ether, etc.

The α-olefin is a compound that is a source of the alkyl group having 3 to 22 carbon atoms in R ²²³ in the general formula (L-1). Examples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-eleven Α-olefins with 3 to 22 carbon atoms, such as olefins, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene.

The hydrosilylation reaction can also be carried out by reacting the aromatic group-containing aromatic compound and the α-olefin with the SiH group-containing polysiloxane in a stepwise or one-time manner in the presence of a catalyst as necessary.

The use amount of the polysilicone having SiH group, the aromatic compound having vinyl group and the α-olefin used in the hydrosilation reaction can be appropriately selected according to the equivalent of the SiH group of the polysilicone having SiH group, or the number average molecular weight, etc. .

Examples of the catalyst used in the hydrosilation reaction include compounds such as platinum and palladium, among which platinum compounds are preferred. Examples of platinum compounds include platinum (IV) chloride and the like.

The reaction conditions of the hydrosilation reaction are not particularly limited and can be adjusted appropriately. The reaction temperature is, for example, 10 to 200°C, preferably 50 to 150°C. The reaction time can be set to 3 to 12 hours when the reaction temperature is 50 to 150°C, for example.

In addition, the hydrosilation reaction is preferably carried out under an inert gas atmosphere. Examples of the inert gas include nitrogen and argon. That is, the reaction can proceed without solvent, but a solvent can also be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

Regarding the content ratio of the (α) component and (β) component of the present embodiment, from the viewpoint of water repellency, the mass ratio is preferably 95:5 to 50:50, more preferably 90:10 to 60:40 It is further preferably 80:20 to 70:30.

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

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

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

Examples of n-alkanes include: tricosane, tetracosane, icosane, hexacosane, hexacosane, octacosane, cosane, trioctane, and thirty-one. Alkane, thirty-dodecane, thirty-three trioxane, thirty-four octane, thirty-five octane, and thirty-six hexane From the viewpoint of water repellency and texture, n-alkanes are preferably triacone, triacone, and tridodecane.

Examples of normal olefins include 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentadecosene, 1-diene Hexadecene, 1-27-ene, 1-28-ene, 29-ene, 30-ene, 31-ene, 32-ene, 30-ene, Thirty-four carbonene, thirty-five carbonene and thirty-six carbonene etc. From the viewpoint of water repellency and texture, the normal olefin is preferably 30-carbonene, 31-carbonene, and 32-carbene.

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

The weight average molecular weight of the (γ) component of 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 (γ) component of the present embodiment is not particularly limited, and it may be, for example, 40 to 90°C. From the viewpoint of water repellency and texture, it is preferably 55 to 85°C, more preferably 60 to 80°C, and It is preferably 65 to 78°C, and particularly preferably 70 to 78°C. (γ) The melting point of the component means the value measured in accordance with JIS K 2235-1991.

The penetration degree of the (γ) component of this embodiment is not particularly limited, and for example, it can be 30 or less. From the viewpoint of water repellency, it is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. The penetration degree of the (γ) component of this embodiment is not particularly limited, and for example, it may be 0.1 or more and 1 or more. (γ) The penetration of the component means the value measured by the same method as JIS K 2235-1991.

The content ratio of the (α) component and (γ) component in the present embodiment is preferably 90:10 to 40:60, more preferably 80:20 to 50:50, and more preferably 70:30 in terms of mass ratio. ~60:40. If the content ratio of the (α) component and the (γ) component is within the above range, the texture of the fiber base material can be sufficiently maintained and excellent water repellency and water permeability resistance can be imparted.

The component (γ) of the present embodiment is preferably used for emulsification or dispersion with an emulsification aid or a dispersion aid in terms of water repellent performance and environment. The aqueous dispersion of the (γ) component of this embodiment can be produced by dispersing the (γ) component in water in the presence of an emulsifier for wax. The production of the aqueous dispersion of (γ) component is preferably carried out by mixing the (γ) component, water, and an emulsifier for wax. The temperature at the time of mixing is not particularly limited, and may be 60 to 90°C, for example. The time at the time of mixing is not particularly limited, and may be, for example, 10 seconds to 10 hours. The mixing is preferably carried out by using a homogeneous mixer.

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

The (δ) component of this embodiment is not particularly limited, and examples thereof include melamine resins, glyoxal resins, and compounds having one or more isocyanate groups or blocked isocyanate groups. Furthermore, the compound having at least one isocyanate group or blocked isocyanate group as the (δ) component does not contain a structural unit having a polyfunctional compound derived from the general formula (I-1) And a urethane resin derived from the structural unit of the isocyanate compound represented by the above general formula (II-1). (δ) A component can be used individually by 1 type or in combination of 2 or more types.

As the melamine resin, a compound having a melamine skeleton can be used, and examples thereof include polymethylolmelamine such as trimethylolmelamine and hexamethylolmelamine; some or all of the methylol groups of polymethylolmelamine have carbon The alkoxymethyl melamine of the alkoxymethyl group having 1 to 6 alkyl groups; part or all of the hydroxymethyl group of the polymethylol melamine becomes the oxymethyl group having the carbonyl group having 2 to 6 carbon atoms The acyloxymethyl melamine and so on. The melamine resin may be either a monomer or a polymer of a dimer or more, or a mixture of these may be used. Furthermore, urea etc. can be used for the partial condensation of melamine. Examples of such melamine resins include Beckamine APM, Beckamine M-3, Beckamine M-3 (60), Beckamine MA-S, Beckamine J-101, Beckamine J-101LF, and Union Kagaku manufactured by DIC Corporation. Unica Resin 380K manufactured by Kogyo Co., Ltd., Riken Resin MM series manufactured by Miki Riken Industrial Co., Ltd., etc.

As the glyoxal resin, previously known ones can be used. Examples of glyoxal resins include 1,3-dimethylglyoxal urea resins, dimethylol dihydroxyethylene urea resins, and dimethylol dihydroxy acrylurea resins. The functional groups of these resins can also be substituted with other functional groups. Examples of such glyoxal resins include Beckamine N-80, Beckamine NS-11, Beckamine LF-K, Beckamine NS-19, Beckamine LF-55P Conc, Beckamine NS-210L, Beckamine manufactured by DIC Corporation. NS-200, Beckamine NF-3, Union Resin GS-20E manufactured by Union Kagaku Kogyo Co., Ltd., Riken Resin RG series manufactured by Miki Riken Industries Co., Ltd., Riken Resin MS series, etc.

When the melamine resin and 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. As such a catalyst, it is not particularly limited as long as it is a commonly used catalyst, and examples include: boron fluoride compounds such as ammonium boron fluoride and boron fluoride subsalt; neutral metal salt such as magnesium chloride and magnesium sulfate Medium; inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, etc. Among these catalysts, organic acids such as citric acid, tartaric acid, malic acid, maleic acid, and lactic acid can also be used as auxiliary catalysts if necessary. Examples of such catalysts include Catalyst ACX, Catalyst 376, Catalyst O, Catalyst M, Catalyst G (GT), Catalyst X-110, Catalyst GT-3, and Catalyst NFC-1 manufactured by DIC Corporation. Unica Catalyst 3-P, Unica Catalyst MC-109, Union Kagaku Kogyo Co., Ltd., Riken Fixer RC series, Riken Fixer MX series, Riken Fixer RZ-5, etc.

As the compound having one or more isocyanate groups or blocked isocyanate groups, monofunctional (mono)isocyanate compounds such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate, and naphthalene isocyanate can be used. Or multifunctional isocyanate compounds.

The polyfunctional isocyanate compound is not particularly limited as long as it has two or more isocyanate groups in the molecule, and a known polyisocyanate compound can be used. Examples of the polyfunctional isocyanate compound include diisocyanate compounds such as alkylene diisocyanate, aryl diisocyanate and cycloalkyl diisocyanate, and modified polyisocyanate compounds such as dimer or terpolymer of these diisocyanate compounds. Wait. The carbon number of the alkylene diisocyanate is preferably 1-12.

Examples of the diisocyanate compound include 2,4 or 2,6-toluene diisocyanate, ethylidene diisocyanate, propylidene diisocyanate, 4,4-diphenylmethane diisocyanate, terephthalic diisocyanate, and tetraisocyanate. Methylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, benzene Diisocyanate, toluene or naphthalene diisocyanate, 4,4'-methylene-bis (phenyl isocyanate), 2,4'-methylene-bis (phenyl isocyanate), 3,4'-methylene- Bis(phenyl isocyanate), 4,4'-ethylidene-bis(phenyl isocyanate), ω,ω'-diisocyanato-1,3-dimethylbenzene, ω,ω'-diiso Cyanate-1,4-dimethylcyclohexane, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1,3- Dimethylcyclohexane, 1-methyl-2,4-diisocyanate cyclohexane, 4,4'-methylene-bis (cyclohexyl isocyanate), 3-isocyanato-methyl-3, 5,5-trimethylcyclohexyl isocyanate, acid-diisocyanate dimer, ω,ω'-diisocyanato diethylbenzene, ω,ω'-diisocyanato dimethyl toluene, ω ,ω'-diisocyanatodiethyltoluene, bis(2-isocyanatoethyl) fumarate, 1,4-bis(2-isocyanato-propan-2-yl ) Benzene, 1,3-bis(2-isocyanato-prop-2-yl)benzene, etc.

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

The modified polyisocyanate compound derived from the diisocyanate compound is not particularly limited as long as it has two or more isocyanate groups, and examples include a biuret structure, an isocyanurate structure, Polyisocyanate of carbamate structure, uretdione structure, allophanate structure, trimer structure, etc., adducts of trimethylolpropane aliphatic isocyanate, etc. In addition, polymeric MDI (MDI = diphenylmethane diisocyanate) can also be used as a polyfunctional isocyanate compound.

Regarding the polyfunctional isocyanate compound, one type may be used alone or two or more types may be used in combination.

The isocyanate group possessed by the multifunctional isocyanate compound may be kept as it is, or it may be a blocked isocyanate group blocked by a blocking agent. As the blocking agent, 3,5-dimethylpyrazole, 3-methylpyrazole, 3,5-dimethyl-4-nitropyrazole, 3,5-dimethyl-4- Pyrazoles such as bromopyrazole and pyrazole; phenol, methylphenol, chlorophenol, isobutylphenol, tertiary butylphenol, isoamylphenol, octylphenol, nonylphenol and other phenols; ε-hexyl Internal amides, delta-valerolactam, γ-butyrolamide and other internal amides; dimethyl malonate, diethyl malonate, acetone acetone, methyl acetoacetate, acetoacetate Active methylene compounds such as ethyl ester; formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime and other oximes; imidazole, 2- Imidazole compounds such as methylimidazole; sodium bisulfite, etc. Among these, from the viewpoint of water repellency, pyrazoles and oximes are preferred.

As the polyfunctional isocyanate compound, a water-dispersible isocyanate that imparts water dispersibility to the polyisocyanate by introducing a hydrophilic group into the polyisocyanate structure to have an interface active effect can also be used. In order to promote the reaction, known catalysts such as organic tin and organic zinc may be used in combination.

The content ratio of the (α) component and the (δ) component in the present embodiment is preferably 95:5 to 60:40 in terms of mass ratio, more preferably 95:5 to 70:30, and still more preferably 90:10 to 80 : 20. If the content ratio of the (α) component and the (δ) component is within the above range, it is easy to obtain a fiber substrate that maintains the texture of the fiber substrate sufficiently, imparts excellent water repellency and water permeability resistance, and has sufficient peel strength.

The water repellent composition of this embodiment may contain additives and the like as necessary. Examples of additives include other water repellents, surfactants, defoamers, pH adjusters, antibacterial agents, mildew inhibitors, colorants, antioxidants, deodorants, various organic solvents, chelating agents, and antistatic agents. , Antibacterial deodorant, flame retardant, softener, anti-crease agent, etc.

As the surfactant, known nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used. The surfactant can be used alone or in combination of two or more.

Examples of the antifoaming agent include: oil-based antifoaming agents such as castor oil, sesame oil, linseed oil, animal and vegetable oils; fatty acid based antifoaming agents such as stearic acid, oleic acid, palmitic acid; isoamyl stearate, Fatty acid ester defoamers such as distearyl succinate, ethylene glycol distearate, butyl stearate, etc.; polyoxyalkylene monohydric alcohol di-third amylphenoxyethanol, 3 -Alcohol-based defoamers such as heptyl alcohol and 2-ethylhexanol; ether-based defoamers such as di-third amylphenoxyethanol 3-heptyl cellosolve nonyl cellosolve 3-heptyl carbitol Foaming agent; phosphate-based antifoaming agents such as tributyl phosphate and tri(butoxyethyl) phosphate; amine-based antifoaming agents such as dipentylamine; polyalkyleneamides, amides such as amides Amine-based defoamer; sodium lauryl sulfate sodium defoamer; mineral oil, etc. The defoamer can be used alone or in combination of two or more.

Examples of pH adjusting agents 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; hydrochloric acid, sulfuric acid, Inorganic acids such as nitric acid, phosphoric acid, and boric acid; alkalis such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonia, alkanolamines, pyridine, and oxoline. The pH adjuster can be used alone or in combination of two or more.

Examples of the organic solvent include aliphatic alcohols having 1 to 8 carbon atoms such as methanol, ethanol, isopropanol, isobutanol, hexanol, and 2-ethylhexanol; acetone, methyl ethyl ketone, methyl alcohol Isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol and other ketones; ethyl acetate, methyl acetate, butyl acetate, methyl lactate, ethyl lactate and other esters; diethyl ether, di Ethers such as isopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, dioxane, methyl tertiary butyl ether, butyl carbitol; ethylene glycol, diethylene glycol, Triethylene glycol, propylene glycol, dipropylene glycol and other glycols; ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, Glycol ethers such as 3-methoxy-3-methyl-1-butanol; ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc. Alcohol esters; amides such as acetamide, acetamide, benzamide, N,N-dimethylformamide, acetanilide. Organic solvents can be used alone or in combination of two or more.

As the antistatic agent, it is preferable to use one that does not easily hinder water repellency. Examples of the antistatic agent include cationic surfactants such as higher alcohol sulfate salts, sulfated oils, sulfonates, quaternary ammonium salts, and imidazoline type quaternary salts, polyethylene glycol type, and polyhydric alcohol esters. Type of nonionic surfactant, imidazoline type quaternary salt, amphetamine type, betaine type and other amphoteric surfactant, polymer compound type antistatic polymer, polyalkylamine, etc. An antistatic agent can be used individually by 1 type or in combination of 2 or more types.

The water-repellent fiber product of this embodiment will be described.

The water-repellent fiber product of the present embodiment includes a fiber base material and the water-repellent composition of the present embodiment attached to the fiber base material.

The fiber substrate can be a fiber product or a fiber material constituting a fiber product.

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

The form of the fiber base material is not particularly limited, and for example, any form such as fiber, yarn, cloth, non-woven fabric, and paper may be used.

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

The manufacturing method of the water-repellent fiber product of this embodiment will be described.

The manufacturing method of the water-repellent fiber product of the present embodiment includes the step of bringing the treatment liquid containing the water-repellent agent composition of the present embodiment above into contact with the fiber substrate.

As a method of treating the fibrous base material with the treatment liquid, for example, processing methods such as dipping, spraying, and coating can be mentioned. In addition, when the water repellent composition contains water, it is preferably dried after being attached to the fiber base material to remove the water.

The water-repellent fiber product of this embodiment can coat a specific part. Examples of the coating process include moisture-permeable water-repellent process and wind-proof process in sports use or outdoor use. As a processing method, for example, in the case of moisture-permeable and waterproof processing, processing can be performed by the following method: a urethane resin or an acrylic resin and the like other than those included in the water repellent composition of the present invention and The coating solution of the medium is applied to one side of the fiber product treated with water repellent and dried.

The adhesion amount of the water repellent composition to the fiber substrate can be adjusted appropriately according to the degree of water repellency required, from the viewpoint of sufficiently maintaining the texture of the fiber substrate and imparting water repellency and water permeability resistance, and also sufficiently ensuring peel strength, Preferably, it is adjusted so that the total adhesion amount of the (α) component, (β) component, and (γ) component contained in the water repellent composition is 0.01 to 10 g relative to 100 g of the fiber base material, and more It is preferably adjusted so that it becomes 0.05 to 5 g.

In addition, after the water repellent composition of the present embodiment is attached to the fiber base material, it is preferably subjected to appropriate heat treatment. The temperature conditions are not particularly limited. If the water repellent composition of the present embodiment is used, the fiber substrate can exhibit sufficiently good water repellency under mild conditions of 100 to 130°C. The temperature conditions can also be high-temperature treatment above 130°C (preferably up to 200°C). In this case, the treatment time can be shortened compared to the previous case where the fluorine-based water repellent is used. Therefore, according to the manufacturing method of the water-repellent fiber product of this embodiment, the deterioration of the fiber base material caused by heat can be suppressed, the texture of the fiber base material becomes soft during the water-repellent treatment, and it can be used under mild heat treatment conditions. Under the condition of low temperature curing, the fiber substrate is provided with sufficient water resistance.

In the case where the water repellent composition of the present embodiment contains the (δ) component, the reaction of the crosslinking agent is sufficiently carried out to more effectively impart water repellency, water repellency, and effectively improve the peel strength. From a viewpoint, it is preferable to heat the fiber base material to which (δ) component adhered at 110-180 degreeC for 1-5 minutes. The adhesion amount of the (δ) component to the fiber base material is preferably 0.1 to 50% by mass based on the weight of the fiber base material, and more preferably 0.1 to 10% by mass.

Each component included in the water repellent composition of the present embodiment can be divided and contained in a plurality of treatment liquids. For example, it can be divided into a processing liquid containing (α) component, (β) component and (γ) component, and a processing liquid containing (δ) component.

The water-repellent fiber product obtained by the production method of the present embodiment can exert sufficient water-repellent even when used outdoors for a long time, and the texture is also excellent. In addition, the above water-repellent fiber product does not use a fluorine-based compound , So it can be made environmentally friendly.

The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments. [Example]

Hereinafter, the present invention will be further described by examples, but the present invention is not limited by these examples.

<Adjustment of acrylic resin dispersion liquid> Using the materials shown in Table 1 and Table 2 {Table, numerical values represent (g)}, polymerization was performed in the order shown below to obtain an acrylic resin dispersion liquid.

(Synthesis Example 1) In a 0.5 L autoclave, 15 g of stearyl acrylate, 5 g of stearyl methacrylate, Surfynol465 (manufactured by Nissin Chemical Co., Ltd., HLB=13) 0.5 g, Surfynol440 (manufactured by Nissin Chemical Co., Ltd., HLB=8) 1 g, Noigen XL-40 (manufactured by Daiichi Pharmaceutical Co., Ltd., polyoxyalkylene branched decyl ether, HLB=10.5) 0.5 g, stearyl trimethyl ammonium sulfate 1 g , 15 g of tripropylene glycol and 54.9 g of water, mixed and stirred at 45 ℃ to make a mixed liquid. The mixture was irradiated with ultrasonic waves to emulsify and disperse all monomers. Then, 0.15 g of azobis(isobutylamidine) dihydrochloride was added to the mixed solution, and 7 g of vinyl chloride was continuously pressed under a nitrogen atmosphere with the internal pressure of the autoclave maintained at 0.3 MPa and the temperature was adjusted. The reaction was carried out at 61°C for 6 hours to obtain an acrylic resin dispersion liquid containing 27% by mass of acrylic resin.

(Synthesis Examples 2 to 13) Except for using the materials shown in Tables 1 and 2, in the same manner as in Synthesis Example 1, an acrylic resin dispersion liquid was obtained. <Adjustment of urethane resin dispersion liquid>

(Synthesis Example 14) In a 1000 ml flask, add di-trimethylolpropane 206.74 g, stearic acid 469.87 g, and p-toluenesulfonic acid 3.4 g. Then, the temperature was raised to 140°C under a nitrogen atmosphere, and then the dehydration reaction was performed at a temperature increase rate of about 0.4°C/min under a nitrogen flow at 140 to 190°C for 5 hours. The nitrogen flow rate is 5 ml per minute. After the reaction, the acid value of the composition was measured. The acid value is 2.0 mgKOH/g.

Then, 101.12 g of the above reactant was taken into a 300 ml flask, and 23.78 g of hexamethylene diisocyanate, 25 g of methyl ethyl ketone, and a bismuth catalyst (NEOSTANN U-600: manufactured by Nitto Chemical Co., Ltd.) were added 0.125 g, the reaction was carried out at 80°C for 7 hours. The reaction proceeded until the NCO% became 0.64%. After the reaction, the temperature was lowered to 40°C, and then, 2.36 g of 3,5-dimethylpyrazole was added to perform a reaction at 40°C for 1 hour to obtain a carbamate resin dispersion containing 83% by mass of the carbamate resin. If the weight average molecular weight of the obtained urethane resin was measured using gel permeation chromatography (HLC-8320GPC (TOSOH CORPORATION)), the weight average molecular weight was 11,700.

The urethane resin contained in the obtained urethane resin dispersion liquid is a compound in which R ^{31 in} the above general formula (I-1) is 4 removed from di-trimethylolpropane A residue derived from a hydroxy group, d is 2, e is 2, W ¹ is an ester group, R ³² is a heptadecyl group, V ¹ is a hydroxy group, and R ^{33 in the} above general formula (II-1) It is obtained by reacting an isocyanate compound having a hexyl group and f of 2, and then obtained by isolating the unreacted isocyanate group with 3,5-dimethylpyrazole.

In a 500 mL stainless steel container, add 40 g of the urethane resin (single ion) obtained above, 50 g of methyl ethyl ketone, and Decaglyn 1-L (nonionic surfactant, manufactured by Daiichi Pharmaceutical) 5 g, Decaglyn 1-SV (nonionic surfactant, manufactured by First Industrial Pharmaceutical) 5 g and ARQUAD T-28 (cationic surfactant, manufactured by LION SPECIALTY CHEMICALS) 5 g, and heated to 50°C to dissolve. Then, 295 g of hot water at 80° C. was added, and emulsification was maintained at 80° C. for 20 minutes using an ultrasonic emulsifier US-600E (manufactured by Nippon Seiki Co., Ltd.). Thereafter, it was cooled to obtain a dispersion liquid containing 10% by mass of the urethane resin.

(Synthesis Example 15) In a 1000 ml flask, add 255.88 g of trimethylolpropane, 542.51 g of stearic acid, and 1.6 g of p-toluenesulfonic acid. Then, the temperature was raised to 140°C under a nitrogen atmosphere, and then the dehydration reaction was performed at 140 to 190°C under a nitrogen flow at a temperature increase rate of about 0.4°C/min for 5 hours. The nitrogen flow rate is 5 ml per minute. After the reaction, the acid value of the composition is measured. The acid value is 2.0 mgKOH/g.

Then, 87.83 g of the above reactant was taken into a 300 ml flask, 37.11 g of hexamethylene diisocyanate, 25 g of methyl ethyl ketone, and 0.125 g of bismuth catalyst were added, and the reaction was carried out at 80° C. for 7 hours. The reaction proceeded until the NCO% became 0.69%. After the reaction, the temperature was lowered to 40° C. Then, 2.37 g of 3,5-dimethylpyrazole was added and the reaction was carried out at 40° C. for 1 hour to obtain a carbamate resin dispersion containing 83% by mass of the carbamate resin. . If the weight average molecular weight of the obtained urethane resin was measured using gel permeation chromatography, the weight average molecular weight was 17,500.

The urethane resin contained in the obtained urethane resin dispersion liquid is a compound in which R ^{31 in} the general formula (I-1) above is obtained by removing three hydroxyl groups from trimethylolpropane The obtained residue, d is 1, e is 2, W ¹ is an ester group, R ³² is a heptadecyl group, V ¹ is a hydroxy group, and R ^{33 in} the general formula (II-1) above is After the hexyl group and the isocyanate compound having f of 2 are reacted, the unreacted remaining isocyanate group is blocked with 3,5-dimethylpyrazole.

In a 500 mL stainless steel container, add 40 g of the urethane resin (single ion) obtained above, 50 g of methyl ethyl ketone, and Decaglyn 1-L (nonionic surfactant, manufactured by Daiichi Pharmaceutical) 5 g, Decaglyn 1-SV (nonionic surfactant, manufactured by First Industrial Pharmaceutical) 5 g and ARQUAD T-28 (cationic surfactant, manufactured by LION SPECIALTY CHEMICALS) 5 g, and heated to 50°C to dissolve. Subsequently, 295 g of hot water at 80° C. was added, and emulsification was carried out using an ultrasonic emulsifier US-600E (manufactured by Nippon Seiki Co., Ltd.) while maintaining 80° C. for 20 minutes. Thereafter, it was cooled to obtain a dispersion liquid containing 10% by mass of the urethane resin.

<Adjustment of organic modified polysiloxane emulsion> (Synthesis Example 16) Into a reaction vessel equipped with a stirrer, thermometer, reflux cooler, nitrogen introduction tube, and dropping funnel, the SiH group equivalent was 63.2 g/mol and the degree of polymerization 63.2 g of methylhydrogenpolysiloxane, 50, was introduced with nitrogen gas, and the mixture was heated until the temperature became 65°C and mixed until it became uniform. The ethylene glycol monobutyl ether-toluene mixed solution of platinum (IV) chloride as a hydrosilation catalyst was added so that the platinum concentration became 5 ppm relative to the reactants in the system. When the temperature of the reactant became 120°C, 168.3 g of 1-dodecene in 1 mole was added dropwise, and the mixture was reacted at 120°C for 6 hours. Confirmation of the completion of the addition reaction can be performed by performing FT-IR (fourier transform infrared radiation) analysis of the obtained organic modified polysiloxane to confirm that it is derived from methylhydrogen polysiloxane The absorption spectrum of the SiH group disappears. In this way, in the above general formula (L-1), a1 is 0, a2 is 50, R ²²² is methyl, R ²²³ is dodecyl, R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ and R ²³⁵ are methyl-organic modified polysiloxane. Furthermore, to 20 parts by mass of the obtained organic modified polysiloxane, 3 parts by mass of ethylene oxide 9 mole adduct of a branched higher alcohol having 12 to 14 carbon atoms were added and mixed. Subsequently, 77 parts by mass of water was added in small amounts while mixing and emulsifying in water to obtain an organically modified polysiloxane emulsion containing 20% by mass of organically modified polysiloxane.

(Synthesis Example 17) Organic modified polysiloxane and organic were obtained in the same manner as in Synthesis Example 16 except that 84.2 g of 1 mole of 1-hexene was used instead of 168.3 g of 1-dodecene of 1 mole. Modified polysiloxane emulsion. In addition, the organically modified polysiloxane system obtains a1 of 0, a2 of 50, R ²²² of methyl, R ²²³ of hexyl, R ²³⁰ , R ²³¹ , R ²³² , and R in the above general formula (L-1) ²³³ , R ²³⁴ and R ²³⁵ are methyl organically modified polysiloxane.

(Synthesis Example 18) Organic modified polysiloxane was obtained in the same manner as in Synthesis Example 16 except that 12.5 moles of 1-octadecene was replaced by 252.5 g of 1 moles of 1-dodecene. Organically modified polysiloxane emulsion. Furthermore, the organically modified polysilicone system obtains the above general formula (L-1) where a1 is 0, a2 is 50, R ²²² is methyl, R ²²³ is octadecyl, R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ and R ²³⁵ are methyl-organic modified polysiloxane.

(Synthesis Example 19) In addition to using 8 moles of 1-dodecene 0.5mol and 126.2g of 1-octadecene 0.5mol instead of 168.3g of 1-dodecene 1mol, other than In Example 16, the organic modified polysiloxane and the organic modified polysiloxane emulsion were obtained in the same manner. Furthermore, the organically modified polysilicone system obtains the above general formula (L-1) where a1 is 0, a2 is 50, R ²²² is methyl, R ²²³ is dodecyl or octadecyl, R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ and R ²³⁵ are methyl-organic modified polysiloxanes.

(Synthesis Example 20) 140.5 g of a copolymer of dimethylsiloxane and methylhydrogensiloxane was used instead of 63.2 g of methylhydrogenpolysiloxane, and 252.5 g of 1 octadecene was used instead of 1 mole Except for 168.3 g of 1-dodecene, the organically modified polysiloxane and the organically modified polysiloxane emulsion were obtained in the same manner as in Synthesis Example 17. The copolymer of dimethylsiloxane and methylhydrogensiloxane has a SiH group equivalent of 140.5 g/mol and a degree of polymerization of 50. In addition, the organically modified polysiloxane system obtains a1 of 25, a2 of 25, R ²²⁰ and R ²²¹ of methyl, R ²²² of methyl, and R ²²³ of octadecyl in the general formula (L-1). , R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ²³⁴ and R ²³⁵ are methyl-organic modified polysiloxane.

<Example of production of emulsified wax> (Production Example 1) Add paraffin wax {melting point 69℃, penetration 12(25℃)} 150 g, pure water 350 g, polyoxyethylene stearyl ether (HLB=10.7) 8.5 g, polyoxyalkylene branch in a high-pressure reaction vessel Chain decyl ether (HLB=14.7) 6.5 g and sealed. Then, the temperature was raised to 110 to 120°C while stirring in the container. Thereafter, while maintaining the high pressure in the container, the emulsion was emulsified under high pressure for 30 minutes to obtain an aqueous dispersion of paraffin. Furthermore, the wax content was adjusted to 30% by mass with pure water to obtain emulsified wax.

(Production Example 2) Paraffin wax {melting point 77℃, penetration 4(25℃)} 150 g was used instead of paraffin wax {melting point 69℃, penetration 12(25℃)} 150 g, except that it was obtained in the same manner as in Production Example 1. Aqueous dispersion of paraffin and emulsified wax.

(Production Example 3) Paraffin wax {melting point 50°C, penetration 22 (25°C)} 150 g was used instead of paraffin wax {melting point 69°C, penetration 12 (25°C)}, except that paraffin wax was obtained in the same manner as in Production Example 1. Aqueous dispersion and emulsifying wax.

<Preparation of test solution> (Example 1) The acrylic resin dispersion liquid obtained in Synthesis Example 1, the organic modified polysiloxane emulsion obtained in Synthesis Example 18, the emulsified wax obtained in Production Example 2, diethylene glycol butyl ether as a medium and NICEPOLE FE-26 (manufactured by Nichiwa Chemical Co., Ltd.) as an antistatic agent was mixed so as to have the composition (parts by mass) shown in Table 3 to obtain a test liquid. Furthermore, the blending amounts of acrylic resin, organically modified polysiloxane and wax in the test solution of Example 1 were 20 parts by mass×27% by mass=5.4 parts by mass, 10 parts by mass×20% by mass=2 parts by mass Parts and 10 parts by mass×30% by mass=3 parts by mass.

The details of the materials shown in Tables 3 to 6 are shown below. ・IE-7045 (trade name, made by Dow Corning Toray (share), dimethyl polysiloxane) ・NICEPOLE FE-26 (trade name, manufactured by Nichiwa Chemical Co., Ltd.)

(Examples 2 to 23 and Comparative Examples 1 to 8) Except for using the materials shown in Tables 3 to 6, the test liquid was obtained in the same manner as in Example 1.

I. Initial water repellency evaluation by spray method for water repellent fiber products The spray water temperature was set to 20°C by the same method as the spray method of JIS L 1092 (2009). In this test, the test liquid prepared with the composition of the examples and the comparative examples is made of acrylic resin, other acrylic resin, urethane resin, organically modified polysiloxane, dimethyl polysiloxane, The treatment liquid is obtained by diluting with water so that the total content of wax and other waxes becomes 1% by mass. Then, the dyed 100% polyester cloth or 100% nylon cloth was immersed in the obtained treatment liquid (pressure absorption rate 60% by mass). Then, the cloth subjected to the immersion treatment was dried at 130°C for 2 minutes, and further heat-treated at 170°C for 1 minute to obtain a water-repellent fiber product. Evaluate the water repellency of water repellent fiber products. The results were evaluated visually according to the following grade. The evaluation results are shown in Tables 3 to 6. Water repellent: status 5: Those with no moisture attached to the surface 4: Those who show slight adhesion on the surface 3: Those who show partial wetting on the surface 2: Those who appear wet on the surface 1: Those showing wetness on the entire surface 0: Those who are completely wet on both sides of Yu Zhengbei

II. Evaluation of durable water repellent by spray method for water repellent fiber products NK ASSIST NY-30 (manufactured by Nichiwa Chemical Co., Ltd.) as a cross-linking agent was added to the test liquid prepared with the composition of the examples and comparative examples so as to be 3 g/L. Then, the total content of acrylic resin, other acrylic resin, urethane resin, organically modified polysiloxane, dimethyl polysiloxane, wax, other wax and crosslinking agent becomes 1% by mass Dilute the test solution with water and adjust the treatment solution. The dyed 100% polyester cloth or 100% nylon cloth is immersed in the treatment liquid (pressure absorption rate 60% by mass). Then, the cloth subjected to the immersion treatment was dried at 130°C for 2 minutes, and further heat-treated at 170°C for 1 minute to obtain a water-repellent fiber product. The obtained water-repellent fiber product was washed 10 times (L-10) by the method 103 of JIS L 0217 (1995), and the water-repellency after air-drying was evaluated in the same manner as the above water-repellent evaluation method. The evaluation results are shown in Tables 3 to 6.

III. Determination of the contact angle of water-repellent fiber products The water-repellent fiber product was obtained in the same manner as II. Evaluation of the durable water-repellent fiber product. 20 μl of ion-exchanged water was added dropwise to the obtained water-repellent fiber product, and the contact angle of the formed water drop was measured. When measuring the contact angle, the automatic contact angle meter DSA25 manufactured by KRUSS is used. The evaluation results are shown in Tables 3 to 6.

IV. Evaluation of water resistance of water repellent fiber products The water-repellent fiber product was obtained in the same manner as II. Evaluation of the durable water-repellent fiber product. Place the obtained water-repellent fiber product in a horizontal and flat place, and add 3 drops of 200 μl of water droplets to the water-repellent fiber product and place it at room temperature. After 10 minutes, 30 minutes, 60 minutes, and 120 minutes, the number of droplets remaining on the water-repellent fiber product with a contact angle of 90° or more in the state of water droplets was used as the evaluation result. The evaluation results are shown in Tables 3 to 6.

V. Texture evaluation of water-repellent fiber products The 100% polyester water-repellent fiber product described in II was evaluated in five grades shown below by the feel. The evaluation criterion is that the texture of the water-repellent fiber product of Comparative Example 1 is 2, and the texture of the water-repellent fiber product of Comparative Example 2 is 5. The evaluation results are shown in Tables 3 to 6. 1: Hard ~ 5: Soft

VI. Evaluation of peel strength of water repellent fiber products The test was conducted according to JIS K 6404-5 (1999). First, NK ASSIST NY-30 (manufactured by Nichiwa Chemical Co., Ltd.) as a cross-linking agent was added to the test liquid prepared with the composition of the examples and comparative examples so as to be 3 g/L. Then, the total content of acrylic resin, other acrylic resin, urethane resin, organically modified polysiloxane, dimethyl polysiloxane, wax, other wax and crosslinking agent becomes 3% by mass Dilute the test solution with water and adjust the treatment solution. Then, the dyed 100% nylon cloth was immersed using the obtained treatment liquid (pressure absorption rate 60% by mass). Then, the cloth subjected to the immersion treatment was dried at 130°C for 2 minutes, and further heat-treated at 160°C for 30 seconds to obtain a base cloth. The seam tape ("MELCO Tape" manufactured by SAN CHEMICALS Co., Ltd.) was heat-bonded to the obtained base fabric at 150°C for 1 minute using a hot pressing device, and the layer between the base fabric and the seam tape The peel strength was measured using Autograph (AG-IS, manufactured by Shimadzu Corporation). The moving speed of the clamp was stretched at 100 mm/min, and the average value of the stress was taken as the peel strength [N/inch]. The results are shown in Tables 3 to 6.

[Table 1]

[Table 2]

[table 3]

[Table 4]

[table 5]

[Table 6]

Claims (5)

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 having a source The urethane resin from the structural unit of the polyfunctional compound represented by the following general formula (I-1) and the structural unit derived from the isocyanate compound represented by the following general formula (II-1), the following general Organically modified polysiloxane and wax represented by formula (L-1); [Chem 1]

[In formula (A-1), R ¹ represents hydrogen or methyl, R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent] R ³¹ [-W ¹ -R ³² ] _d [-V ¹ ] _e (I-1) [In 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, R ³¹ represents an organic group of (d+e) valence, W ¹ It is expressed as a divalent group of an ester group, an amide group, a carbamate group or a urea group, R ³² represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms, and V ¹ represents a hydroxyl group, an amine group or Carboxyl group; wherein, two or more of e V ¹ are hydroxy and/or amine groups] R ³³ [-NCO] _f (II-1) [In formula (II-1), R ³³ represents an organic group of f valence, f represents an integer from 2 to 7] [Chemical 2]

[In formula (L-1), R ²²⁰ , R ²²¹ and R ²²² each independently represent a hydrogen atom, a methyl group, an ethyl group or a C 1-4 alkoxy group, and R ²²³ represents a carbon number having an aromatic ring The hydrocarbon group of 8-40, or the alkyl group of 3-22 carbon atoms, R ²³⁰ , R ²³¹ , R ²³² , R ²³³ , R ^234, and R ²³⁵ each independently represent a hydrogen atom, a methyl group, an ethyl group, and a carbon number 1 to 4 alkoxy groups, hydrocarbon groups having 8 to 40 carbon atoms with aromatic rings, or alkyl groups 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 , When a1 is 2 or more, multiple R ²²⁰ and R ²²¹ may be the same or different, and when a2 is 2 or more, multiple R ²²² and R ²²³ may be the same or different ]. The water repellent composition for fiber according to claim 1, wherein the acrylic resin further has a structural unit derived from at least one monomer (E) of vinyl chloride and vinylidene chloride. The water repellent composition for fibers according to claim 1 or 2, which further contains a crosslinking agent. A water-repellent fiber product comprising a fiber base material and the water-repellent composition for fibers attached to the fiber base material according to any one of claims 1 to 3. A method for manufacturing a water-repellent fiber product, comprising a step of contacting a treatment liquid containing the water-repellent composition for fibers according to any one of claims 1 to 3 with a fiber substrate.