TW202030301A - Water repellant composition, water-repellent fiber product, and method for manufacturing water-repellent fiber product - Google Patents

Abstract

This water repellant composition includes a non-fluorinated polymer ([alpha]) containing constituent units derived from a (meth)acrylic acid ester monomer (A1) represented by general formula (A-1) and constituent units derived from a compound (A2) represented by general formula (A-2), and a silicone resin ([beta]). [In formula (A-1), R1 represents hydrogen or a methyl group, and R2 represents a C12-30 univalent hydrocarbon group which may have a substituent.] [In formula (A-2), R11 represents hydrogen or a methyl group, R12 represents a C1-6 divalent hydrocarbon group, Z represents an ester group or an amide group, and W represents a group represented by -CO-R13 (in which R13 represents a C1-4 univalent hydrocarbon group), a group represented by -NH-CO-NH2, or a group represented by formula (A-3).].

Description

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

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

Conventionally, a fluorine-based water repellent containing a fluorine-based compound has been known, and a fiber product obtained by treating a fiber product or the like with the fluorine-based water repellent agent to impart water repellency to the surface of the fiber product is known. Such a fluorine-based water repellent is usually produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group. Although fiber products treated with fluorine-based water repellent exhibit excellent water repellency, monomers with fluoroalkyl groups have obvious concerns about environmental impact. Therefore, there is an increasing international demand for non-fluorine-based A non-fluorine-based water repellent with high-performance water repellency that rivals the water repellent.

Therefore, in recent years, research has been conducted on non-fluorine-based water repellents that do not contain fluorine-based compounds. For example, Patent Document 1 below discloses a surface treatment agent as an aqueous emulsion containing a non-fluoropolymer having repeating units derived from a specific (meth)acrylate monomer, and specific interfacial activity Agent, and liquid medium containing water. In the following Patent Document 2, a water-repellent composition containing an acrylic copolymer is disclosed as a fluorine-free polymerizable monomer containing a specific (meth)acrylate and a specific The polymerizable monomer of an aromatic ring or a specific cycloalkane is polymerized at a specific ratio. Patent Document 3 below discloses a fiber processing agent containing at least one of a silicon-based compound, a wax-based compound, and a wax-zirconium-based compound. Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2015-172198 Patent Document 2: Japanese Patent Laid-Open No. 2015-221952 Patent Document 3: Japanese Patent Laid-Open No. 2006-124866

[The problem to be solved by the invention]

If the conventional non-fluorine-based water repellent system wants to impart sufficient water repellency to the fiber product, it is necessary to treat the fiber product under the condition that the water repellent component becomes a high concentration. The fiber products treated under this condition have the following problems: the texture becomes hard, and nail marks (also called scratches) are prone to appear when rubbing the fiber surface with nails.

In addition, fiber products have a problem in that if water droplets adhering to the surface remain for a long time, they will be immersed in water. Therefore, water-repellent fiber products are required not only to have water repellency and durable water repellency, but also to have water repellency that the water droplets attached to the surface of the fiber roll off immediately.

The present invention was completed in view of the above circumstances, and its object is to provide a water-repellent fiber product that is excellent in water repellency, durable water repellency, and water repellency, has good texture, and is hard to scratch, and a water repellent composition capable of realizing the same And the manufacturing method of water-repellent fiber products. [Technical means to solve the problem]

The present invention provides a water repellent composition comprising: a non-fluorine-based polymer (α) containing a structural unit derived from a (meth)acrylate monomer (A1) represented by the following general formula (A-1) And a structural unit derived from the compound (A2) represented by the following general formula (A-2); and polysiloxane resin (β).

[於式(A-1)中，R¹ 表示氫或甲基，R² 表示可具有取代基之碳數為12～30之1價之烴基]。[化1]

[In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 to 30 carbon atoms that may have a substituent].

[於式(A-2)中，R¹¹ 表示氫或甲基，R¹² 表示碳數為1～6之2價之烴基，Z表示酯基或醯胺基，W表示以-CO-R¹³ (於式中，R¹³ 表示碳數為1～4之1價之烴基)表示之基、以-NH-CO-NH₂ 表示之基、或以下述式(A-3)表示之基。 [化3]

][化2]

[In formula (A-2), R ¹¹ represents hydrogen or methyl, R ¹² represents a divalent hydrocarbon group with a carbon number of 1 to 6, Z represents an ester group or an amide group, and W represents -CO-R ¹³ (In the formula, R ¹³ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms), a group represented by -NH-CO-NH ₂ or a group represented by the following formula (A-3). [化3]

]

According to the water-repellent composition of the present invention, by combining the above-mentioned specific non-fluorine-based polymer (α) and silicone resin (β), it is possible to obtain excellent water repellency, durable water repellency, water repellency and texture. Water-repellent fiber products, the obtained fiber products are hard to scratch. The reason for obtaining such an effect is estimated by the inventors as follows. The above-mentioned non-fluorine-based polymer (α) has an ester group or an amide group, and a ureido group or a ketone group as a structural unit derived from the compound (A2), whereby it is considered that it has the property of being easy to agglomerate. Characteristic non-fluorine-based polymer (α) and silicone resin (β) composition treated fiber is considered to be easy to form uneven structure on the fiber surface. Therefore, the inventors believe that the non-fluorine-based polymer (α) and silicone resin (β) are attached to the fiber even under low-concentration processing conditions that do not impair the texture of the fiber and hardly cause scratches. It can also provide sufficient water repellency, durable water repellency, and water repellency by forming an uneven structure.

In addition, fiber products etc. subjected to water-repellent processing may be processed by coating a predetermined portion with urethane resin or acrylic resin. In this case, the fiber product is required not only to have sufficient water repellency, but also difficult to peel off the coating of the coated part. The difficulty of peeling off the coating can be evaluated by measuring the stress (peel strength) required to peel the coating film from the fiber product subjected to water repellent processing. According to the water repellent composition of the present invention, the obtained fiber product can have sufficient peel strength to the coating.

From the viewpoint of water repellency, durable water repellency, and peel strength, the non-fluorine-based polymer (α) may further contain a structural unit derived from at least one monomer (VC) of vinyl chloride and vinylidene chloride.

Furthermore, the present invention provides a water-repellent fiber product comprising a fiber product to which the water-repellent composition of the present invention is attached.

The water-repellent fiber product of the present invention is excellent in water repellency, durable water repellency, water repellency, and texture, and is hard to scratch. In addition, the water-repellent fiber product of the present invention can have sufficient peel strength to the coating.

In addition, the present invention provides a method for producing a water-repellent fiber product, which includes a step of treating the fiber product with a treatment liquid containing the water-repellent composition of the present invention.

According to the method for producing a water-repellent fiber product of the present invention, a water-repellent fiber product that is excellent in water repellency, durable water repellency, water repellency, and texture, and is hard to scratch. In addition, the water-repellent fiber product manufactured by the method of the present invention can have sufficient peel strength to the coating. [Effects of Invention]

According to the present invention, it is possible to provide a water-repellent fiber product that is excellent in water repellency, durable water repellency, and water repellency, has a good texture, and is hard to scratch, as well as a water-repellent composition capable of realizing the same, and a method for manufacturing the water-repellent fiber product .

The water repellent composition of this embodiment contains a non-fluorine-based polymer (α) and a silicone resin (β).

＜Non-fluorine-based polymer (α)＞ The non-fluorine-based polymer (α) contains structural units derived from the (meth)acrylate monomer (A1) represented by the following general formula (A-1) (hereinafter, also referred to as "(A1) component") and derived from A structural unit of the compound (A2) represented by the following general formula (A-2) (hereinafter also referred to as "(A2) component").

[於式(A-1)中，R¹ 表示氫或甲基，R² 表示可具有取代基之碳數為12～30之1價之烴基]。[化4]

[In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 to 30 carbon atoms that may have a substituent].

[於式(A-2)中，R¹¹ 表示氫或甲基，R¹² 表示碳數為1～6之2價之烴基，Z表示酯基或醯胺基，W表示以-CO-R¹³ (R¹³ 表示碳數為1～4之1價之烴基)表示之基、以-NH-CO-NH₂ 表示之基、或以下述式(A-3)表示之基。 [化6]

][化5]

[In formula (A-2), R ¹¹ represents hydrogen or methyl, R ¹² represents a divalent hydrocarbon group with a carbon number of 1 to 6, Z represents an ester group or an amide group, and W represents -CO-R ¹³ (R ¹³ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms), a group represented by -NH-CO-NH ₂ or a group represented by the following formula (A-3). [化6]

]

Here, "(meth)acrylate" means "acrylate" or its corresponding "methacrylate", and it also means "(meth)acrylic acid", "(meth)acrylamide", etc. The same meaning.

The said (A1) component has a C12-30 monovalent hydrocarbon group which may have a substituent. The hydrocarbon group may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may further have an alicyclic or aromatic cyclic ring. Among them, from the viewpoint of water repellency and texture, it is preferably a linear one, and more preferably a linear alkyl group. In this case, the water repellency is more excellent. When a monovalent hydrocarbon group having 12 to 30 carbon atoms has a substituent, examples of the substituent include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, and ( One or more of meth)acryloxy groups. This embodiment is based on the above general formula (A-1), and R ^{2 is} preferably an unsubstituted hydrocarbon group.

From the same viewpoint as the above, the carbon number of the above-mentioned hydrocarbon group is preferably 12-24.

The carbon number of the above-mentioned hydrocarbon group is more preferably 12-22. When the carbon number is in this range, water repellency and texture become particularly excellent. A particularly preferred hydrocarbon group is a linear alkyl group having 18 to 22 carbon atoms.

Examples of the above-mentioned (A1) component include stearyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, and (meth)acrylic acid. Pentadecyl ester, heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate And behenyl (meth)acrylate.

The above-mentioned component (A1) may have at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group that can react with a crosslinking agent. In this case, the durable water repellency of the obtained fiber product can be further improved. The isocyanate group can also form a blocked isocyanate group protected by a blocking agent. In addition, when the component (A1) has an amine group, the texture of the obtained fiber product can be further improved.

The (A1) component is preferably a monofunctional (meth)acrylate monomer having one polymerizable unsaturated group in one molecule.

The said (A1) component may be used individually by 1 type, and may be used in combination of 2 or more types.

In the above formula (A-2), R ¹² may be linear or branched, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may further have an alicyclic ring.

In the above formula (A-2), when Z is an ester group, R ¹² is a hydrocarbon group with a carbon number of 2 to 4, and W is a group represented by -NH-CO-NH ₂ or the above formula (A -3) The base of expression. When Z is an amide group, it is preferable that R ¹² is a hydrocarbon group having 2 to 4 carbons, W is a group represented by -CO-R ¹³ and R ¹³ has 1 to 2 carbons.

The component (A2) is not particularly limited, and examples include diacetone acrylamide, 2-methacrylic acid [2-(2-oxo-2-imidazolidinyl) ethyl ester], N-[2 -(2-Pendant oxyimidazolidin-3-yl)ethyl]methacrylamide. Among them, from the viewpoint of the durable water repellency of fiber products, as the above-mentioned (A2) component, diacetone acrylamide and 2-methacrylic acid [2-(2-oxo-2- Imidazolidinyl) ethyl ester].

The said (A2) component may be used individually by 1 type, and may be used in combination of 2 or more types.

The content ratio of the structural unit derived from the component (A1) and the structural unit derived from the component (A2) of the non-fluorine-based polymer (α) of this embodiment is preferably the mass of the component (A1) and the component (A2) The mass ratio (A1)/(A2) is 99.9/0.1 to 70/30, more preferably 99.8/0.2 to 80/20, and still more preferably 99.7/0.3 to 90/10. If (A1)/(A2) is within the above range, the durable water repellency and water repellency of the obtained fiber product will become better.

The total mass of the mass of the (A1) component and the mass of the (A2) component to be formulated is preferably 60-100% by mass relative to the total amount of the monomer components constituting the non-fluorine-based polymer (α), more preferably 70 -99% by mass, more preferably 80-98% by mass.

From the viewpoint of peel strength, the non-fluorine-based polymer (α) preferably contains at least one monomer (VC) of vinyl chloride and vinylidene chloride in addition to the components (A1) and (A2) ( Hereinafter, it is also referred to as "(VC) component") as a monomer component.

From the viewpoint of maintaining the texture of the fiber product, the (VC) component is preferably vinyl chloride.

From the viewpoints of water repellency, durable water repellency, and peel strength, the quality of the (VC) component to be formulated is preferably 10 parts by mass relative to the total mass of the (A1) component and the mass of the (A2) component. Part by mass or more, more preferably 20 parts by mass or more. From the viewpoint of water repellency, durable water repellency and texture, the quality of the (VC) component to be formulated is preferably 100 parts by mass relative to the total mass of the (A1) component and the mass of the (A2) component. Parts or less, more preferably 75 parts by mass or less.

In terms of improving the emulsion stability of the non-fluorine-based polymer (α) in the composition during emulsion polymerization or dispersion polymerization and after polymerization, the non-fluorine-based polymer (α) is preferably in addition to (A1) In addition to components and (A2) components, it contains 7-18 compounds selected from (B1) HLB (Hydrophile Lipophile Balance) represented by the following general formula (I-1), and (B2) HLB 7～ 18 is a compound represented by the following general formula (II-1), and (B3) HLB of 7-18 is obtained by adding an alkylene oxide with 2 to 4 carbon atoms to fats and oils having a hydroxyl group and a polymerizable unsaturated group At least one reactive emulsifier (B) (hereinafter also referred to as "(B) component") among the compounds of is used as a monomer component.

[於式(I-1)中，R³ 表示氫或甲基，X表示碳數為1～6之直鏈或者支鏈之伸烷基，Y¹ 表示包含碳數為2～4之伸烷氧基之2價之基]。[化7]

[In the formula (I-1), R ³ represents hydrogen or methyl, X represents a linear or branched alkylene having 1 to 6 carbon atoms, and Y ¹ represents an alkylene having 2 to 4 carbon atoms. The divalent group of oxy].

[於式(II-1)中，R⁴ 表示具有聚合性不飽和基之碳數為13～17之1價之不飽和烴基，Y² 表示包含碳數為2～4之伸烷氧基之2價之基]。[化8]

[In formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group with a carbon number of 13-17 having a polymerizable unsaturated group, and Y ² represents an alkoxy group containing a carbon number of 2 to 4 The base of 2 prices].

The so-called "reactive emulsifier" is an emulsifying and dispersing agent with free radical reactivity, that is, a surfactant having more than one polymerizable unsaturated group in the molecule, and is a monomer capable of interacting with (meth)acrylate Body copolymerizer.

In addition, the so-called "HLB" refers to the HLB value calculated by the Griffin method that treats the ethoxylate group as a hydrophilic group, and all other groups are regarded as lipophilic groups.

The HLB of the above-mentioned (B1) to (B3) compounds used in this embodiment is 7-18, which is combined during emulsion polymerization or dispersion polymerization of the non-fluoropolymer (α) of this embodiment and after polymerization In terms of emulsification stability (hereinafter referred to simply as emulsification stability) in the product, 9-15 are preferred. Furthermore, in terms of the storage stability of the water-repellent composition, it is more preferable to use two or more reactive emulsifiers (B) having different HLBs within the above range in combination.

In the reactive emulsifier (B1) represented by the above-mentioned general formula (I-1) used in this embodiment, R ³ is hydrogen or methyl, and is used in combination with (A1) component and/or (A2) component In terms of copolymerization, methyl is more preferred. X is a linear or branched alkylene group having 1 to 6 carbon atoms. In terms of the emulsification stability of the non-fluorinated polymer (α) of this embodiment, it is more preferably 2 to 3 carbon atoms. The straight-chain alkyl extension. Y ¹ is a divalent group containing an alkoxy group having 2 to 4 carbon atoms. The type, combination, and addition amount of the alkoxy group of Y ¹ can be appropriately selected so as to be within the range of the above-mentioned HLB. In addition, when there are two or more alkoxylate groups, they may have a block addition structure or a random addition structure.

The compound represented by the above general formula (I-1) is preferably a compound represented by the following general formula (I-2).

[於式(I-2)中，R³ 表示氫或甲基，X表示碳數為1～6之直鏈或者支鏈之伸烷基，A¹ O表示碳數為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地選擇，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9]

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

In the compound represented by the above-mentioned general formula (I-2), R ³ is hydrogen or a methyl group, and more preferably a methyl group in terms of the copolymerizability with the (A1) component and/or (A2) component. X is a linear or branched alkylene group having 1 to 6 carbon atoms. In terms of the emulsification stability of the non-fluorinated polymer (α) of this embodiment, it is more preferably 2 to 3 carbon atoms. The straight-chain alkyl extension. 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 be within the range of the above-mentioned HLB. In terms of the emulsion stability of the non-fluorine-based polymer (α) of the present embodiment, m is preferably an integer of 1 to 80, and more preferably an integer of 1 to 60. When m is 2 or more, m A ¹ O may be the same or different. In addition, when there are two or more types of A ¹ O, they may have a block addition structure or a random addition structure.

The reactive emulsifier (B1) represented by the above general formula (I-2) can be obtained by a previously known method, and is not particularly limited. Moreover, it can be easily obtained from commercially available products, for example, "Latemul PD-420", "Latemul PD-430", and "Latemul PD-450" manufactured by Kao Co., Ltd. can be cited.

In the reactive emulsifier (B2) represented by the above-mentioned general formula (II-1) used in this embodiment, R ⁴ is a monovalent unsaturated with a carbon number of 13-17 having a polymerizable unsaturated group The hydrocarbyl groups include tridecenyl, tridecadienyl, tetradecenyl, tetradecadienyl, pentadecenyl, pentadecenyl, pentadecenyl, Heptadecenyl, heptadecadienyl, heptatrienyl and the like. In terms of the emulsion stability of the non-fluorine-based polymer (α) of this embodiment, 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 type, combination, and addition amount of the alkoxy group of Y ² can be appropriately selected so as to be within the range of the above-mentioned HLB. In addition, when there are two or more alkoxylate groups, they may have a block addition structure or a random addition structure. In terms of the emulsion stability of the non-fluorine-based polymer (α) of this embodiment, the alkoxylate group is more preferably an ethoxylate group.

The compound represented by the above general formula (II-1) is preferably a compound represented by the following general formula (II-2).

[於式(II-2)中，R⁴ 表示具有聚合性不飽和基之碳數為13～17之1價之不飽和烴基，A² O表示碳數為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地選擇，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]。[化10]

[In formula (II-2), R ⁴ represents a monovalent unsaturated hydrocarbon group having a carbon number of 13-17 having a polymerizable unsaturated group, and A ² O represents an alkoxy group having a carbon number of 2 to 4, n can be appropriately selected so as to be within the range of the above-mentioned HLB. Specifically, it is preferably an integer of 1 to 50. When n is 2 or more, n A ² O may be the same or different].

R of the compound represented by the aforementioned general formula (II-2) ⁴ include the above general formula (II-1) are the same as R ^4.

A ² O is an alkoxy group having 2 to 4 carbon atoms. Regarding the emulsification stability of the non-fluorine-based polymer (α) of the present embodiment, the type and combination of A ² O and the number of n can be appropriately selected so as to be within the range of the above-mentioned HLB. In terms of the emulsification stability of the non-fluorine-based polymer (α) of this embodiment, A ² O is more preferably an ethoxylate group, and n is preferably an integer of 1-50, more preferably 5-20 An integer is more preferably an integer of 8-14. When n is 2 or more, n A ² O may be the same or different. In addition, when there are two or more types of A ² O, they may have a block addition structure or a random addition structure.

The reactive emulsifier (B2) represented by the general formula (II-2) used in this embodiment can be synthesized by adding alkylene oxide to a phenol having a corresponding unsaturated hydrocarbon group by a previously known method. It is not particularly limited. For example, it can be synthesized by using alkali catalysts such as caustic soda and caustic potash, and adding a predetermined amount of alkylene oxide at 120 to 170°C under pressure.

Among the above-mentioned phenols having corresponding unsaturated hydrocarbon groups, in addition to industrially manufactured pure products or mixtures, those that exist as pure products or mixtures extracted and refined from plants and the like are also included. For example, 3-[8(Z),11(Z),14-pentadecatrienyl]phenol, 3-[8(Z),11() extracted from the shell of cashew nuts, etc. and collectively referred to as cardanol Z)-pentadecenyl]phenol, 3-[8(Z)-pentadecenyl]phenol, 3-[11(Z)-pentadecenyl]phenol, etc.

The reactive emulsifier (B3) used in this embodiment is a compound obtained by adding an HLB of 7 to 18 and adding an alkylene oxide of 2 to 4 to fats and oils having a hydroxyl group and a polymerizable unsaturated group. Examples of fats and oils having a hydroxyl group and a polymerizable unsaturated group include hydroxy unsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidic acid, eicosapentaenoic acid, Docosapentaenoic acid, etc.) fatty acid monoglyceride or diglyceride, containing at least one hydroxyunsaturated fatty acid (ricinoleic acid, transricinoleic acid, 2-hydroxyeicosatetraenoic acid, etc.) ) Triglycerides of fatty acids. In terms of the emulsification stability of the non-fluorine-based polymer (α) of this embodiment, it is preferably an alkylene oxide adduct of triglyceride of fatty acid containing at least one hydroxyunsaturated fatty acid, and more preferably It is an alkylene oxide adduct of castor oil (triglyceride of fatty acid containing ricinoleic acid) with a carbon number of 2 to 4, and more preferably an ethylene oxide adduct of castor oil. Furthermore, the number of added moles of alkylene oxide can be appropriately selected so as to be within the range of the above-mentioned HLB, and it is more preferable in terms of the emulsion stability of the non-fluorine-based polymer (α) of the present embodiment 20-50 mol, more preferably 25-45 mol. Moreover, when there are two or more types of alkylene oxides, they may have a block addition structure or a random addition structure.

The reactive emulsifier (B3) used in this embodiment can be synthesized by adding alkylene oxide to fats and oils having a hydroxyl group and a polymerizable unsaturated group by a conventionally known method, and is not particularly limited. For example, it can be synthesized by using alkali catalysts such as caustic soda and caustic potash, and adding a prescribed amount of triglycerides of fatty acids containing ricinoleic acid, ie castor oil, at 120-170°C under pressure. Alkylene oxide.

From the viewpoint of improving the water repellency of the obtained fiber product and the emulsion stability of the non-fluorine-based polymer (α) in the present embodiment during and after the emulsion polymerization or dispersion polymerization in the composition, this embodiment The composition ratio of the monomers of the component (B) of the non-fluorine-based polymer (α) is preferably 0.5 to 20% by mass relative to the total amount of the monomer components constituting the non-fluorine-based polymer (α), and more It is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.

In terms of improving the durable water repellency of the obtained fiber product, the non-fluorine-based polymer (α) included in the water repellent composition of this embodiment is preferably excluding the components (A1) and (A2) , Containing at least one second (meth)acrylate monomer (C) selected from the group consisting of (C1), (C2), (C3) and (C4) below (hereinafter also referred to as " C component") as a monomer component.

[於式(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種官能基之碳數為1～11的1價之鏈狀烴基。其中，分子內之(甲基)丙烯醯氧基之數量為2以下]。(C1) A (meth)acrylate monomer represented by the following general formula (C-1) [Chemical Formula 11]

[In the formula (C-1), R ⁵ represents hydrogen or methyl, and R ⁶ represents a group selected from hydroxyl, amino, carboxy, epoxy, isocyanate and (meth)acryloxy groups. At least one functional group in the group is a monovalent chain hydrocarbon group having 1 to 11 carbon atoms. Wherein, the number of (meth)acryloxy groups in the molecule is 2 or less].

[於式(C-2)中，R⁷ 表示氫或甲基，R⁸ 表示可具有取代基之碳數為1～11之1價之環狀烴基]。(C2) (Meth)acrylate monomer represented by the following general formula (C-2) [Chemical Formula 12]

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

[於式(C-3)中，R⁹ 表示未經取代之碳數為1～4之1價之鏈狀烴基]。(C3) Methacrylate monomer represented by the following general formula (C-3) [Chemical 13]

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

[於式(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價之有機基]。(C4) A (meth)acrylate monomer represented by the following general formula (C-4) [Chemical Formula 14]

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

The above-mentioned (C1) monomer system has a (meth)acrylate monomer having a monovalent chain hydrocarbon group with 1 to 11 carbons in the ester portion, and the monovalent chain hydrocarbon group with 1 to 11 carbons has At least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloxy group. In terms of being capable of reacting with a crosslinking agent, the above-mentioned monovalent chain hydrocarbon group having 1 to 11 carbon atoms preferably has one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group. At least one functional group in the group. When the non-fluorine-based polymer (α) containing monomers (C1) having the groups capable of reacting with the cross-linking agent and the cross-linking agent are processed together on the fiber product, the obtained can be maintained The texture of the fiber product improves the durable water repellency. The isocyanate group may also be a blocked isocyanate group protected by a blocking agent.

The above-mentioned 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 further have a substituent in addition to the above-mentioned functional group. Among them, in terms of improving the durable water repellency of the obtained fiber product, a linear and/or saturated hydrocarbon group is preferred.

Specific (C1) monomers include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 1,1-bis( Acrylic oxymethyl) ethyl isocyanate and the like. These monomers may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, in terms of improving the durable water repellency of the obtained fiber products, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, 1,1-bis(acrylic acid) are preferred. (Oxymethyl)ethyl isocyanate. Furthermore, in terms of improving the texture of the obtained fiber product, dimethylaminoethyl (meth)acrylate is preferred.

From the viewpoint of water repellency, the mass of the (C1) component to be formulated is preferably 3 parts by mass or more relative to the total of the mass of the (A1) component and the mass of the (A2) component 100 parts by mass, and more preferably 5 parts by mass or more. From the viewpoint of water repellency, the mass of the (C1) component to be formulated is preferably 30 parts by mass or less relative to the total of the mass of the (A1) component and the mass of the (A2) component 100 parts by mass, and more preferably 25 parts by mass or less.

The above-mentioned (C2) monomer system has a (meth)acrylate monomer having a monovalent cyclic hydrocarbon group with a carbon number of 1 to 11 in the ester moiety. Examples of the cyclic hydrocarbon group include iso?, cyclohexyl, and two Cyclopentyl and others. These cyclic hydrocarbon groups may have substituents such as alkyl groups. However, when the substituent is a hydrocarbon group, a hydrocarbon group whose total carbon number of the substituent and the cyclic hydrocarbon group is 11 or less can be selected. Moreover, the case where these cyclic hydrocarbon groups are directly bonded to an ester bond is preferable from the viewpoint of improving durable water repellency. The cyclic hydrocarbon group may be alicyclic or aromatic. In the case of the alicyclic type, it may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Specific monomers include iso-(meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, and the like. These monomers may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, in terms of improving the durable water repellency of the obtained fiber product, iso(meth)acrylate and cyclohexyl methacrylate are preferred, and iso(meth)acrylate is more preferred.

From the viewpoint of water repellency, the mass of the (C2) component to be formulated is preferably 3 parts by mass or more relative to the total of the mass of the (A1) component and the mass of the (A2) component 100 parts by mass, and more preferably 5 parts by mass or more. From the viewpoint of water repellency, the mass of the (C2) component to be formulated is preferably 30 parts by mass or less relative to the total mass of the (A1) component and the mass of the (A2) component 100 parts by mass, more preferably 25 parts by mass or less.

The mono-system of (C3) is a methacrylate monomer in which an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms is directly bonded to the ester bond of the ester portion. As the chain hydrocarbon group having 1 to 4 carbon atoms, a straight chain hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms are preferred. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, and tertiary butyl. Specific compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and methacrylic acid. Tertiary butyl ester. These monomers may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, in terms of improving the durable water repellency of the obtained fiber product, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferred, and methyl methacrylate is more preferred. .

From the viewpoint of water repellency, the mass of the (C3) component to be formulated is preferably 3 parts by mass or more relative to the total of the mass of the (A1) component and the mass of the (A2) component 100 parts by mass, and more preferably 5 parts by mass or more. From the viewpoint of water repellency, the mass of the (C3) component to be formulated is preferably 30 parts by mass or less relative to the total mass of the (A1) component and the mass of the (A2) component 100 parts by mass, more preferably 25 parts by mass or less.

The above-mentioned (C4) single-system (meth)acrylate monomer having 3 or more polymerizable unsaturated groups in one molecule. In this embodiment, it is preferable that T in the general formula (C-4) is a (meth)acryloxy group and has 3 or more (meth)acryloxy groups in one molecule. The (meth)acrylate monomer. In formula (C-4), p T may be the same or different. As specific compounds, for example, ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trihydroxymethyl Methyl propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. These monomers may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, in terms of improving the durable water repellency of the obtained fiber product, tetramethylolmethane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferable.

From the viewpoint of water repellency, the quality of the (C4) component to be formulated is preferably 3 parts by mass or more relative to 100 parts by mass of the total of the mass of the (A1) component and the mass of the (A2) component, and more preferably 5 parts by mass or more. From the viewpoint of water repellency, the mass of the (C4) component to be formulated is preferably 30 parts by mass or less relative to the total of the mass of the (A1) component and the mass of the (A2) component 100 parts by mass, and more preferably 25 parts by mass or less.

From the viewpoint of the water repellency and texture of the obtained fiber product, the total composition ratio of the monomers of the above component (C) of the non-fluorine-based polymer (α) of this embodiment is preferably relative to that of the non-fluorine-based polymer The total amount of the monomer components of the substance (α) is 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass.

From the viewpoint of water repellency, the quality of the (C) component to be blended is preferably 3 parts by mass or more relative to the total of the mass of the (A1) component and the mass of the (A2) component 100 parts by mass, and more preferably 5 parts by mass or more. From the standpoint of water repellency, the mass of the (C) component to be formulated is preferably 30 parts by mass or less relative to the total of the mass of the (A1) component and the mass of the (A2) component 100 parts by mass, and more preferably 25 parts by mass or less.

The non-fluorine-based polymer (α) contained in the water repellent composition of this embodiment may contain, in addition to the components (A1) and (A2), those capable of being copolymerized with them within a range that does not impair the effects of the present invention Monofunctional monomer (D) (hereinafter, also referred to as "(D) component").

As the (D) component, for example, (meth)acrylic acid, (meth)acrylate having a hydrocarbon group other than the (A) component and (C) component, (meth)acrylic acid, and fumarene Esters, maleates, fumaric acid, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, ethylene, benzene Ethylene and other non-fluorine-free vinyl monomers other than (VC) components. Furthermore, (meth)acrylates having a hydrocarbon group other than the components (A) and (C) may have vinyl groups, hydroxyl groups, amino groups, epoxy groups, isocyanate groups, and blocked isocyanates in the hydrocarbon groups. Substituents such as acid groups may also have substituents other than those capable of reacting with crosslinking agents, such as quaternary ammonium groups, and may also have ether bonds, ester bonds, amide bonds, or urethane bonds, etc. . Examples of (meth)acrylates other than (A) component and (C) component include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and ethylene glycol Di(meth)acrylate etc. Among them, (meth)acrylic acid is more preferable in terms of improving the peel strength of the obtained fiber product to the coating.

From the viewpoint of water repellency, the mass of the (D) component to be formulated is preferably 3 parts by mass or more with respect to the total of the mass of the (A1) component and the mass of the (A2) component 100 parts by mass, and more preferably 5 parts by mass or more. From the viewpoint of water repellency, it is preferable that the mass of the monomer (D) formulated is 40 parts by mass or less with respect to 100 parts by mass of the total mass of the component (A1) and the mass of the component (A2). More preferably, it is 35 parts by mass or less.

The non-fluorine-based polymer (α) of this embodiment has at least one functional group selected from the group consisting of hydroxyl, amino, carboxyl, epoxy, and isocyanate that can react with a crosslinking agent It is preferable in terms of improving the durable water repellency of the obtained fiber product. The isocyanate group can also form a blocked isocyanate group protected by a blocking agent. In addition, the case where the non-fluorine-based polymer (α) has an amine group is preferable in that it also improves the texture of the obtained fiber product.

The weight average molecular weight of the non-fluorine-based polymer (α) of the present embodiment is preferably 30,000 or more. If the weight average molecular weight is 30,000 or more, the water repellency of the obtained fiber product tends to be further improved. Furthermore, the weight average molecular weight of the non-fluorine-based polymer (α) is more preferably 100,000 or more. In this case, the obtained fiber product can more fully exhibit water repellency. The upper limit of the weight average molecular weight of the non-fluorine-based polymer (α) is preferably about 5 million.

The so-called weight average molecular weight of the non-fluorine-based polymer (α) refers to the use of a GPC (Gel Permeation Chromatography) device (GPC "HLC-8020" manufactured by Tosoh Corporation) at a column temperature of 40 Measured with tetrahydrofuran in the eluent at a temperature of ℃ and a flow rate of 1.0 ml/min. The value is converted from standard polystyrene. In addition, the pipe string is formed by connecting 3 TSK-GEL G5000HHR, G4000HHR, G3000HHR manufactured by Tosoh Corporation.

In this embodiment, the melt viscosity at 105°C of the non-fluorine-based polymer (α) is preferably 1000 Pa·s or less. When the melt viscosity at 105°C is 1000 Pa·s or less, it tends to be easy to maintain the texture of the obtained fiber product. In addition, when the melt viscosity of the non-fluorine-based polymer (α) is 1000 Pa·s or less, when the non-fluorine-based polymer (α) is emulsified or dispersed to form a water repellent composition, it can suppress Since the fluorine-based polymer (α) precipitates or precipitates, it tends to be easy to maintain the storage stability of the water-repellent composition well. Furthermore, the melt viscosity at 105°C is more preferably 500 Pa·s or less. In this case, the obtained fiber product or the like is one that fully exhibits water repellency and has better texture.

The so-called “melt viscosity at 105°C” refers to the use of an overhead flow tester (for example, CFT-500 manufactured by Shimadzu), which is placed in a cylinder equipped with a die (length 10 mm, diameter 1 mm) g of non-fluorine-based polymer, keep it at 105°C for 6 minutes, apply a load of 100 kg·f/cm ² through the plunger and measure the viscosity.

<Polysiloxane resin (β)> Examples of the polysiloxane resin (β) include silicone resin and silicone oil. The so-called silicone resin is an organopolysiloxane containing MQ, MDQ, MT, MTQ, MDT or MDTQ as a constituent, and is solid at 25°C and has a three-dimensional structure. Here, M, D, T, and Q represent (R'') ₃ SiO _0.5 unit, (R'') ₂ SiO unit, R'' SiO _1.5 unit, and SiO ₂ unit, respectively. R" represents a monovalent aliphatic hydrocarbon group with 1 to 10 carbons or a monovalent aromatic hydrocarbon group with 6 to 15 carbons.

Polysiloxane resins are generally known as MQ resins, MT resins, or MDT resins, and there are cases where they have parts denoted as MDQ, MTQ, or MDTQ.

Polysiloxane resin can also be obtained as a solution by dissolving it in a suitable solvent. As the solvent, for example, relatively low molecular weight methyl polysiloxane, decamethylcyclopentasiloxane, octylmethylcyclotetrasiloxane, n-hexane, isopropanol, dichloromethane, 1,1,1- Trichloroethane and mixtures of these solvents, etc.

As a solution of polysiloxane resin, for example, KF7312J (polysiloxane containing trimethylsilyl group: decamethylcyclopentasiloxane=50:50 mixture) commercially available from Shin-Etsu Chemical Co., Ltd. can be cited, KF7312F (polysiloxane containing trimethylsilyl group: octylmethylcyclotetrasiloxane = 50: 50 mixture), KF9021L (polysiloxane containing trimethylsilyl group: low viscosity methyl polysiloxane = 50:50 mixture), KF7312L (polysiloxane containing trimethylsilyl: low viscosity methylpolysiloxane = 50:50 mixture), etc.

As a separate polysiloxane resin, for example, MQ-1600 solid Resin (polysiloxane containing trimethylsilyl group), MQ-1640 Flake Resin (containing trimethylsilyl group) commercially available from Toray Dow Corning Co., Ltd. Polysiloxane, polypropylsilsesquioxane) etc. The above-mentioned commercially available products are as follows: including trimethylsilyl-containing polysiloxanes, including MQ, MDQ, MT, MTQ, MDT or MDTQ.

The so-called polysiloxane oil-based linear organopolysiloxane may also have an organic group in at least any one of the side chain and the terminal of the organopolysiloxane. Examples of such silicone oils include pure silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil; amino modified silicone oil , Epoxy modified silicone oil, methanol modified silicone oil, mercapto modified silicone oil, carboxyl modified silicone oil, polyether modified silicone oil, alkyl modified silicone Oxygen oil, aralkyl modified polysiloxane oil, alkyl aralkyl modified polysiloxane oil, higher fatty acid ester modified polysiloxane oil, higher aliphatic amide modified polysiloxane oil, as follows Organically modified silicone oil and other modified silicone oil represented by general formula (1). Furthermore, in the following general formula (1), each structural unit may be a block or random, and may be arranged alternately.

[於式(1)中，R²⁰ 、R²¹ 及R²² 分別獨立地表示氫原子、甲基、乙基或碳數為1～4之烷氧基，R²³ 表示具有芳香族環之碳數為8～40之烴基、或碳數為3～22之烷基，R³⁰ 、R³¹ 、R³² 、R³³ 、R³⁴ 及R³⁵ 分別獨立地表示氫原子、甲基、乙基、碳數為1～4之烷氧基、具有芳香族環之碳數為8～40之烴基、或碳數為3～22之烷基，a表示0以上之整數，b表示1以上之整數，(a＋b)為10～200，於a為2以上之情形時，存在複數個之R²⁰ 及R²¹ 可分別相同亦可不同，於b為2以上之情形時，存在複數個之R²² 及R²³ 可分別相同亦可不同]。[化15]

[In formula (1), R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and R ²³ represents the number of carbon atoms having an aromatic ring It is a hydrocarbon group of 8-40 or an alkyl group of 3-22 carbons, R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom, a methyl group, an ethyl group, and a carbon number Is an alkoxy group of 1 to 4, a hydrocarbon group of 8 to 40 carbons with an aromatic ring, or an alkyl group of 3 to 22 carbons, a represents an integer of 0 or more, b represents an integer of 1 or more, (a+b ) Is 10 to 200. When a is 2 or more, there may be a plurality of R ²⁰ and R ²¹ which may be the same or different. When b is 2 or more, there may be a plurality of R ²² and R ²³ They are the same or different].

Among such polysiloxane resins, from the viewpoint of water repellency and the dispersibility of the water repellent composition to an aqueous medium, polysiloxane oil is preferred, and methyl hydrogen polysiloxane oil and amino group are more preferred. Modified silicone oil, epoxy modified silicone oil, methanol modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, alkyl aralkyl modified silicone Oxygen oil, in terms of further improving the water repellency and durable water repellency of the obtained fiber product, it is more preferably alkyl-modified polysiloxane, or it can further improve the texture of the obtained fiber product and further reduce In terms of generation of scratches, amino-modified silicone, methyl hydrogen silicone, and dimethyl silicone are more preferred.

In the organically modified polysiloxane oil represented by the above general formula (1), the alkoxy group having a carbon number of 1 to 4 may be linear or branched. As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc. are mentioned, for example. In terms of being industrially easy to manufacture and easy to obtain, R ²⁰ , R ²¹ and R ^{22 are} preferably each independently a hydrogen atom or a methyl group, more preferably a methyl group.

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

[於式(2)中，R⁴⁰ 表示碳數為2～6之伸烷基，R⁴¹ 表示單鍵或碳數為1～4之伸烷基，c表示0～3之整數。於c為2或3之情形時，存在複數個之R⁴¹ 可相同亦可不同]。[化16]

[In formula (2), R ⁴⁰ represents an alkylene group having a carbon number of 2-6, R ⁴¹ represents a single bond or an alkylene group having a carbon number of 1 to 4, and c represents an integer of 0-3. When c is 2 or 3, there are a plurality of R ⁴¹ which may be the same or different].

The aforementioned alkylene group may be linear or branched.

[於式(3)中，R⁴² 表示碳數為2～6之伸烷基，R⁴³ 表示單鍵或碳數為1～4之伸烷基，d表示0～3之整數。於d為2或3之情形時，存在複數個之R⁴³ 可相同亦可不同]。[化17]

[In formula (3), R ⁴² represents an alkylene group having a carbon number of 2-6, R ⁴³ represents a single bond or an alkylene group having a carbon number of 1 to 4, and d represents an integer of 0-3. When d is 2 or 3, there are a plurality of R ⁴³ which may be the same or different].

The aforementioned 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 industrial ease of production and easy availability.

In the group represented by the above general formula (2), R ^{40 is} preferably an alkylene group having a carbon number of 2 to 4, and c is preferably 0 or 1 in terms of industrial ease of manufacture and availability. , More preferably 0.

In the group represented by the above general formula (3), R ^{42 is} preferably an alkylene group having a carbon number of 2 to 4, and d is preferably 0 or 1 in terms of industrial ease of manufacture and availability. , More preferably 0.

As the above-mentioned hydrocarbon group having an aromatic ring with 8 to 40 carbon atoms, in terms of being industrially easy to manufacture and easy to obtain, the above-mentioned aralkyl group having 8 to 40 carbon atoms and the above-mentioned general formula are preferred. (2) The base indicated is more preferably the above-mentioned aralkyl group having 8 to 40 carbon atoms in terms of improving the water repellency of the obtained fiber product.

The aforementioned alkyl group having 3 to 22 carbon atoms may be linear or branched. Examples of alkyl groups having 3 to 22 carbon atoms include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, myristyl, cetyl, stearyl, etc. . The alkyl group having 3 to 22 carbon atoms is preferably an alkyl group having 8 to 20 carbon atoms, and more preferably an alkyl group having 12 to 18 carbon atoms in terms of improving the water repellency of the obtained fiber product. base.

In the organically modified silicone oil represented by the above general formula (1), R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are each independently a hydrogen atom, a methyl group, an ethyl group, and a carbon An alkoxy group having 1 to 4, a hydrocarbon group having 8 to 40 carbons having an aromatic ring, or an alkyl group having 3 to 22 carbons. In terms of being industrially easy to manufacture and easy to obtain, R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ^{35 are} preferably each independently a hydrogen atom, a methyl group, an ethyl group, or a carbon number of The alkoxy group of 1 to 4 is more preferably a methyl group.

In the organically modified polysiloxane oil represented by the above general formula (1), a is an integer of 0 or more. In terms of easy manufacturing, easy access to, and more excellent peel strength of the obtained fiber product to the resin coating in the industry, a is preferably 40 or less, and more preferably 30 or less.

In the organically modified silicone oil represented by the general formula (1), (a+b) is 10 to 200. In terms of industrial ease of manufacture and easy access, (a+b) is preferably 20-100, more preferably 40-60. If (a+b) is within the above range, it tends to be easier to manufacture or handle the polysiloxane itself.

The organically modified silicone oil represented by the above general formula (1) can be synthesized by a previously known method. The organically modified polysiloxane oil represented by the above general formula (1) can be obtained by, for example, hydrogenating an aromatic compound having a vinyl group and/or an α-olefin and a polysiloxane having a SiH group. reaction.

Examples of the above-mentioned polysiloxane having SiH groups include methylhydrogenpolysiloxane having a degree of polymerization of 10 to 200, or a copolymer of dimethylsiloxane and methylhydrosiloxane. Among them, in terms of industrial ease of manufacture and easy availability, methyl hydrogen polysiloxane is preferred.

The above-mentioned aromatic compound having a vinyl group is a compound that becomes a source of a hydrocarbon group having an aromatic ring and a carbon number of 8-40 in R ²³ in the above general formula (1). Examples of aromatic compounds having vinyl groups include styrene, α-methylstyrene, vinyl naphthalene, allyl phenyl ether, allyl naphthyl ether, and allyl-p-cumyl benzene. Base ether, allyl-o-phenylphenyl ether, allyl-tris(phenylethyl)-phenyl ether, allyl-tris(2-phenylpropyl)phenyl ether, etc.

The above-mentioned α-olefin is a compound that becomes a source of an alkyl group having 3 to 22 carbon atoms in R ²³ in the above general formula (1). Examples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 1-undecene. , 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and other α-olefins with carbon numbers of 3-22.

The above-mentioned hydrosilation reaction can also be carried out by the following method: if necessary, in the presence of a catalyst, the above-mentioned aromatic compound with vinyl group and the above-mentioned α-olefin are combined with the above-mentioned polysilicon with SiH group in stages or at one time. Oxygen reacts.

The amount of the polysiloxane with SiH group, the aromatic compound with vinyl group, and the α-olefin used in the hydrosilation reaction can be appropriately based on the SiH group equivalent of the polysiloxane with SiH group, or the number average molecular weight, etc. select.

As the catalyst used in the hydrosilation reaction, for example, compounds such as platinum and palladium can be cited, and among them, platinum compounds are preferred. As a platinum compound, platinum (IV) chloride etc. are mentioned, for example.

The reaction conditions of the hydrosilation reaction are not particularly limited and can be appropriately adjusted. The reaction temperature is, for example, 10 to 200°C, preferably 50 to 150°C. The reaction time can be 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. As an inert gas, nitrogen, argon, etc. are mentioned, for example. Although the reaction will advance under solvent-free conditions, solvents can also be used. As a solvent, dioxane, methyl isobutyl ketone, toluene, xylene, butyl acetate, etc. are mentioned, for example.

Examples of the amino-modified silicone oil include compounds having an organic group containing an amino group and/or an imine group in at least any one of the side chain and the terminal of the organopolysiloxane. As such an organic group, an organic group represented by -R-NH ₂ and an organic group represented by -R-NH-R'-NH _{2 can be} cited. Examples of R and R'include divalent groups such as vinyl and propylene groups. Part or all of the amine group and/or imine group may also be a blocked amine group and/or imine group. The blocked amine group and/or imine group can be obtained by the following method: for example, the amine group and/or imine group is treated with a blocking agent. Examples of blocking agents include fatty acids with 2 to 22 carbons, acid anhydrides of fatty acids with 2 to 22 carbons, halides of fatty acids with 2 to 22 carbons, and aliphatic monomers with 1 to 22 carbons. Isocyanates, etc.

From the viewpoint of water repellency, the functional group equivalent of the amino-modified silicone oil is preferably 100 to 20000 g/mol, more preferably 150 to 12000 g/mol, and even more preferably 200 to 4000 g/mol .

The amino-modified silicone oil is preferably liquid at 25°C. The dynamic viscosity of the amino-modified silicone oil at 25°C is preferably 10 to 100,000 mm ² /s, more preferably 10 to 30,000 mm ² /s, and still more preferably 10 to 5,000 mm ² /s. When the dynamic viscosity at 25°C is 100,000 mm ² /s or less, it tends to be easier to ensure workability. The so-called dynamic viscosity at 25°C refers to the value measured by the method described in JIS (Japanese Industrial Standards) K 2283:2000 (Ubbelohde viscometer).

As amino-modified silicone oil, it can also be easily obtained as a commercially available product. As commercially available products, for example, KF8005, KF-868, KF-864, KF-393, KF-8021 (all manufactured by Shin-Etsu Chemical Co., Ltd., trade names), TSF-4709, XF42-B1989 (Momento High-tech Materials Japan Co., Ltd. (manufactured, trade name), BY16-872, SF-8417, BY16-853U, BY16-892 (all manufactured by Toray Dow Corning Co., Ltd., trade name), etc.

In addition, silicone oils other than amino-modified silicone oils can also be easily obtained as commercially available products. As a commercially available product, for example, KF-101 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, epoxy-modified silicone oil), X-22-3701E (manufactured by Shin-Etsu Chemical Co., Ltd., trade name , Carboxyl modified silicone oil), SF8428 (manufactured by Toray Dow Corning Co., Ltd., trade name, methanol-modified silicone oil), KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, methyl hydrogen Polysiloxane oil), X-22-715 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, higher fatty acid ester modified polysiloxane oil), KF-96-3000cp (manufactured by Shin-Etsu Chemical Co., Ltd., product Name, dimethyl polysiloxane oil), SF8416 (manufactured by Toray Dow Corning Co., Ltd., trade name, alkyl-modified polysiloxane oil), SH203 (manufactured by Toray Dow Corning Co., Ltd., trade name, alkyl aromatic Alkyl modified polysiloxane oil), SF8410 (manufactured by Toray Dow Corning Co., Ltd., trade name, polyether modified polysiloxane oil), etc.

The silicone resin (β) may be used alone or in combination of two or more kinds.

In terms of the water repellency, texture, and scratches of the obtained fiber product, the content of the non-fluorine polymer (α) and silicone resin (β) contained in the water repellent composition of this embodiment is not The ratio (α)/(β) of the mass of the fluoropolymer (α) to the mass of the silicone resin (β) is preferably 2.5/97.5-97.5/2.5, and more preferably 5/95-97.5/5, More preferably, it is 10/90-90/10, Especially preferably, it is 15/85-85/15.

In the water-repellent composition of this embodiment, silica modified by a hydrophilizing agent and a hydrophobizing agent (silica having a hydrophilic group and a hydrophobic group on the surface of the silica) can also be used in combination. As such silica having a hydrophilic group and a hydrophobic group on the surface of the silica, for example, REOLOSIL HG-09 (manufactured by Tokuyama Co., Ltd., trade name), AEROSIL NA50H, RA200H, RA200HS (above are Japan AEROSIL (Stock) Manufacturing, trade name) etc.

In the water repellent composition of this embodiment, additives and the like may be added as needed. Examples of additives include other water repellents, surfactants, defoamers, pH adjusters, antibacterial agents, antifungal agents, colorants, antioxidants, deodorants, various organic solvents, chelating agents, and antistatic agents , Catalyst, cross-linking agent, antibacterial deodorant, flame retardant, softener, anti-wrinkle agent, etc.

As the surfactant, well-known nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used. A surfactant may be used individually by 1 type, or may be used in combination of 2 or more types.

Examples of defoamers include fat-based defoamers such as castor oil, sesame oil, linseed oil, animal and vegetable oils; fatty acid-based defoamers such as stearic acid, oleic acid, and palmitic acid; isoamyl stearate, amber Fatty acid ester defoamers such as distearic acid distearate, ethylene glycol distearate, butyl stearate, etc.; polyoxyalkylene monohydric alcohol (monohydric alcohol), di-tertiary amylphenoxy Alcohol defoamers such as ethanol, 3-heptanol and 2-ethylhexanol; di-tertiary pentyl phenoxy ethanol, 3-heptyl cellosolve, nonyl cellosolve, 3-heptyl card Ether-based defoamers such as ethanol; phosphate-based defoamers such as tributyl phosphate and tris(butoxyethyl) phosphate; amine-based defoamers such as dipentylamine; polyalkylene amine, Amide-based defoamers such as amide polyamines; sulfate-based defoamers such as sodium lauryl sulfate; mineral oil, etc. A defoamer may be used individually by 1 type, or may be used in combination of 2 or more types.

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, and nitric acid. , Phosphoric acid, boric acid and other inorganic acids; sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonia, alkanolamine, pyridine, pyridine and other alkalis. The pH adjusting agent may be used alone or in combination of two or more kinds.

Examples of organic solvents 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, etc. Ethyl 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 , Diisopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, dioxane, methyl tertiary butyl ether, butyl carbitol and other ethers; ethylene glycol, diethyl 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 mono Glycol ethers such as methyl ether and 3-methoxy-3-methyl-1-butanol; ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetic acid Glycol esters such as esters; amides such as formamide, acetamide, benzamide, N,N-dimethylformamide, and acetaniline. An organic solvent can be used individually by 1 type or in combination of 2 or more types.

As the antistatic agent, it is preferable to use one that hardly inhibits water repellency. Examples of antistatic agents include cationic surfactants such as higher alcohol sulfate ester salts, sulfated oils, sulfonates, quaternary ammonium salts, imidazoline type quaternary salts, polyethylene glycol type, and polyol ester type. Nonionic surfactants, imidazoline type quaternary salt, amphoteric surfactants such as alanine type, betaine type, high molecular compound type electropolymer, polyalkylamine, etc. An antistatic agent can be used individually by 1 type or in combination of 2 or more types.

Next, the manufacturing method of the water repellent composition of this embodiment is demonstrated.

The composition containing the non-fluorine-based polymer (α) can be produced by a radical polymerization method. Furthermore, in the radical polymerization method, in terms of the performance and environment of the obtained water repellent, it is preferable to perform polymerization by an emulsion polymerization method or a dispersion polymerization method.

For example, the non-fluorine-based polymer (α) can be obtained by subjecting the (A1) component and (A2) component to emulsion polymerization or dispersion polymerization in a medium. More specifically, for example, the (A1) component, (A2) component, and optionally (B) component, (C) component and (D) component, and emulsification adjuvant or dispersion adjuvant are added to the medium, and the The mixed liquid is emulsified or dispersed to obtain an emulsion or dispersion. The polymerization reaction can be started by adding a polymerization initiator to the obtained emulsion or dispersion, and the monomer and the reactive emulsifier can be polymerized. Furthermore, as a method of emulsifying or dispersing the above-mentioned mixed liquid, a homomixer, a high-pressure emulsifier, an ultrasonic wave, and the like can be cited.

As the above-mentioned emulsification adjuvant or dispersion adjuvant (hereinafter also referred to as "emulsification adjuvant etc."), in addition to the above-mentioned reactive emulsifier (B), a nonionic surfactant, a cationic surfactant, One or more of anionic surfactants and amphoteric surfactants. The content of the emulsification adjuvant and the like is preferably 0.5 to 30 parts by mass relative to 100 parts by mass of the total monomers, more preferably 1 to 20 parts by mass, and still more preferably 1 to 10 parts by mass. If the content of the emulsification adjuvant or the like is 0.5 parts by mass or more, the dispersion stability of the mixed liquid tends to be further improved compared with the case where the content of the emulsification adjuvant or the like is less than 0.5 parts by mass. If the content of the emulsification auxiliary agent or the like is 30 parts by mass or less, the water repellency of the obtained non-fluorine-based polymer tends to be further improved compared to the case where the content of the emulsification auxiliary agent or the like exceeds 30 parts by mass.

Examples of cationic surfactants include monoalkyltrimethylammonium salts with 8-24 carbons, dialkyldimethylammonium salts with 8-24 carbons, and monoalkyls with 8-24 carbons. Amino acetates, dialkylamino acetates with 8-24 carbons, quaternary alkylimidazoline salts with 8-24 carbons, etc. Among them, from the viewpoints of emulsification and processing stability, monoalkyltrimethylammonium salts having 12 to 18 carbon atoms and dialkyldimethylammonium salts having 12 to 18 carbon atoms are preferred salt.

These cationic surfactants may be used individually by 1 type, and may be used in combination of 2 or more types.

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 alcohols include linear or branched alcohols or enols having 8 to 24 carbon atoms, and acetylenic alcohols represented by the following general formula (AL-1) or the following general formula (AL-2).

[於式中，R⁵¹ 及R⁵² 分別獨立地表示碳數為1～8之具有直鏈或者支鏈之烷基、或碳數為2～8之具有直鏈或者支鏈之烯基]。[化18]

[In the formula, R ⁵¹ and R ⁵² each independently represent a linear or branched alkyl group having 1 to 8 carbons, or a linear or branched alkenyl group having 2 to 8 carbons].

[於式中，R⁵³ 表示碳數為1～8之具有直鏈或者支鏈之烷基、或碳數為2～8之具有直鏈或者支鏈之烯基]。[化19]

[In the formula, R ⁵³ represents a linear or branched alkyl group having 1 to 8 carbons, or a linear or branched alkenyl group having 2 to 8 carbons].

Examples of polycyclic phenols include monohydric phenols such as phenol or naphthol, which may have a hydrocarbon group with 1 to 12 carbon atoms, or styrenes (styrene, α-methylstyrene, vinyl toluene, etc.). ) Adducts or other benzyl chloride reactants, etc. Examples of amines include linear or branched aliphatic amines having 8 to 44 carbon atoms.

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

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

As polyhydric alcohol fatty acid esters, a condensation reaction product of a polyhydric alcohol and a carboxylic acid having a carbon number of 2 to 30 (carbon containing a carboxyl group) can be cited. As such polyhydric alcohol fatty acid esters, for example, sorbitan esters containing sorbitol anhydride (alcohol) and a carboxylic acid having a carbon number of 2 to 30 (carbon containing a carboxyl group) and the like can be cited.

The carbon number of the carboxylic acid constituting the sorbitan ester is 2-30, preferably 5-21. The sorbitan ester may be a monocarboxylic acid ester of sorbitol anhydride and 1 carboxylic acid, a dicarboxylic acid ester of sorbitol and 2 carboxylic acids, and a tricarboxylic acid ester of sorbitol and 3 carboxylic acids, etc., preferably Monocarboxylic acid ester.

The sorbitan ester may be a compound represented by the following general formula (4) or the following general formula (5).

[於式(4)中，R⁶¹ 表示碳數為1～22之烷基或碳數為2～22之烯基，R⁶⁴ 、R⁶⁵ 及R⁶⁶ 表示氫、以-CO-R⁶¹ 表示之基、或-(CH₂ CH₂ O)_e -(R⁶² O)_f -R⁶³ (R⁶² 表示碳數為3以上之伸烷基，R⁶³ 表示氫、碳數為1～22之烷基或碳數為2～22之烯基，e表示2以上之整數，f表示0以上之整數)]。[化20]

[In the formula (4), R ⁶¹ represents an alkyl group having 1 to 22 carbons or an alkenyl group having 2 to 22 carbons, R ⁶⁴ , R ⁶⁵ and R ⁶⁶ represent hydrogen, which is represented by -CO-R ⁶¹ Group, or -(CH ₂ CH ₂ O) _e -(R ⁶² O) _f -R ⁶³ (R ⁶² represents an alkylene group with 3 or more carbons, and R ⁶³ represents hydrogen, an alkyl group with 1 to 22 carbons Or an alkenyl group having 2 to 22 carbon atoms, e represents an integer of 2 or more, and f represents an integer of 0 or more)].

[於式(5)中，R⁶¹ 表示碳數為1～22之烷基或碳數為2～22之烯基，R⁶⁴ 、R⁶⁵ 及R⁶⁶ 表示氫、以-CO-R⁶¹ 表示之基、或-(CH₂ CH₂ O)_e -(R⁶² O)_f -R⁶³ (R⁶² 表示碳數為3以上之伸烷基，R⁶³ 表示氫、碳數為1～22之烷基或碳數為2～22之烯基，e表示2以上之整數，f表示0以上之整數)]。[化21]

[In the formula (5), R ⁶¹ represents an alkyl group having 1 to 22 carbons or an alkenyl group having 2 to 22 carbons, R ⁶⁴ , R ⁶⁵ and R ⁶⁶ represent hydrogen, which is represented by -CO-R ⁶¹ Group, or -(CH ₂ CH ₂ O) _e -(R ⁶² O) _f -R ⁶³ (R ⁶² represents an alkylene group with 3 or more carbons, and R ⁶³ represents hydrogen, an alkyl group with 1 to 22 carbons Or an alkenyl group having 2 to 22 carbon atoms, e represents an integer of 2 or more, and f represents an integer of 0 or more)].

As the compound represented by the above general formula (4) or (5), for example, sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleic acid Esters, sorbitan sesquistearate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan mono Stearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan tristearate, etc.

Examples of fats and oils include vegetable fats, animal fats, vegetable waxes, animal waxes, mineral waxes, hardened oils, and the like.

Among them, from the viewpoints of less impact on water repellency, less impact on light resistance, and better emulsification of the copolymer, it is preferable that the carbon number of the straight or branched chain is 8-24 The alcohol or enol, and the alkynyl alcohol represented by the above general formula (AL-1) or the above general formula (AL-2), more preferably linear or branched alcohols with 8 to 24 carbon atoms, and The acetylenic alcohol represented by the above general formula (AL-1) or the above general formula (AL-2).

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 phenylene oxide. Ethane, epichlorohydrin, etc. From the viewpoints that the effect on water repellency is less and the emulsification of the non-fluorine-based polymer (α) becomes better, the alkylene oxide is preferably ethylene oxide or 1,2-propylene oxide, and more Preferably it is ethylene oxide.

The number of added moles of alkylene oxide is preferably 1 to 200, more preferably 3 to 100, and still more preferably 5 to 50. If the number of added moles of alkylene oxide is within the above range, it becomes easy to obtain water repellency and product stability at a high level.

In the non-fluorine-based polymer (α) of this embodiment, when a nonionic surfactant having an HLB of 7 to 18 is used as the nonionic surfactant, a better aqueous dispersion can be obtained. Here, the so-called HLB is based on Griffin's HLB, and is obtained by changing Griffin's formula to the following formula. Here, the hydrophilic group means an oxirane group. HLB=(hydrophilic group×20)/molecular weight

The HLB of the above-mentioned non-ionic surfactant used in this embodiment is 7-18. Emulsification in the composition during and after the emulsification polymerization or dispersion polymerization of the non-fluorine-based polymer (α) of this embodiment In terms of stability (hereinafter, simply referred to as emulsion stability), 9-15 are preferred. Furthermore, in terms of the 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 combination. Furthermore, from the viewpoint of emulsion stability and water repellency, it is preferable to use a cationic surfactant and a nonionic surfactant in combination.

As the medium for emulsion polymerization or dispersion polymerization, water is preferred, and water and an organic solvent may be mixed as necessary. The organic solvent at this time is not particularly limited as long as it is an organic solvent miscible with water. Examples include alcohols such as methanol or ethanol, esters such as ethyl acetate, and ketones such as acetone or methyl ethyl ketone. , Diethyl ether and other ethers, propylene glycol, dipropylene glycol, tripropylene glycol and other glycols. Furthermore, the ratio of water to organic solvent is not particularly limited.

As the polymerization initiator, known polymerization initiators such as azo-based, peroxide-based, or redox-based polymerization initiators can be suitably used. The content of the polymerization initiator is preferably 0.01 to 2 parts by mass relative to 100 parts by mass of all monomers. If the content of the polymerization initiator is in the above range, a non-fluorine-based polymer (α) having a weight average molecular weight of 30,000 or more can be produced efficiently.

In addition, in the polymerization reaction, chain transfer agents such as dodecyl mercaptan and tert-butanol can also be used for the purpose of adjusting the molecular weight. The content of the chain transfer agent is preferably 0.3 parts by mass or less with respect to 100 parts by mass of all monomers, and more preferably 0.1 parts by mass or less. When the content of the chain transfer agent is 0.3 parts by mass or less, there is a tendency that excessive decrease in molecular weight can be suppressed, and it becomes easy to efficiently produce a non-fluorine-based polymer (α) having a weight average molecular weight of 30,000 or more.

Furthermore, in order to adjust the molecular weight, a polymerization inhibitor may also be used. A non-fluorine-based polymer (α) having a desired weight average molecular weight can be easily obtained by adding a polymerization inhibitor.

The temperature of the polymerization reaction is preferably 20°C to 150°C. If the temperature is 20°C or higher, compared with the case where the temperature is less than 20°C, it tends to be easier to fully polymerize. When the temperature is 150°C or less, the control of the reaction heat becomes easier than when the temperature exceeds 150°C.

In the polymerization reaction, the weight average molecular weight of the obtained non-fluorinated polymer (α) can be adjusted by increasing or decreasing the content of the polymerization initiator, chain transfer agent, and polymerization inhibitor. The melt viscosity at 105°C is adjusted by the content of the body and the content of the polymerization initiator. Furthermore, when it is desired to reduce the melt viscosity at 105°C, it is only necessary to reduce the content of monomers having more than two polymerizable functional groups or increase the content of the polymerization initiator.

From the standpoint of the storage stability and operability of the composition, the content of the non-fluorinated polymer (α) in the polymer emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization is preferably relative to the emulsion Or the total amount of the dispersion is 10 to 50% by mass, more preferably 20 to 40% by mass.

The water repellent composition of this embodiment can be prepared by mixing a composition containing the non-fluorine-based polymer (α) obtained by the above-mentioned method and the silicone resin (β). The silicone resin (β) may be a commercially available product or the like.

The water-repellent fiber product of the present embodiment includes a fiber product to which the non-fluorine-based polymer (α) and the silicone resin (β) of the present embodiment described above are adhered.

The manufacturing method of the water-repellent fiber product of this embodiment is demonstrated.

The water-repellent fiber product of this embodiment can be obtained by treating the fiber product with a treatment liquid containing the above-mentioned water-repellent composition, thereby making the non-fluorine-based polymer (α) and the silicone resin (β) ) Attach to fiber products. The material of the fiber product is not particularly limited. Examples include natural fibers such as cotton, linen, silk, and wool, semi-synthetic fibers such as rayon, and acetate; nylon, polyester, polyurethane, polypropylene, etc. Synthetic fibers and such composite fibers, blended fibers, etc. The form of the fiber product can also be any form such as fiber, yarn, cloth, non-woven fabric, and paper.

As a method of treating the fiber product with the above-mentioned treatment liquid, for example, processing methods such as dipping, spraying, and coating can be cited. Moreover, when the water-repellent composition contains water, it is preferable to dry it in order to remove water after adhering to a fiber product.

The adhesion amount of the water repellent composition to the fiber product can be appropriately adjusted according to the required degree of water repellency, but from the viewpoint of water repellency and texture, it is preferable to use the non-fluorine-based compound contained in the water repellent composition The total adhesion amount of the polymer (α) and the silicone resin (β) is adjusted to be 0.01 to 10 g per 100 g of the fiber product, and more preferably to be 0.05 to 5 g.

In addition, after the non-fluorine-based polymer (α) and silicone resin (β) of the present embodiment are attached to the fiber product, it is preferable to appropriately perform a heat treatment. The temperature conditions are not particularly limited. If the water-repellent composition of this embodiment is used, the fiber product can exhibit sufficiently good water repellency under mild conditions of 100 to 130°C. The temperature condition can also be a high-temperature treatment of 130°C or more (preferably up to 200°C). In this case, the treatment time can be shortened compared to the previous case using a fluorine-based water repellent. Therefore, according to the water-repellent fiber product of this embodiment, it is possible to suppress the deterioration of the fiber product due to heat, the texture of the fiber product becomes soft during the water-repellent treatment, and the fiber can be treated under mild heat treatment conditions, that is, under low-temperature curing conditions. The product imparts sufficient water repellency.

In particular, when it is desired to improve the durable water repellency, it is preferable to include the above-mentioned steps of treating the fiber product with a treatment liquid containing a water repellent composition, and to make melamine resin, glyoxal resin, and One or more isocyanate groups or blocked isocyanate groups are represented by a cross-linking agent attached to the fiber product and the fiber product is heated for water-repellent processing. Furthermore, when it is desired to further improve the durable water repellency, the water-repellent composition preferably contains a non-fluorine-based polymer (α) obtained by copolymerizing a monomer having a functional group capable of reacting with the crosslinking agent.

As the melamine resin, a compound having a melamine skeleton can be used, for example, polymethylol melamine such as trimethylol melamine and hexamethylol melamine; part or all of the methylol groups of polymethylol melamine have a carbon number of Alkoxymethyl alkoxymethyl melamine of 1 to 6 alkyl groups; polymethylol melamine in which part or all of the methylol groups become oxymethyl groups with 2 to 6 carbon atoms Acetoxymethyl melamine and the like. These melamine resins may be any of monomers or polymers of dimers or more, or a mixture of these may also be used. Furthermore, a part of melamine co-condensed with urea etc. can also be used. Examples of such melamine resins include Beckamine APM, Beckamine M-3, Beckamine M-3(60), Beckamine MA-S, Beckamine J-101, and Beckamine J-101LF, Union Chemical Industries manufactured by DIC Co., Ltd. Unicar resin 380K manufactured by Co., Ltd., Riken resin MM series manufactured by Miki Riken Industry Co., Ltd., etc.

As the glyoxal resin, previously known ones can be used. Examples of the glyoxal resin include 1,3-dimethylglyoxal urea resin, dimethylol dihydroxy ethylidene resin, dimethylol dihydroxy ethylidene resin, and the like. The functional groups of these resins can also be substituted by 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 Co., Ltd. NS-200, Beckamine NF-3, Uniresin GS-20E manufactured by Union Chemical Industry Co., Ltd., Riken resin RG series manufactured by Miki Riken Industry Co., Ltd., and Riken resin MS series, etc.

From the viewpoint of promoting the reaction, it is preferable to use a catalyst in the melamine resin and the glyoxal resin. Such catalysts are not particularly limited as long as they are commonly used catalysts. Examples include fluoroboride compounds such as ammonium borofluoride and borofluoride salts; neutral metal salt catalysts such as magnesium chloride and magnesium sulfate; Inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, etc. In these catalysts, organic acids such as citric acid, tartaric acid, malic acid, maleic acid, lactic acid, etc. can also be used as auxiliary catalysts. As such a catalyst, for example, Catalyst ACX, Catalyst 376, Catalyst O, Catalyst M, Catalyst G (GT), Catalyst X-110, Catalyst GT-3, and Catalyst NFC-1, Union manufactured by DIC Co., Ltd. Unicar Catalyst 3-P and Unicar Catalyst MC-109 manufactured by Chemical Industry Co., Ltd., Riken fixer RC series, Riken fixer MX series, and Riken fixer RZ-5 manufactured by Miki Riken Industry Co., Ltd.

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

As a polyfunctional isocyanate compound, if it is a compound which has 2 or more isocyanate groups in a molecule|numerator, it will not specifically limit, A well-known polyisocyanate compound can be used. Examples of polyfunctional isocyanate compounds include diisocyanate compounds such as alkylene diisocyanates, aryl diisocyanates, and cycloalkyl diisocyanates, and modified polyisocyanate compounds such as dimers or trimers of these diisocyanate compounds. . The carbon number of the alkylene diisocyanate is preferably 1-12.

As the diisocyanate compound, for example, 2,4 or 2,6-toluene diisocyanate, ethylene diisocyanate, propylene diisocyanate, 4,4-diphenylmethane diisocyanate, p-phenylene diisocyanate, tetramethylene diisocyanate Isocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, benzene diisocyanate, toluene Diisocyanate or naphthalene diisocyanate, 4,4'-methylene-bis(phenyl isocyanate), 2,4'-methylene-bis(phenyl isocyanate), 3,4'-methylene Group-bis(phenyl isocyanate), 4,4'-ethylene-bis(phenyl isocyanate), ω,ω'-diisocyanato-1,3-dimethylbenzene, ω ,ω'-diisocyanato-1,4-dimethylcyclohexane, ω,ω'-diisocyanato-1,4-dimethylbenzene, ω,ω'-diisocyanate -1,3-dimethylcyclohexane, 1-methyl-2,4-diisocyanate cyclohexane, 4,4'-methylene-bis(cyclohexyl isocyanate), 3-isocyanate -Methyl-3,5,5-trimethylcyclohexyl isocyanate, acid-diisocyanate dimer, ω,ω'-diisocyanate diethylbenzene, ω,ω'-diisocyanate dimethyltoluene, ω ,ω'-diisocyanate diethyl toluene, fumarate bis(2-isocyanatoethyl) ester, 1,4-bis(2-isocyanato-prop-2-yl)benzene, And 1,3-bis(2-isocyanato-prop-2-yl)benzene.

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

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

A polyfunctional isocyanate compound can be used individually by 1 type or in combination of 2 or more types.

The isocyanate group possessed by the polyfunctional isocyanate compound may be in its original form or 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-bromo Pyrazoles such as pyrazole and pyrazole; phenols such as phenol, methyl phenol, chlorophenol, isobutyl phenol, tertiary butyl phenol, isoamyl phenol, octyl phenol, nonyl phenol, etc.; ε-hexyl Endoamides, δ-valerolactam, γ-butyrolactamide and other internal amines; dimethyl malonate, diethyl malonate, acetone, methyl acetylacetate, and acetic acid Active methylene compounds such as ethyl ester; Oximes such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime; imidazole, 2- Imidazole compounds such as methylimidazole; sodium bisulfite, etc. Among them, 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 impart an interfacial effect. Furthermore, in order to promote the reaction, known catalysts such as organotin and organozinc may be used in combination.

A crosslinking agent or a catalyst can be used individually by 1 type or in combination of 2 or more types.

The crosslinking agent can be attached to the object to be treated by the following method: for example, the object to be treated (fiber product) is immersed in a treatment liquid prepared by dissolving the crosslinking agent in an organic solvent or emulsified and dispersed in water. The treatment liquid of the material is dried. Furthermore, by heating the crosslinking agent attached to the object to be processed, the reaction between the crosslinking agent, the object to be processed and the non-fluorine-based polymer (α) can be promoted. In order to fully promote the reaction of the crosslinking agent and effectively improve the washing durability, the heating at this time is preferably carried out at 110 to 180°C for 1 to 5 minutes. The steps of attaching and heating the crosslinking agent can also be performed simultaneously with the step of treating with the treatment liquid containing the above-mentioned water repellent composition. In the case of simultaneous execution, for example, after the treatment liquid containing the water-repellent composition and the crosslinking agent is attached to the object to be treated and the water is removed, the crosslinking agent attached to the object is further heated. In consideration of the simplification of the water repellent processing step, the reduction of heat, and the economic efficiency, it is preferably carried out simultaneously with the processing step of the water repellent composition.

In addition, if the crosslinking agent is used excessively, the texture may be damaged. The above-mentioned crosslinking agent is preferably used in an amount of 0.1 to 50% by mass, and particularly preferably used in an amount of 0.1 to 10% by mass with respect to the object to be processed (fiber product).

The water-repellent fiber product of this embodiment obtained in this way can also fully exhibit its water-repellency even when it is used outdoors for a long time. Moreover, the water-repellent fiber product does not use fluorine compounds, so it can be made environmentally friendly. By.

The water-repellent fiber product of this embodiment can be coated on a predetermined part. Examples of coating processing include moisture-permeable and waterproof processing or wind-proof processing for sports or outdoor use. As a processing method, for example, in the case of moisture-permeable and water-repellent processing, the processing can be carried out by applying a coating solution containing urethane resin or acrylic resin and the like to the water-repellent fiber One side of the product is dried.

As mentioned above, although the preferable embodiment of this invention was described, this invention is not limited to the said embodiment.

For example, in the case of manufacturing the non-fluorine-based polymer (α) included in the water repellent composition of the present invention, the above-mentioned embodiment adopts radical polymerization to carry out the polymerization reaction, but it can also be carried out by irradiation such as ultraviolet rays and electrons. The polymerization reaction is carried out by photopolymerization of ionizing radiation such as beams, gamma rays, etc.

Furthermore, in the present invention, the fiber product is treated with the water-repellent composition to form a water-repellent fiber product. However, as a product treated with the water-repellent composition, it is not limited to the use of fiber products, and may be metal or glass. , Resin and other items.

In this case, the method of attaching the water-repellent composition to the above-mentioned article and the amount of the water-repellent agent can be arbitrarily determined according to the type of the object to be treated, etc. Example

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

<Preparation of polymer dispersion> The mixed solution having the composition shown in Tables 1 and 2 (in the table, the numerical value represents (g)) was polymerized in the order shown below to obtain a dispersion liquid of a polymer or a hydrophobic compound.

(Synthesis example 1) Put 23.4 g of stearyl acrylate, 0.6 g of diacetone acrylamide, and Noigen XL-100 (manufactured by First Industrial Pharmaceutical Co., Ltd., polyoxyalkylene branched decyl ether, HLB=14.7) in the autoclave. g, Noigen XL-60 (manufactured by First Industrial Pharmaceutical Co., Ltd., polyoxyalkylene branched decyl ether, HLB=12.5) 1.3 g, Noigen XL-40 (manufactured by First Industrial Pharmaceutical Co., Ltd., polyoxyethylene Alkyl branched decyl ether, HLB=10.5) 0.5 g, 0.4 g of stearyl trimethylammonium sulfate, 12.5 g of tripropylene glycol, and 54.9 g of water were mixed and stirred at 45°C to prepare a mixed solution. The mixed liquid is irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.2 g of azobis(isobutylamidine) dihydrochloride was added to the mixed solution, and under a nitrogen environment, 6 g of vinyl chloride was continuously pressed into the autoclave to maintain the internal pressure of the autoclave at 0.3 MPa, and at 60 Radical polymerization was carried out at ℃ for 6 hours to obtain a non-fluorine-based polymer (α) dispersion containing 30.0% by mass of the non-fluorine-based polymer (α).

(Synthesis example 2-8) Except that the materials described in Table 1 were used, polymerization was carried out in the same manner as in Synthesis Example 1 to obtain non-fluorine-based polymer (α) dispersion liquids each containing 30.0% by mass of the non-fluorine-based polymer (α).

(Comparative synthesis examples 1 to 5) Except for using the materials described in Table 2, polymerization was carried out in the same manner as in Synthesis Example 1, and other non-fluorine-based polymer dispersions containing 30.0% by mass of other non-fluorine-based polymers were obtained.

(Comparative Synthesis Example 6) Put 240.3 g of 1,4-butanediol, 758.5 g of stearic acid and 1.2 g of p-toluenesulfonic acid in a 1000 mL flask, and carry out dehydration reaction at 130～200℃ for 4 hours under nitrogen flow to obtain the product Things. The acid value and hydroxyl value of the obtained product were measured, and the acid value was 0.5 mgKOH/g and the hydroxyl value was 162.1 mgKOH/g. Put 574.1 g of the above product, 270.5 g of hexamethylene diisocyanate and 0.9 g of a bismuth catalyst (Nitto Kasei Co., Ltd., Neostan U-600) into another container, and perform the treatment at 80°C for 3 hours reaction. The reaction proceeds until the NCO% becomes 8.0. After the reaction, the temperature was lowered to 40°C, then 154.6 g of 3,5-dimethylpyrazole was put in, and the reaction was performed at 40°C for 1 hour to obtain a hydrophobic compound. Put the obtained hydrophobic compound 40 g, methyl ethyl ketone 50 g, Decaglyn 1-L (nonionic surfactant, manufactured by Daiichi Industrial Pharmaceutical) 5 g, Decaglyn 1-SV in a 500 mL stainless steel container (Non-ionic surfactant, manufactured by Daiichi Kogyo Pharmaceutical) 5 g and Arquad T-28 (cationic surfactant, manufactured by Lion Specialty Chemicals) 5 g, heated to 50°C to dissolve. Then, 295 g of hot water at 80°C was added, and an ultrasonic emulsification machine US-600E (Nippon Seiki Seisakusho Co., Ltd.) was used to emulsify for 20 minutes while maintaining 80°C. After that, cooling is performed to obtain a 10% dispersion of the hydrophobic compound.

[Table 1] Synthesis example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Monomer (A1) Stearyl Acrylate 23.4 23.4 29.4 - - 23.4 22.8 20.4 Lauryl Acrylate - - - 23.4 - - - - Behenyl acrylate - - - - 23.4 - - - Monomer (A2) Diacetone acrylamide 0.6 0.6 0.6 0.6 0.6 - 0.6 0.6 2-methacrylic acid [2-(2-oxo-2-imidazolidinyl) ethyl ester] - - - - - 0.6 0.6 - Monomer (C) Decyl acrylate - - - - - - - - 2-hydroxyethyl acrylate - - - - - - - - Diethylaminoethyl methacrylate - - - - - - - - Isomethacrylate - - - - - - - 3 Monomer (D) Styrene - - - - - - - - Monomer (VC) Vinyl chloride 6 - - 6 6 6 6 6 Vinylidene Chloride - 6 - - - - - - Emulsifier (nonionic surfactant) (HLB) Noigen XL-100 (14.7) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Noigen XL-60 (12.5) 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 Noigen XL-40 (10.5) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Emulsification auxiliary Stearyl Trimethyl Ammonium Sulfate 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 medium Tripropylene glycol 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 water 54.9 54.9 54.9 54.9 54.9 54.9 54.3 54.9 Initiator Azobis(isobutylamidine) dihydrochloride 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2

[Table 2] Comparative Synthesis Example 1 Comparative Synthesis Example 2 Comparative Synthesis Example 3 Comparative Synthesis Example 4 Comparative Synthesis Example 5 Monomer (A1) Stearyl Acrylate twenty four 23.4 23.4 - 23.7 Lauryl Acrylate - - - - - Behenyl acrylate - - - - - Monomer (A2) Diacetone acrylamide - - - 0.6 - 2-methacrylic acid [2-(2-oxo-2-imidazolidinyl) ethyl ester] - - - - - Monomer (C) Decyl acrylate - - - twenty four - 2-hydroxyethyl acrylate - 0.6 - - 0.3 Diethylaminoethyl methacrylate - - 0.6 - - Isomethacrylate - - - - - Monomer (D) Styrene - - - - 6 Monomer (VC) Vinyl chloride 6 6 6 6 - Vinylidene Chloride - - - - - Emulsifier (nonionic surfactant) (HLB) Noigen XL-100 (14.7) 0.2 0.2 0.2 0.2 0.2 Noigen XL-60 (12.5) 1.3 1.3 1.3 1.3 1.3 Noigen XL-40 (10.5) 0.5 0.5 0.5 0.5 0.5 Emulsification auxiliary Stearyl Trimethyl Ammonium Sulfate 0.4 0.4 0.4 0.4 0.4 medium Tripropylene glycol 12.5 12.5 12.5 12.5 12.5 water 54.9 54.9 54.9 54.3 54.3 Initiator Azobis(isobutylamidine) dihydrochloride 0.2 0.2 0.2 0.2 0.2

Furthermore, each polymer in the polymer dispersion obtained in Synthesis Examples 1 to 8 and Comparative Synthesis Examples 1 to 5 was confirmed by gas chromatography (GC-15APTF, manufactured by Shimadzu Corporation) More than 98% of all monomers are polymerized.

The details of the materials shown in Tables 1 and 2 are as follows. Noigen XL-100 (14.7) (manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., polyoxyalkylene branched decyl ether, HLB=14.7) Noigen XL-60(12.5) (manufactured by First Industrial Pharmaceutical Co., Ltd., polyoxyalkylene branched decyl ether, HLB=12.5) Noigen XL-40(10.5) (manufactured by First Industrial Pharmaceutical Co., Ltd., polyoxyalkylene branched decyl ether, HLB=10.5)

＜Preparation of dispersion liquid containing polysiloxane resin＞ (Preparation Example 1) Mix 20 parts by mass of SF 8416 (alkyl-modified polysiloxane, manufactured by Toray Dow Corning Co., Ltd., trade name) as a silicone resin, SPAN60 (sorbitan-based nonionic surfactant, HLB=4.7, Kao (Stock) Manufacturing) 1 part by mass, TWEEN80 (Sorbitan anhydride-based nonionic surfactant, HLB=15.0, manufactured by Kao Corporation) 1 part by mass, and 5 parts by mass of diethylene glycol butyl ether. Next, 73.0 parts by mass of water was added little by little to the obtained mixture and mixed to obtain a dispersion liquid containing 20% by mass of polysiloxane resin (β).

(Preparation examples 2～4) The following resin was used as the silicone resin, except that it was the same as Preparation Example 1 to obtain a silicone resin dispersion containing 20% by mass of the silicone resin. (Preparation Example 2) BY 16-872 (aminopolysiloxane, manufactured by Toray Dow Corning Co., Ltd., trade name) (Preparation Example 3) KF-9901 (methyl hydrogen polysiloxane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) (Preparation Example 4) KF-96-3000cs (Dimethicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name)

(Preparation Example 5) Mixed KF8005 (amino-modified polysiloxane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 18.5 parts by mass, 0.15 parts by mass formic acid, and 5 moles of ethylene oxide with branched alcohols with 12 to 14 carbon atoms The adduct is 0.5 parts by mass. Next, 80.85 parts by mass of water was added little by little to the obtained mixture and mixed to obtain a dispersion liquid containing 18.5% by mass of the amino-modified silicone.

Add dimethyl polysiloxane (6cs, Toray Dow Corning) to 15 parts by mass of MQ-1600 (polysiloxane resin = trimethylsilyl-containing polysiloxane, manufactured by Toray Dow Corning Co., Ltd., trade name) (Stock) Manufacturing, trade name) 15 parts by mass, and mixed until the silicone resin is dissolved to obtain a mixture. 18.5 parts by mass of the obtained mixture and 0.5 parts by mass of the 5 mol adduct of ethylene oxide of a branched alcohol having 12 to 14 carbon atoms were mixed. Next, 81 parts by mass of water was added little by little and mixed to obtain a dispersion liquid containing a total of 18.5% by mass of polysiloxane resin and dimethyl polysiloxane.

Mix the above-mentioned amine modified polysiloxane dispersion with the dispersion containing polysiloxane resin and dimethyl polysiloxane at a ratio of 100:117 to obtain 9.2:5.4:5.4 containing amine modification by mass ratio A 20% by mass polysiloxane resin dispersion of polysiloxane, polysiloxane resin, and dimethyl polysiloxane is used as polysiloxane resin (β).

<Preparation of water repellent composition> (Examples 1-15, Comparative Examples 1-9) Mix the non-fluorine-based polymer (α) dispersion, other non-fluorine-based polymer dispersions, or hydrophobic compound dispersions so as to have the composition shown in Tables 3 to 5 (in the table, the numerical value is represented by (mass%)) Liquid, a silicone resin (β) dispersion liquid and water to obtain a water repellent composition.

(Evaluation of water repellency of fiber products) According to the spray method of JIS L 1092 (2009), the shower water temperature was set to 20°C and tested. In this test, the dyed polyester 100% fabric or polyester (PET)/polyurethane (PU) blended fabric (polyester/polyurethane=80/20) will be implemented The water repellent composition of the Examples and Comparative Examples was immersed in the water-repellent composition, dried at 130°C for 2 minutes, and then heat-treated at 170°C for 30 seconds to evaluate the water repellency of the obtained cloth. The results are evaluated by visual inspection according to the following grades. In addition, when the characteristics are slightly good, attach a "+" to the level, and when the characteristics are slightly poor, attach a "-" to the level. The results are shown in Tables 3 to 5. Water repellency: state 5: No wetness attached to the surface 4: The surface shows slightly adhered and wet ones 3: The surface partially shows wetness 2: The surface exhibits wetness 1: The overall surface is wet 0: Fully wet on the front and back

(Texture evaluation of fiber products) The texture is evaluated using the following: After immersing the dyed polyester 100% cloth in the treatment liquid of the water repellent composition of the examples and comparative examples, drying at 130°C for 2 minutes, and then Heat treatment at 170°C for 30 seconds. The results are evaluated according to the 5 levels shown below by operation. The results are shown in Tables 3 to 5. 1: Harder～5: Soft

(Evaluation of Durable Water Repellency of Fiber Products) According to the spray method of JIS L 1092 (2009), the shower water temperature was set to 20°C for the test. In the water-repellent composition of the Examples and Comparative Examples, a blocked isocyanate-based crosslinking agent (NK assist NY-50) was added so as to have a concentration of 0.03% by mass to prepare a treatment liquid. Next, the dyed polyester 100% cloth is immersed in the prepared treatment solution. After the immersion treatment, it was dried at 130°C for 2 minutes, and the cloth (L-0) obtained by heat treatment at 170°C for 60 seconds was evaluated in the same manner as the above water repellency evaluation method (L-0), and 30 times (L- 30) The water repellency of the cloth after washing in the 103 method of JIS L 0217 (1995). In addition, in the case of polyester (PET)/polyurethane (PU) blended fabric (polyester/polyurethane=80/20), except for changing the heat treatment temperature from 170°C to 160°C Other than that, the evaluation was performed in the same manner as in the case of 100% polyester cloth. The results are shown in Tables 3 to 5.

(Peel strength of fiber products to coating) According to JIS K 6404-5 (1999) test. In this test, the fabric obtained in the following manner was used as the base fabric: After immersing the dyed nylon 100% fabric in the water repellent composition of the Examples and Comparative Examples, it was dried at 130°C 2 Minutes, and then heat treatment at 170°C for 30 seconds. Use a thermo-compression bonding device to heat-bond the hot melt adhesive tape (“MELCO TAPE” manufactured by Sun Kasei Co., Ltd.) at 105°C to the obtained base fabric for 1 minute, using an automatic stereograph (AG-IS, Shimadzu Corporation (manufactured by Shimadzu Corporation) measured the peel strength between the base fabric and the seam tape. Pull the moving speed of the gripper at 100 mm/min, and set the average value of the stress as the peel strength [N/inch]. The results are shown in Tables 3 to 5.

(Evaluation of moisture resistance of fiber products) In accordance with the spray method of JIS L 1092 (2009), the shower water temperature was set to 20°C for testing, and the water repellency of the spray was confirmed by visual inspection, and evaluated according to the following 5 levels. In this test, the dyed polyester/polyurethane blended fabric (polyester/polyurethane=80/20) is used in the water repellent composition of the examples and comparative examples After the immersion treatment, it was dried at 130°C for 2 minutes, and then heat-treated at 170°C for 30 seconds to evaluate the wetting resistance of the obtained cloth. In addition, when the characteristics are slightly good, attach a "+" to the level, and when the characteristics are slightly poor, attach a "-" to the level. The results are shown in Tables 3 to 5. Wetting resistance: state 5: The water in contact with the cloth remains in the form of tiny droplets, and the water jumps from the surface of the cloth 4: The water in contact with the cloth remains in the form of tiny droplets, rolling off the surface of the cloth 3: The water in contact with the cloth remains in the shape of a large droplet, rolling off the surface of the cloth 2: The water in contact with the cloth does not keep the shape of drops, and it immediately falls off the surface of the cloth 1: The water in contact with the cloth does not retain water droplets, one side meanders and the other side gradually drops

(Scratch evaluation of fiber products) Scratch marks are evaluated using the following: After immersing dyed polyester 100% cloth in the water repellent composition of the Examples and Comparative Examples, drying at 130°C for 2 minutes, and then at 170°C After 30 seconds of heat treatment. Scratch the surface of the processed cloth with your nails, and visually evaluate it according to the following 5 levels. The results are shown in Tables 3 to 5. 5: Obvious nail marks are confirmed 4: Nail marks are confirmed 3: Fewer nail marks are confirmed 2: Nail marks are hardly confirmed 1: No nail marks

[table 3] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Non-fluorine-based polymer (α) Synthesis example 1 0.24 0.12 2.4 1.2 0.24 0.24 0.24 0.15 Synthesis Example 2 - - - - - - - - Synthesis Example 3 - - - - - - - - Synthesis Example 4 - - - - - - - - Synthesis Example 5 - - - - - - - - Synthesis Example 6 - - - - - - - - Synthesis Example 7 - - - - - - - - Synthesis Example 8 - - - - - - - - Other non-fluorine-based polymers Comparative Synthesis Example 1 - - - - - - - - Comparative Synthesis Example 2 - - - - - - - - Comparative Synthesis Example 3 - - - - - - - - Comparative Synthesis Example 4 - - - - - - - - Comparative Synthesis Example 5 - - - - - - - - Hydrophobic compound Comparative Synthesis Example 6 - - - - - - - - Silicone resin (β) Preparation Example 1 0.06 0.06 0.6 0.6 - - - - Preparation Example 2 - - - - 0.06 - - - Preparation Example 3 - - - - - 0.06 - - Preparation Example 4 - - - - - - 0.06 - Preparation Example 5 - 0.12 1.2 - - - 0.15 Water repellency (polyester) Wash 0 times (L-0) 5 5 5 5 5 5 4+ 5 Wash 30 times (L-30) 4+ 4+ 5 5 4 4 4 4 Water repellency (PET/PU) Wash 0 times (L-0) 5 5 5 5 5 4+ 4+ 4 Wash 30 times (L-30) 5 4+ 5 5 4 4 4- 4- Wetting resistance (PET/PU) Wash 0 times (L-0) 5 5 5 5 4 3 3 4 Peel strength N/inch 15.6 15.0 15.6 15.0 13.6 15.1 15.3 14.8 Texture (polyester) 4 5 3 4 5 4 4 5 Scratches (polyester) 4 5 3 4 4 5 5 5

[Table 4] Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Comparative example 1 Non-fluorine-based polymer (α) Synthesis example 1 - - - - - - - - Synthesis Example 2 0.24 - - - - - - - Synthesis Example 3 - 0.24 - - - - - - Synthesis Example 4 - - 0.24 - - - - - Synthesis Example 5 - - - 0.24 - - - - Synthesis Example 6 - - - - 0.24 - - - Synthesis Example 7 - - - - - 0.24 - - Synthesis Example 8 - - - - - - 0.24 - Other non-fluorine-based polymers Comparative Synthesis Example 1 - - - - - - - 0.24 Comparative Synthesis Example 2 - - - - - - - - Comparative Synthesis Example 3 - - - - - - - - Comparative Synthesis Example 4 - - - - - - - - Comparative Synthesis Example 5 - - - - - - - - Hydrophobic compound Comparative Synthesis Example 6 - - - - - - - - Silicone resin (β) Preparation Example 1 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 Preparation Example 2 - - - - - - - - Preparation Example 3 - - - - - - - - Preparation Example 4 - - - - - - - - Preparation Example 5 - - - - - - - - Water repellency (polyester) Wash 0 times (L-0) 5 5 4 5 5- 5- 5 3+ Wash 30 times (L-30) 4 4 3- 4+ 4 4+ 4+ 1 Water repellency (PET/PU) Wash 0 times (L-0) 5 4+ 4 4+ 5- 5- 5 3 Wash 30 times (L-30) 4 4 3- 4 4 4+ 4+ 1 Wetting resistance (PET/PU) Wash 0 times (L-0) 5 4 3 4 4 5 5 2 Peel strength N/inch 13.5 5.3 15.4 15.5 15.0 15.1 16.5 14.8 Texture (polyester) 4 5 4 4 4 4 3 3 Scratches (polyester) 4 4 5 4 4 4 4 4

[table 5] Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8 Comparative example 9 Non-fluorine-based polymer (α) Synthesis example 1 - - - - - 0.3 - 0.12 Synthesis Example 2 - - - - - - - - Synthesis Example 3 - - - - - - - - Synthesis Example 4 - - - - - - - - Synthesis Example 5 - - - - - - - - Synthesis Example 6 - - - - - - - - Synthesis Example 7 - - - - - - - - Synthesis Example 8 - - - - - - - - Other non-fluorine-based polymers Comparative Synthesis Example 1 2.4 - - - - - - - Comparative Synthesis Example 2 - 0.24 - - - - - - Comparative Synthesis Example 3 - - 0.24 - - - - - Comparative Synthesis Example 4 - - - 0.24 - - - - Comparative Synthesis Example 5 - - - - 0.3 - - - Hydrophobic compound Comparative Synthesis Example 6 - - - - - - - 0.18 Silicone resin (β) Preparation Example 1 0.6 0.06 0.06 0.06 - - 0.3 - Preparation Example 2 - - - - - - - - Preparation Example 3 - - - - - - - - Preparation Example 4 - - - - - - - - Preparation Example 5 - - - - - - - - Water repellency (polyester) Wash 0 times (L-0) 5 3 3 1 2 3 1 2+ Wash 30 times (L-30) 4 2 1 1 1 2 1 1 Water repellency (PET/PU) Wash 0 times (L-0) 5 3 3 1 2- 3 1 2+ Wash 30 times (L-30) 4 2 1 1 1 2 1 1 Wetting resistance (PET/PU) Wash 0 times (L-0) 5 2 2 1 1 2 1 1 Peel strength N/inch 14.8 13.6 14.6 14.5 5.8 15.2 5.2 4.5 Texture (polyester) 1 2 3 3 2 2 3 3 Scratches (polyester) 4 1 3 2 2 1 2 2

Claims (4)

A water repellent composition comprising: a non-fluorine-based polymer (α) containing a structural unit derived from a (meth)acrylate monomer (A1) represented by the following general formula (A-1) and derived from The structural unit of the compound (A2) represented by the general formula (A-2); and polysiloxane resin (β); [化1]

[In the formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 to 30 carbon atoms that may have a substituent] [Chemical 2]

[In formula (A-2), R ¹¹ represents hydrogen or methyl, R ¹² represents a divalent hydrocarbon group with a carbon number of 1 to 6, Z represents an ester group or an amide group, and W represents -CO-R ¹³ (In the formula, R ¹³ represents a monovalent hydrocarbon group with 1 to 4 carbon atoms), a group represented by -NH-CO-NH ₂ or a group represented by the following formula (A-3), [化3]

]. The water repellent composition of claim 1, wherein the non-fluorine-based polymer (α) further contains a structural unit derived from at least one monomer (VC) of vinyl chloride and vinylidene chloride. A water-repellent fiber product comprising a fiber product to which the water-repellent composition of claim 1 or 2 is attached A method for manufacturing a water-repellent fiber product, which includes a step of treating the fiber product with a treatment liquid containing the water-repellent composition of claim 1 or 2.