JP2022081600A - Water repellent assistant, non-fluorine-based water repellent composition and manufacturing method of water repellent fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water repellent assistant capable of enhancing durable water repellency of a non-fluorine-based water repellent.

SOLUTION: A water repellent assistant for non-fluorine-based water repellent contains organo modified silicone represented by the following general formula (1), where R²⁰, R²¹ and R²² represent each independently a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms, R²³ represents a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring or an alkyl group having 3 to 22 carbon atoms, R³⁰, R³¹, R³², R³³, R³⁴ and R³⁵ represent each independently a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon groups, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring or an alkoxy group having 3 to 22 carbon atoms, a represents an integer of 0 or more, b represents an integer of 1 or more and (a+b) is 10 to 200.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a water repellent aid, a non-fluorine water repellent composition, and a method for producing a water repellent fiber product.

Conventionally, a fluorine-based water repellent agent having a fluorine-containing group is known, and a textile product having a water-repellent surface imparted to the surface of a textile product or the like by treating the fluorine-based water repellent agent is known. .. Such a fluorine-based water repellent is generally produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group.

Although textile products treated with a fluorine-based water repellent exhibit excellent water repellency, it is necessary to adjust the orientation of the fluoroalkyl group in order to develop water repellency. After the agent is attached, the heat treatment must be performed at a temperature exceeding 130 ° C. However, heat treatment at high temperature requires high energy, and there is a problem in the international trend of energy saving.

Further, the monomer having a fluoroalkyl group is not economically satisfactory because it is expensive, and further, the monomer having a fluoroalkyl group is persistent and therefore has a problem in terms of the environment. There is.

On the other hand, in the field of water-repellent processing of textile products, a water-repellent agent capable of giving excellent water repellency to textile products even at a low concentration and a low heat treatment temperature is desired in order to stabilize quality and reduce costs. ..

Therefore, in recent years, research has been conducted on non-fluorine-based water repellents that do not contain fluorine. For example, Non-Patent Document 1 discloses a water repellent agent obtained by emulsifying and dispersing a hydrocarbon compound such as paraffin or wax, a fatty acid metal salt or an alkylurea.

Further, Patent Document 1 proposes a water repellent agent obtained by emulsifying and dispersing a specific non-fluorine-based polymer for the purpose of providing water repellency comparable to that of a conventional fluorine-based water repellent agent.

"Superhydrophobic processing, the whole picture of processing agents and new trends in moisture permeable and waterproof materials", published by Osaka Chemical Marketing Center, 1996, p. 7-9

Japanese Unexamined Patent Publication No. 2006-328624

However, with conventional water repellents, durable water repellency may not be sufficiently obtained.

The present invention has been made in view of the above circumstances, and is a water-repellent aid capable of improving the durable water repellency of a non-fluorine-based water-repellent agent, and a non-fluorine-based water-repellent agent composition using the same. , And a method for producing a water repellent textile product.

The present invention provides a water-repellent aid for non-fluorine-based water-repellent agents, which comprises an organomodified silicone represented by the following general formula (1).

［式（１）中、Ｒ^２０、Ｒ^２１及びＲ^２２はそれぞれ独立に、水素原子、メチル基、エチル基又は炭素数１～４のアルコキシ基を表し、Ｒ^２３は、芳香族環を有する炭素数８～４０の炭化水素基、又は炭素数３～２２のアルキル基を表し、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４及びＲ^３５はそれぞれ独立に、水素原子、メチル基、エチル基、炭素数１～４のアルコキシ基、芳香族環を有する炭素数８～４０の炭化水素基、又は炭素数３～２２のアルキル基を表し、ａは０以上の整数を表し、ｂは１以上の整数を表し、（ａ＋ｂ）は１０～２００であり、ａが２以上の場合、複数存在するＲ^２０及びＲ^２１はそれぞれ同一であっても異なっていてもよく、ｂが２以上の場合、複数存在するＲ^２２及びＲ^２３はそれぞれ同一であっても異なっていてもよい。］

[In the 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 is a carbon having an aromatic ring. Represents a hydrocarbon group of 8 to 40 or an alkyl group of 3 to 22 carbons, where R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independent hydrogen atoms, methyl groups and ethyls, respectively. A group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 3 to 22 carbon atoms, a represents an integer of 0 or more, and b represents 1. Representing the above integers, (a + b) is 10 to 200, and when a is 2 or more, a plurality of R ²⁰ and R ²¹ may be the same or different, and when b is 2 or more. , A plurality of R ²² and R ²³ may be the same or different from each other. ]

According to the water repellent aid of the present invention, the durable water repellency of the non-fluorine water repellent can be improved by using it in combination with the non-fluorine water repellent.

The present invention also provides a non-fluorine-based water repellent composition containing the above-mentioned water-repellent aid according to the present invention and a non-fluorine-based water repellent.

The non-fluorine-based water repellent may contain a non-fluorine-based polymer containing a structural unit derived from the (meth) acrylic acid ester monomer (A) represented by the following general formula (A-1). good.

［式（Ａ－１）中、Ｒ^１は水素又はメチル基を表し、Ｒ^２は置換基を有していてもよい炭素数１２以上の１価の炭化水素基を表す。］

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

The non-fluorinated polymer has (B1) a compound represented by the following general formula (I-1) having an HLB of 7 to 18, and (B2) a compound represented by the following general formula (II-1) having an HLB of 7 to 18. At least one selected from the compounds represented and compounds in which an alkylene oxide having 2 to 4 carbon atoms is added to a fat or oil having a (B3) HLB of 7 to 18 and having a hydroxyl group and a polymerizable unsaturated group. It may further contain a structural unit derived from the reactive emulsifier (B).

［式（Ｉ－１）中、Ｒ^３は水素又はメチル基を表し、Ｘは炭素数１～６の直鎖もしくは分岐のアルキレン基を表し、Ｙ^１は炭素数２～４のアルキレンオキシ基を含む２価の基を表す。］

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

［式（ＩＩ－１）中、Ｒ^４は重合性不飽和基を有する炭素数１３～１７の１価の不飽和炭化水素基を表し、Ｙ^２は炭素数２～４のアルキレンオキシ基を含む２価の基を表す。］

[In formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² contains an alkyleneoxy group having 2 to 4 carbon atoms. Represents a divalent group. ]

The non-fluorinated polymer may further contain a structural unit derived from at least one of vinyl chloride and vinylidene chloride, the monomer (E).

The non-fluorine-based water repellent is a non-emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization of an emulsion or dispersion containing the (meth) acrylic acid ester monomer (A) represented by the general formula (A-1). It may contain a fluoropolymer.

The emulsion or dispersion is a compound represented by the general formula (I-1) in which (B1) HLB is 7 to 18, and the general formula (II-1) in which (B2) HLB is 7 to 18. ) And (B3) a compound having an HLB of 7 to 18 and having an alkylene oxide having 2 to 4 carbon atoms added to a fat or oil having a hydroxyl group and a polymerizable unsaturated group. It may further contain the reactive emulsifier (B) of the species.

The emulsion or the dispersion may further contain a monomer (E) of at least one of vinyl chloride and vinylidene chloride.

In the non-fluorine-based water repellent composition according to the present invention, the content of the organomodified silicone may be 1 to 50 parts by mass with respect to 100 parts by mass of the non-fluorine-based polymer.

The present invention also provides a method for producing a water-repellent textile product, which comprises a step of treating the textile product with a treatment liquid containing the non-fluorine-based water repellent composition according to the present invention.

According to the method for producing a water-repellent fiber product of the present invention, a non-fluorine-based water-repellent composition containing the water-repellent aid according to the present invention is used to stabilize a water-repellent fiber product having excellent durability and water repellency. Can be manufactured. Further, the method for producing a water-repellent fiber product of the present invention does not require heat treatment at a high temperature, so that energy can be saved, and a non-fluorine-based water-repellent agent is used, so that it is environmentally friendly. The load can be reduced.

According to the present invention, it is possible to provide a water-repellent aid capable of improving the durable water repellency of a non-fluorine-based water-repellent agent and a non-fluorine-based water-repellent agent composition containing the same.

Further, the non-fluorine-based water-repellent composition of the present invention is a water-repellent composition containing no fluoroalkyl group or a compound having fluorine, but exhibits excellent water repellency, and is a substitute for the fluorine-based water repellent. It can be used as a fluorine source, and it is possible to eliminate concerns about the impact on the environment. It is usually preferable to heat-treat after adhering the water-repellent composition to a textile product or the like, but the non-fluorine-based water-repellent composition of the present invention does not use a monomer having a fluoroalkyl group. High water repellency can be exhibited even when heat-treated under mild conditions of 130 ° C or lower, and when heat-treated at a high temperature exceeding 130 ° C, the heat treatment time is set to the case of a fluorine-based water repellent. Can be shorter than. Therefore, since deterioration due to heat of the object to be treated is suppressed, the texture becomes flexible and the amount of heat required for heat treatment can be reduced, which is also excellent in terms of cost.

Furthermore, according to the present invention, as an emulsifying dispersant used for emulsification or dispersion polymerization of a non-fluorinated polymer, a water repellent composition is prepared by using a specific reactive emulsifier instead of a general surfactant. The amount of surfactant contained in can be reduced. As a result, it is possible to suppress a decrease in water repellency of the obtained textile product or the like, and it is possible to realize higher water repellency than the conventional non-fluorine-based water repellent.

The water-repellent aid for the non-fluorine-based water-repellent agent of the present embodiment contains an organomodified silicone represented by the following general formula (1). In the following general formula (1), each structural unit may be a block, random, or may be arranged alternately.

［式（１）中、Ｒ^２０、Ｒ^２１及びＲ^２２はそれぞれ独立に、水素原子、メチル基、エチル基又は炭素数１～４のアルコキシ基を表し、Ｒ^２３は、芳香族環を有する炭素数８～４０の炭化水素基、又は炭素数３～２２のアルキル基を表し、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４及びＲ^３５はそれぞれ独立に、水素原子、メチル基、エチル基、炭素数１～４のアルコキシ基、芳香族環を有する炭素数８～４０の炭化水素基、又は炭素数３～２２のアルキル基を表し、ａは０以上の整数を表し、ｂは１以上の整数を表し、（ａ＋ｂ）は１０～２００であり、ａが２以上の場合、複数存在するＲ^２０及びＲ^２１はそれぞれ同一であっても異なっていてもよく、ｂが２以上の場合、複数存在するＲ^２２及びＲ^２３はそれぞれ同一であっても異なっていてもよい。］

[In the 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 is a carbon having an aromatic ring. Represents a hydrocarbon group of 8 to 40 or an alkyl group of 3 to 22 carbons, where R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independent hydrogen atoms, methyl groups and ethyls, respectively. A group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 3 to 22 carbon atoms, a represents an integer of 0 or more, and b represents 1. Representing the above integers, (a + b) is 10 to 200, and when a is 2 or more, a plurality of R ²⁰ and R ²¹ may be the same or different, and when b is 2 or more. , A plurality of R ²² and R ²³ may be the same or different from each other. ]

In the organomodified silicone of the present embodiment, the above-mentioned alkoxyl group having 1 to 4 carbon atoms may be linear or branched. Examples of the alkoxyl group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. In terms of easy industrial production and easy availability, R ²⁰ , R ²¹ and R ²² are preferably hydrogen atoms or methyl groups independently, and more preferably methyl groups.

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

［式（２）中、Ｒ^４０は、炭素数２～６のアルキレン基を表し、Ｒ^４１は、単結合又は炭素数１～４のアルキレン基を表し、ｃは０～３の整数を表す。ｃが２又は３の場合、複数存在するＲ^４１は同一であっても異なっていてもよい。］

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

The above alkylene group may be linear or branched.

［式（３）中、Ｒ^４２は、炭素数２～６のアルキレン基を表し、Ｒ^４３は、単結合又は炭素数１～４のアルキレン基を表し、ｄは０～３の整数を表す。ｄが２又は３の場合、複数存在するＲ^４３は同一であっても異なっていてもよい。］

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

The above alkylene group may be linear or branched.

Examples of the aralkyl group having 8 to 40 carbon atoms include a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, and a naphthylethyl group. Of these, a phenylethyl group and a phenylpropyl group are preferable because they are industrially easy to manufacture and easily available.

Among the groups represented by the above general formula (2), an alkylene group having 2 to 4 carbon atoms is preferable for R ⁴⁰ , and c is 0 or 1, in that it is easy to industrially produce and obtain. It is preferably present, and more preferably 0.

Among the groups represented by the general formula (3), R ⁴² is preferably an alkylene group having 2 to 4 carbon atoms, and d is 0 or 1, in that it is easy to industrially manufacture and obtain. It is preferably present, and more preferably 0.

The hydrocarbon group having an aromatic ring and having 8 to 40 carbon atoms is an aralkyl group having 8 to 40 carbon atoms and a general formula (above) in that it is easy to industrially produce and obtain. The group represented by 2) is preferable, and the above-mentioned aralkyl group having 8 to 40 carbon atoms is more preferable in that the water repellency of the obtained textile product can be improved.

The above-mentioned alkyl group having 3 to 22 carbon atoms may be linear or branched. Examples of the alkyl group having 3 to 22 carbon atoms include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a myristyl group, a cetyl group and a stearyl group. As the alkyl group having 3 to 22 carbon atoms, an alkyl group having 8 to 20 carbon atoms is preferable, and an alkyl group having 12 to 18 carbon atoms is more preferable, because the water repellency of the obtained textile product can be improved.

In the organomodified silicone of the present embodiment, R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independently hydrogen atom, methyl group, ethyl group, alkoxy group having 1 to 4 carbon atoms, and fragrance. It is a hydrocarbon group having a group ring and having 8 to 40 carbon atoms, or an alkyl group having 3 to 22 carbon atoms. R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independent hydrogen atoms, methyl groups, ethyl groups or 1 carbon atoms in that they are industrially easy to manufacture and easily available. It is preferably an alkoxy group of ~ 4, and more preferably a methyl group.

In the organomodified silicone of the present embodiment, a is an integer of 0 or more. The a is preferably 40 or less, and more preferably 30 or less, in that it is easy to industrially manufacture and obtain, and the peel strength of the obtained textile product with respect to the resin coating is more excellent.

In the organomodified silicone of the present embodiment, (a + b) is 10 to 200. The value of (a + b) is preferably 20 to 100, more preferably 40 to 60, in that it is industrially easy to manufacture and easily available. When (a + b) is within the above range, the silicone itself tends to be easily manufactured and handled.

The organomodified silicone of the present embodiment can be synthesized by a conventionally known method. The organomodified silicone of the present embodiment can be obtained, for example, by hydrosilylating a silicone having a SiH group with an aromatic compound having a vinyl group and / or an α-olefin.

Examples of the above-mentioned silicone having a SiH group include methylhydrogen silicone having a degree of polymerization of 10 to 200, a copolymer of dimethylsiloxane and methylhydrogensiloxane, and the like. Among these, methylhydrogen silicone is preferable because it is industrially easy to manufacture and easily available.

The above-mentioned aromatic compound having a vinyl group is a compound from which a hydrocarbon group having an aromatic ring and having 8 to 40 carbon atoms has an aromatic ring in ^R23 in the above general formula (1). Examples of the aromatic compound having a vinyl group include styrene, α-methylstyrene, vinylnaphthalene, allylphenyl ether, allylnaphthyl ether, allyl-p-cumylphenyl ether, allyl-o-phenylphenyl ether, and allyl-tri. (Phenylethyl) -phenyl ether, allyl-tri (2-phenylpropyl) phenyl ether and the like can be mentioned.

The α-olefin is a compound from which an alkyl group having 3 to 22 carbon atoms is derived in R ²³ in the general formula (1). Examples of the α-olefin include propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, and the like. Examples thereof include α-olefins having 3 to 22 carbon atoms such as 1-hexadecene and 1-octadecene.

The hydrosilylation reaction is carried out by reacting the silicone having a SiH group with the aromatic compound having a vinyl group stepwise or at once in the presence of a catalyst, if necessary. May be good.

The amounts of the silicon having a SiH group, the aromatic compound having a vinyl group and the α-olefin used in the hydrosilylation reaction are appropriately selected according to the SiH group equivalent amount of the silicone having a SiH group, the number average molecular weight and the like, respectively. obtain.

Examples of the catalyst used in the hydrosilylation reaction include compounds such as platinum and palladium, and platinum compounds are particularly preferable. Examples of the platinum compound include platinum chloride (IV) and the like.

The reaction conditions for the hydrosilylation 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, for example, 3 to 12 hours when the reaction temperature is 50 to 150 ° C.

Further, the hydrosilylation reaction is preferably carried out in an inert gas atmosphere. Examples of the inert gas include nitrogen, argon and the like. Although the reaction proceeds even in the absence of a solvent, a solvent may be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, butyl acetate and the like.

The non-fluorine-based water repellent composition of the present embodiment will be described.

The non-fluorine-based water repellent composition of the present embodiment contains the water-repellent aid of the present embodiment and the non-fluorine-based water repellent.

The above-mentioned non-fluorine-based water-repellent agent is excellent in storage stability and can give sufficient water repellency to textile products even without heat treatment, and is a water-repellent fiber product having excellent texture and water repellency. Is a structural unit derived from the (meth) acrylic acid ester monomer (A) represented by the following general formula (A-1) (hereinafter, also referred to as “component (A)”). It is preferable to contain a non-fluorine-based polymer containing.

［式（Ａ－１）中、Ｒ^１は水素又はメチル基を表し、Ｒ^２は置換基を有していてもよい炭素数１２以上の１価の炭化水素基を表す。］

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

Here, "(meth) acrylic acid ester" means "acrylic acid ester" or "methacrylic acid ester" corresponding thereto, and is synonymous with "(meth) acrylic acid", "(meth) acrylamide" and the like. be.

The (meth) acrylic acid ester monomer (A) represented by the above general formula (A-1) used in the present embodiment is 1 having 12 or more carbon atoms which may have a substituent. It has a valent hydrocarbon group. The hydrocarbon group may be linear or branched, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be an alicyclic or aromatic cyclic group. May have. Among these, those having a linear shape are preferable, and those having a linear alkyl group are more preferable. In this case, the water repellency becomes better. When a monovalent hydrocarbon group having 12 or more carbon atoms has a substituent, the substituents include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group and a (meth) acryloyloxy group. And more than one of them. In the present embodiment, in the above general formula (A-1), R ² is preferably an unsubstituted hydrocarbon group.

The hydrocarbon group preferably has 12 to 24 carbon atoms. If the number of carbon atoms is less than 12, sufficient water repellency cannot be exhibited when the non-fluorine-based polymer is attached to a textile product or the like. On the other hand, when the carbon number exceeds 24, the texture of the textile product tends to be coarser and harder when the non-fluorine-based polymer is attached to the textile product or the like, as compared with the case where the carbon number is in the above range. ..

The number of carbon atoms of the hydrocarbon group is more preferably 12 to 21. When the number of carbon atoms is in this range, the water repellency and texture become particularly excellent. Particularly preferred as the hydrocarbon group is a linear alkyl group having 12 to 18 carbon atoms.

Examples of the component (A) include stearyl (meth) acrylate, cetyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, and (meth) acrylic acid. Pentadecyl, (meth) heptadecyl acrylate, (meth) nonadecylate acrylate, (meth) eicosyl acrylate, (meth) hen-eicosyl acrylate, behenyl (meth) acrylate, ceryl (meth) acrylate, mericyl (meth) acrylate Can be mentioned.

The component (A) can 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 the cross-linking agent. In this case, the durable water repellency of the obtained textile product can be further improved. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. Further, when the component (A) has an amino group, the texture of the obtained textile product can be further improved.

The component (A) is preferably a monofunctional (meth) acrylic acid ester monomer having one polymerizable unsaturated group in one molecule.

As the component (A), one type may be used alone, or two or more types may be used in combination.

The component (A) is preferably a combination of the acrylic acid ester monomer (a1) and the methacrylic acid ester monomer (a2) in terms of the durable water repellency of the obtained textile product. The ratio (a1) / (a2) of the mass of the component (a1) to be blended to the mass of the component (a2) is preferably 30/70 to 90/10, preferably 40/60 to 85/15. Is more preferable, and 50/50 to 80/20 is even more preferable. When (a1) / (a2) is within the above range, the durable water repellency of the obtained textile product becomes better. When (a1) / (a2) exceeds 90/10 or is less than 30/70, the durable water repellency of the obtained textile product tends to decrease.

The total composition ratio of the monomers of the component (A) in the non-fluorine-based polymer is the total amount of the monomer components constituting the non-fluorine-based polymer in terms of water repellency and durable water repellency of the obtained textile product. It is preferably 50 to 100% by mass, more preferably 55 to 97% by mass, and even more preferably 60 to 95% by mass.

The weight average molecular weight of the non-fluorinated polymer is preferably 100,000 or more. If the weight average molecular weight is less than 100,000, the water repellency of the obtained textile product tends to be insufficient. Further, the weight average molecular weight of the non-fluorinated polymer is more preferably 500,000 or more. In this case, the obtained textile product can exhibit more sufficient water repellency. The upper limit of the weight average molecular weight of the non-fluorinated polymer is preferably about 5 million.

In the present embodiment, the melt viscosity of the non-fluorinated polymer at 105 ° C. is preferably 1000 Pa · s or less. When the melt viscosity at 105 ° C. exceeds 1000 Pa · s, the texture of the obtained textile product tends to be coarse and hard. Further, if the melt viscosity of the non-fluorine polymer is too high, when the non-fluorine polymer is emulsified or dispersed to form a water repellent composition, the non-fluorine polymer may precipitate or settle, and the non-fluorine polymer may precipitate or precipitate. The storage stability of the liquid composition tends to decrease. The melt viscosity at 105 ° C. is more preferably 500 Pa · s or less. In this case, the obtained textile product or the like exhibits sufficient water repellency and has a better texture.

"Melting viscosity at 105 ° C." means using an elevated flow tester (for example, CFT-500 manufactured by Shimadzu Corporation) and putting 1 g of a non-fluorinated polymer in a cylinder equipped with a die (length 10 mm, diameter 1 mm). Viscosity measured by holding at 105 ° C. for 6 minutes and applying a load of 100 kg ・ f / cm ² with a plunger.

When the weight average molecular weights of the non-fluorine-based polymers are the same, the higher the blending ratio of the non-fluorine-based (meth) acrylic acid ester monomer, the higher the water repellency of the attached textile product tends to be. Further, by copolymerizing the copolymerizable non-fluorine-based monomer, it is possible to improve the performance such as durable water repellency and texture of the attached textile product.

The non-fluorine polymer is added to the component (A) in that it can improve the water repellency of the obtained textile product and the emulsification stability of the non-fluorine polymer during emulsification polymerization or dispersion polymerization and in the composition after polymerization. (B1) The compound represented by the following general formula (I-1) having an HLB of 7 to 18, and (B2) the compound represented by the following general formula (II-1) having an HLB of 7 to 18. And (B3) at least one reactive emulsifier (B) selected from compounds in which an alkylene oxide having 2 to 4 carbon atoms is added to a fat or oil having a hydroxyl group and a polymerizable unsaturated group having an HLB of 7 to 18. ) (Hereinafter, also referred to as "component (B)") is preferably contained as a monomer component.

［式（Ｉ－１）中、Ｒ^３は水素又はメチル基を表し、Ｘは炭素数１～６の直鎖もしくは分岐のアルキレン基を表し、Ｙ^１は炭素数２～４のアルキレンオキシ基を含む２価の基を表す。］

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

［式（ＩＩ－１）中、Ｒ^４は重合性不飽和基を有する炭素数１３～１７の１価の不飽和炭化水素基を表し、Ｙ^２は炭素数２～４のアルキレンオキシ基を含む２価の基を表す。］

[In formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² contains an alkyleneoxy group having 2 to 4 carbon atoms. Represents a divalent group. ]

A "reactive emulsifier" is an emulsion dispersant having radical reactivity, that is, a surfactant having one or more polymerizable unsaturated groups in the molecule, such as a (meth) acrylic acid ester. It can be copolymerized with a monomer.

Further, "HLB" is an HLB value calculated by the Griffin method, with the ethyleneoxy group being regarded as a hydrophilic group and all other groups being regarded as lipophilic groups.

The HLBs of the compounds (B1) to (B3) used in the present embodiment are 7 to 18, and the emulsion is stable during the emulsion polymerization or dispersion polymerization of the non-fluorinated polymer and in the composition after the polymerization. In terms of sex (hereinafter, simply referred to as emulsion stability), 9 to 15 are preferable. Further, it is more preferable to use two or more kinds of reactive emulsifiers (B) having different HLBs within the above range in combination in terms of storage stability of the non-fluorine-based water repellent.

In the reactive emulsifier (B1) represented by the above general formula (I-1) used in the present embodiment ^, R3 is a hydrogen or a methyl group, and in terms of copolymerizability with the component (A). It is more preferably a methyl group. X is a linear or branched alkylene group having 1 to 6 carbon atoms, and a linear alkylene group having 2 to 3 carbon atoms is more preferable from the viewpoint of emulsion stability of the non-fluorinated polymer of the present embodiment. Y ¹ is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. The type, combination and ^number of alkyleneoxy groups in Y1 can be appropriately selected so as to be within the above range of HLB. Further, when there are two or more alkyleneoxy groups, they can have a block addition structure or a random addition structure.

As the compound represented by the general formula (I-1), the compound represented by the following general formula (I-2) is preferable.

［式（Ｉ－２）中、Ｒ^３は水素又はメチル基を表し、Ｘは炭素数１～６の直鎖もしくは分岐のアルキレン基を表し、Ａ^１Ｏは炭素数２～４のアルキレンオキシ基を表し、ｍは上記ＨＬＢの範囲内になるように適宜選択することができ、具体的には、１～８０の整数が好ましく、ｍが２以上のときｍ個のＡ^１Ｏは同一であっても異なっていてもよい。］

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

In the compound represented by the general formula (I- ² ), R3 is a hydrogen or a methyl group, and more preferably a methyl group in terms of copolymerizability with the component (A). X is a linear or branched alkylene group having 1 to 6 carbon atoms, and a linear alkylene group having 2 to 3 carbon atoms is more preferable from the viewpoint of emulsion stability of the non-fluorinated polymer. A ¹ O is an alkyleneoxy group having 2 to 4 carbon atoms. The types and combinations of A ¹ O and the number of m can be appropriately selected so as to be within the above HLB range. In terms of the emulsion stability of the non-fluorinated polymer, 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. Further, when there are two or more types of A ¹ O, they can have a block addition structure or a random addition structure.

The reactive emulsifier (B1) represented by the general formula (I-2) can be obtained by a conventionally known method, and is not particularly limited. Further, it can be easily obtained from a commercially available product, and examples thereof include "Latemuru PD-420", "Latemuru PD-430", and "Latemuru PD-450" manufactured by Kao Corporation.

In the reactive emulsifier (B2) represented by the above general formula (II-1) used in the present embodiment, ^R4 is a monovalent unsaturated hydrocarbon having 13 to 17 carbon atoms having a polymerizable unsaturated group. Examples of the hydrogen group include a tridecenyl group, a tridecazienyl group, a tetradecenyl group, a tetradienyl group, a pentadecenyl group, a pentadecazineyl group, a pentadecatorienyl group, a heptadecenyl group, a heptadecadienyl group and a heptadecatorienyl group. .. In terms of the emulsion stability of the non-fluorinated polymer, ^R4 is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

Y ² is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. The type, combination and number of alkyleneoxy groups in Y ² can be appropriately selected so as to be within the above range of HLB. Further, when there are two or more alkyleneoxy groups, they can have a block addition structure or a random addition structure. Ethyleneoxy groups are more preferable as alkyleneoxy groups in terms of emulsion stability of non-fluorinated polymers.

As the compound represented by the general formula (II-1), the compound represented by the following general formula (II-2) is preferable.

［式（ＩＩ－２）中、Ｒ^４は重合性不飽和基を有する炭素数１３～１７の１価の不飽和炭化水素基を表し、Ａ^２Ｏは炭素数２～４のアルキレンオキシ基を表し、ｎは上記ＨＬＢの範囲内になるように適宜選択することができ、具体的には、１～５０の整数が好ましく、ｎが２以上のときｎ個のＡ^２Ｏは同一であっても異なっていてもよい。］

[In the formula (II-2), ^R4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and A2O represents an alkyleneoxy group having ² to 4 carbon atoms. Represented, n can be appropriately selected so as to be within the range of the above HLB. Specifically, an integer of 1 to 50 is preferable, and when n is ² or more, n A2Os are the same. May be different. ]

The ^R4 in the compound represented by the general formula (II-2) may be the same as the ^R4 in the general formula (II-1) described above.

A ² O is an alkyleneoxy group having 2 to 4 carbon atoms. In terms of the emulsion stability of the non-fluorinated polymer, the type and combination of A2O and the number of ⁿ can be appropriately selected so as to be within the above HLB range. In terms of emulsion stability of the non-fluorinated polymer, A ² O is more preferably an ethyleneoxy group, n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, and even more preferably an integer of 8 to 14. .. When n is 2 or more, n A ² O may be the same or different. Further, when there are two or more types of A ² O, they can have a block addition structure or a random addition structure.

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

The phenol having the corresponding unsaturated hydrocarbon group includes not only industrially produced pure products or mixtures, but also those existing as pure products or mixtures extracted and purified from plants and the like. For example, 3- [8 (Z), 11 (Z), 14-pentadecatrienyl] phenol, 3- [8 (Z), 11 (Z), extracted from cashew nut shells and the like and collectively referred to as cardanol. -Pentadecazienyl] phenol, 3- [8 (Z) -pentadecenyl] phenol, 3- [11 (Z) -pentadecenyl] phenol and the like can be mentioned.

The reactive emulsifier (B3) used in the present embodiment is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a fat or oil having a hydroxyl group and a polymerizable unsaturated group having an HLB of 7 to 18. .. 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, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.). Examples include mono or diglycerides of good fatty acids, triglycerides of fatty acids containing at least one hydroxy unsaturated fatty acid (ricinol acid, lysinoelysinic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of emulsion stability of non-fluoropolymers, an alkylene oxide adduct of triglyceride of a fatty acid containing at least one hydroxy unsaturated fatty acid is preferable, and castor oil (triglyceride of fatty acid containing ricinoleic acid) has 2 to 4 carbon atoms. The alkylene oxide adduct of the above is more preferable, and the ethylene oxide adduct of castor oil is further preferable. Further, the number of moles of alkylene oxide added can be appropriately selected so as to be within the above range of HLB, and 20 to 50 mol is more preferable, and 25 to 45 mol is more preferable in terms of emulsion stability of the non-fluorinated polymer. Is even more preferable. Further, when there are two or more kinds of alkylene oxides, they can have a block addition structure or a random addition structure.

The reactive emulsifier (B3) used in the present embodiment can be synthesized by adding an alkylene oxide to a fat or oil having a hydroxyl group and a polymerizable unsaturated group by a conventionally known method, and is particularly limited. It's not a thing. For example, it can be synthesized by adding a predetermined amount of alkylene oxide to triglyceride of a fatty acid containing ricinoleic acid, that is, castor oil using an alkaline catalyst such as caustic soda or caustic potassium at 120 to 170 ° C. under pressure. ..

The composition ratio of the monomer of the above component (B) in the non-fluorine polymer is the water repellency of the obtained textile product and the emulsion stability during the emulsion polymerization or dispersion polymerization of the non-fluorine polymer and in the composition after the polymerization. From the viewpoint of improving the properties, the content is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, based on the total amount of the monomer components constituting the non-fluorinated polymer. It is more preferably to 10% by mass.

The non-fluorine polymer contained in the non-fluorine water repellent can improve the durable water repellency of the obtained textile product, and in addition to the component (A), the following (C1), (C2), (C3), It contains at least one second (meth) acrylic acid ester monomer (C) (hereinafter, also referred to as “C component”) selected from the group consisting of (C4) and (C5) as a monomer component. Is preferable.

［式（Ｃ－１）中、Ｒ^５は水素又はメチル基を表し、Ｒ^６はヒドロキシル基、アミノ基、カルボキシル基、エポキシ基、イソシアネート基及び（メタ）アクリロイルオキシ基からなる群より選ばれる少なくとも１種の官能基を有する炭素数１～１１の１価の鎖状炭化水素基を表す。ただし、分子内における（メタ）アクリロイルオキシ基の数は２以下である。］ A (meth) acrylic acid ester monomer represented by the following general formula (C-1) other than (C1) and (C5).

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

［式（Ｃ－２）中、Ｒ^７は水素又はメチル基を表し、Ｒ^８は置換基を有していてもよい炭素数１～１１の１価の環状炭化水素基を表す。］ (C2) (Meta) acrylic acid ester monomer represented by the following general formula (C-2)

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

［式（Ｃ－３）中、Ｒ^９は無置換の炭素数１～４の１価の鎖状炭化水素基を表す。］ (C3) Methacrylic acid ester monomer represented by the following general formula (C-3)

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

［式（Ｃ－４）中、Ｒ^１０は水素又はメチル基を表し、ｐは２以上の整数を表し、Ｓは（ｐ＋１）価の有機基を表し、Ｔは重合性不飽和基を有する１価の有機基を表す。］ (C4) (Meta) acrylic acid ester monomer represented by the following general formula (C-4)

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

［式（Ｃ－５）中、Ｒ^１１は水素又はメチル基を表し、Ｒ^１２はクロロ基及びブロモ基からなる群より選ばれる少なくとも１種の官能基とヒドロキシル基とを有する炭素数３～６の１価の鎖状飽和炭化水素基を表す。］ (C5) (Meta) acrylic acid ester monomer represented by the following general formula (C-5)

[In the formula (C-5), R ¹¹ represents a hydrogen or a methyl group, and R ¹² has at least one functional group selected from the group consisting of a chloro group and a bromo group and a hydroxyl group and has 3 to 6 carbon atoms. Represents the monovalent chain saturated hydrocarbon group of. ]

The monomer of (C1) 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) acryloyloxy group in the ester moiety. It is a (meth) acrylic acid ester monomer having a monovalent chain hydrocarbon group of 1 to 11, and is a (meth) acrylic acid ester monomer other than the above (C5). The monovalent chain hydrocarbon group having 1 to 11 carbon atoms is at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group because it can react with a cross-linking agent. It is preferable to have a functional group. When a non-fluorine polymer containing a (C1) monomer having a group capable of reacting with these cross-linking agents is treated into a textile product together with a cross-linking agent, the texture of the obtained fiber product is maintained. Durable water repellency can be improved. The isocyanate group may be a blocked isocyanate group protected by a blocking agent.

The chain hydrocarbon group may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, the chain hydrocarbon group may further have a substituent in addition to the above functional group. Above all, it is preferable that it is linear and / or a saturated hydrocarbon group in that the durable water repellency of the obtained textile product can be improved.

Specific examples of the (C1) monomer include 2-hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, and 1,1-bis (acryloyloxymethyl) ethyl. Examples thereof include isocyanate. These monomers may be used alone or in combination of two or more. Among them, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate are preferable because the durable water repellency of the obtained textile product can be improved. Further, dimethylaminoethyl (meth) acrylate is preferable in terms of improving the texture of the obtained textile product.

The composition ratio of the monomer of (C1) in the non-fluorine-based polymer is 1 with respect to the total amount of the monomer components constituting the non-fluorine-based polymer from the viewpoint of water repellency and texture of the obtained textile product. It is preferably to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass.

The monomer (C2) is a (meth) acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester moiety, and the cyclic hydrocarbon group includes an isobornyl group. Examples thereof include a cyclohexyl group and a dicyclopentanyl group. These cyclic hydrocarbon groups may have a substituent such as an alkyl group. However, when the substituent is a hydrocarbon group, a hydrocarbon group having a total of 11 or less carbon atoms of the substituent and the cyclic hydrocarbon group is selected. Further, it is preferable that these cyclic hydrocarbon groups are directly bonded to the ester bond from the viewpoint of improving durable water repellency. The cyclic hydrocarbon group may be an alicyclic group or an aromatic group, and in the case of an alicyclic group, it may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Specific examples of the monomer include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate and the like. These monomers may be used alone or in combination of two or more. Among them, isobornyl (meth) acrylate and cyclohexyl methacrylate are preferable, and isobornyl methacrylate is more preferable, because the durable water repellency of the obtained textile product can be improved.

The composition ratio of the monomer of (C2) in the non-fluorine-based polymer is 1 with respect to the total amount of the monomer components constituting the non-fluorine-based polymer from the viewpoint of water repellency and texture of the obtained textile product. It is preferably to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass.

The monomer (C3) is a methacrylic acid ester 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 moiety. As the chain hydrocarbon group having 1 to 4 carbon atoms, a linear hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms are preferable. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group and the like. Specific examples of the compound include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and t-butyl methacrylate. These monomers may be used alone or in combination of two or more. Among them, methyl methacrylate, isopropyl methacrylate and t-butyl methacrylate are preferable, and methyl methacrylate is more preferable, because the durable water repellency of the obtained textile product can be improved.

The composition ratio of the monomer of (C3) in the non-fluorine-based polymer is 1 with respect to the total amount of the monomer components constituting the non-fluorine-based polymer from the viewpoint of water repellency and texture of the obtained textile product. It is preferably to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass.

The monomer (C4) is a (meth) acrylic acid ester monomer having 3 or more polymerizable unsaturated groups in one molecule. In the present embodiment, T in the above general formula (C-4) is a (meth) acryloyloxy group, and a polyfunctional (meth) acrylic acid ester simple having 3 or more (meth) acryloyloxy groups in one molecule. A quantity is preferred. In the formula (C-4), the p Ts may be the same or different. Specific compounds include, for example, ethoxylated isocyanuric acid triacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and the like. Examples thereof include dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate. These monomers may be used alone or in combination of two or more. Among them, tetramethylolmethanetetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferable in that the durable water repellency of the obtained textile product can be improved.

The composition ratio of the monomer of the above (C4) in the non-fluorine-based polymer is 1 with respect to the total amount of the monomer components constituting the non-fluorine-based polymer from the viewpoint of water repellency and texture of the obtained textile product. It is preferably to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass.

The monomer (C5) has a monovalent chain saturated hydrocarbon group having 3 to 6 carbon atoms and having at least one functional group selected from the group consisting of a chloro group and a bromo group and a hydroxyl group. .. In the monomer of (C5) above, R ¹¹ is a hydrogen or a methyl group. From the viewpoint of durable water repellency of the obtained textile product, R ¹¹ is preferably a methyl group.

^R12 is a monovalent chain saturated hydrocarbon group having 3 to 6 carbon atoms and having at least one functional group selected from the group consisting of a chloro group and a bromo group and a hydroxyl group. The chain saturated hydrocarbon group may be linear or branched. When the chain saturated hydrocarbon group is linear, the durable water repellency of the obtained textile product becomes more excellent. The carbon number of the chain saturated hydrocarbon group is preferably 3 to 4, more preferably 3 in terms of the durable water repellency of the obtained textile product.

The chain saturated hydrocarbon group preferably has one or two chloro groups and one hydroxyl group in terms of durable water repellency of the obtained textile product, and one chloro group and one chloro group. It is more preferable to have one hydroxyl group. In terms of the durable water repellency of the obtained textile product, the chain saturated hydrocarbon group has a hydroxyl group at the β-position (the carbon atom next to the carbon atom bonded to CH ₂ = CR ¹¹ (CO) O-). It is more preferable to have. Specific examples of the chain saturated hydrocarbon group include 3-chloro-2-hydroxybutyl group, 3-chloro-2-hydroxybutyl group, 5-chloro-2-hydroxypentyl group, and 3-chloro-2. -Hydroxy-2-methylpropyl group and 3-bromo-2-hydroxypropyl group can be mentioned.

Specific examples of the (C5) monomer include (meth) acrylic acid 3-chloro-2-hydroxypropyl, (meth) acrylic acid 3-chloro-2-hydroxybutyl, and (meth) acrylic acid 5-. Included are chloro-2-hydroxypentyl and 3-bromo-2-hydroxypropyl (meth) acrylate. Of these, 3-chloro-2-hydroxypropyl (meth) acrylate is preferable, and 3-chloro-2-hydroxypropyl methacrylate is more preferable, because the durable water repellency of the obtained textile product can be improved.

The composition ratio of the monomer of the above (C5) in the non-fluorine-based polymer is 1 to 30 with respect to the total amount of the monomer components constituting the non-fluorine-based polymer in terms of the durable water repellency of the obtained textile product. It is preferably by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass.

The total composition ratio of the monomers of the above-mentioned component (C) in the non-fluorine-based polymer is the total amount of the monomer components constituting the non-fluorine-based polymer from the viewpoint of water repellency and texture of the obtained textile product. It is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass.

The non-fluorine polymer contained in the non-fluorine water repellent is a monofunctional monomer (D) (hereinafter, copolymerizable with the component (A), the component (B) and the component (C), which can be copolymerized with the component (A), the component (B) and the component (C). , "(D) component") can be contained within a range that does not impair the effects of the present invention.

Examples of the monomer of (D) include (meth) acryloylmorpholine, (meth) acrylic acid ester having a hydrocarbon group other than the components (A) and (C), (meth) acrylic acid, and fumaric acid. Esters, maleic acid esters, fumaric acid, maleic acid, (meth) acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, ethylene, styrene and other fluorine-free vinyl monomers other than the (E) component, etc. Can be mentioned. The (meth) acrylic acid ester having a hydrocarbon group other than the component (A) and the component (C) has a vinyl group, a hydroxyl group, an amino group, an epoxy group and an isocyanate group, and a blocked isocyanate group in the hydrocarbon group. It may have a substituent other than a group capable of reacting with a cross-linking agent such as a quaternary ammonium group, and may have an ether bond, an ester bond, an amide bond, or a urethane bond. Etc. may be possessed. Examples of the (meth) acrylic acid ester other than the component (A) and the component (C) include methyl acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate and the like. Can be mentioned. Among them, (meth) acryloyl morpholine is more preferable because it can improve the peel strength of the obtained textile product against the coating.

The composition ratio of the monomer of the component (D) in the non-fluorine-based polymer is based on the total amount of the monomer components constituting the non-fluorine-based polymer from the viewpoint of water repellency and texture of the obtained textile product. It is preferably 10% by mass or less.

The non-fluorine polymer contained in the non-fluorine water repellent has 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 capable of reacting with a cross-linking agent. However, it is preferable because it improves the durable water repellency of the obtained textile product. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. Further, it is preferable that the non-fluorine-based polymer has an amino group because it improves the texture of the obtained textile product.

The non-fluorine polymer contained in the non-fluorine water repellent can improve the water repellency of the obtained textile product and the peel strength against the coating, and in addition to the component (A), at least one of vinyl chloride and vinylidene chloride. It is preferable that one kind of monomer (E) (hereinafter, also referred to as “component (E)”) is contained as a monomer component.

The monomer (E) of at least one of vinyl chloride and vinylidene chloride used in the present embodiment is preferably vinyl chloride in terms of the water repellency of the obtained textile product and the peel strength with respect to the coating.

The composition ratio of the monomer of the component (E) in the non-fluorine-based polymer is based on the total amount of the monomer components constituting the non-fluorine-based polymer from the viewpoint of improving the peel strength with respect to the coating of the obtained textile product. It is preferably 1 to 45% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 35% by mass.

Additives and the like can be added to the water repellent composition of the present embodiment, if necessary. Examples of the additive include other water repellents, cross-linking agents, antibacterial deodorants, flame retardants, antistatic agents, softeners, wrinkle-proofing agents and the like.

Next, a method for producing a non-fluorine-based water repellent agent containing a non-fluorine-based polymer will be described.

The non-fluorine-based water repellent agent containing the non-fluorine-based polymer can be produced by a radical polymerization method. Further, among the radical polymerization methods, it is preferable to polymerize by an emulsion polymerization method or a dispersion polymerization method from the viewpoint of the performance of the obtained water repellent and the environment.

For example, a non-fluorine-based polymer can be obtained by emulsion polymerization or dispersion polymerization of the (meth) acrylic acid ester monomer (A) represented by the above general formula (A-1) in a medium. More specifically, for example, the component (A) and, if necessary, the component (B), the component (C), the component (D) and the component (E), and an emulsifying aid or dispersion in the medium. Auxiliary agents are added and the mixture is emulsified or dispersed to give an emulsion or dispersion. By adding a polymerization initiator to the obtained emulsion or dispersion, the polymerization reaction is started, and the monomer and the reactive emulsifier can be polymerized. Examples of the means for emulsifying or dispersing the above-mentioned mixed solution include a homomixer, a high-pressure emulsifier, ultrasonic waves, and the like.

Examples of the emulsification aid or dispersion aid (hereinafter, also referred to as “emulsification aid, etc.”) include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants other than the reactive emulsifier (B). One or more selected from surfactants can be used. The content of the emulsifying aid and the like is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and 1 to 10 parts by mass with respect to 100 parts by mass of the total monomer. Is more preferable. When the content of the emulsification aid or the like is less than 0.5 parts by mass, the dispersion stability of the mixed solution tends to be lower than that when the content of the emulsification aid or the like is in the above range. When the content of the emulsifying aid or the like exceeds 30 parts by mass, the water repellency of the obtained non-fluorine-based polymer tends to decrease as compared with the case where the content of the emulsifying auxiliary agent or the like is in the above range.

Water is preferable as the medium for emulsion polymerization or dispersion polymerization, and water and an organic solvent may be mixed if necessary. The organic solvent at this time is not particularly limited as long as it is an organic solvent that can be mixed with water, but for example, alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, and diethyl. Examples thereof include ethers such as ether and glycols such as propylene glycol, dipropylene glycol and tripropylene glycol. The ratio of water to the organic solvent is not particularly limited.

As the polymerization initiator, known polymerization initiators such as azo type, peroxide type, and redox type can be appropriately used. The content of the polymerization initiator is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total monomer. When the content of the polymerization initiator is within the above range, a non-fluorine-based polymer having a weight average molecular weight of 100,000 or more can be efficiently produced.

Further, in the polymerization reaction, a chain transfer agent such as dodecyl mercaptan or t-butyl alcohol may 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, and more preferably 0.1 parts by mass or less with respect to 100 parts by mass of all the monomers. If the content of the chain transfer agent exceeds 0.3 parts by mass, the molecular weight is lowered, and it tends to be difficult to efficiently produce a non-fluorine-based polymer having a weight average molecular weight of 100,000 or more.

A polymerization inhibitor may be used for adjusting the molecular weight. By adding a polymerization inhibitor, a non-fluorinated polymer having a desired weight average molecular weight can be easily obtained.

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

In the polymerization reaction, the weight average molecular weight of the obtained non-fluoropolymer can be adjusted by increasing or decreasing the contents of the above-mentioned polymerization initiator, chain transfer agent and polymerization inhibitor, and the melt viscosity at 105 ° C. is polyfunctional. It can be adjusted by increasing or decreasing the content of the monomer and the content of the polymerization initiator. If it is desired to reduce the melt viscosity at 105 ° C., the content of the monomer having two or more polymerizable functional groups may be reduced, or the content of the polymerization initiator may be increased.

The content of the non-fluorinated polymer in the polymer emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization is 10 to 50 with respect to the total amount of the emulsion or dispersion from the viewpoint of storage stability and handleability of the composition. The mass is preferably%, and more preferably 20 to 40% by mass.

The non-fluorine-based water-repellent composition of the present embodiment can be produced by mixing the water-repellent aid of the present embodiment with the non-fluorine-based water-repellent agent.

The blending amount of the organomodified silicone represented by the above general formula (1) in the non-fluorine-based water repellent composition of the present embodiment is 1 to 10% by mass in terms of the durable water repellency of the obtained textile product. It is preferably 3 to 7% by mass, and more preferably 3 to 7% by mass.

Further, the blending amount of the organomodified silicone represented by the above general formula (1) in the non-fluorine water repellent composition of the present embodiment is 100 mass by mass of the non-fluorine polymer in terms of the durable water repellency of the obtained textile product. It is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 10 to 25 parts by mass.

A method for manufacturing the water-repellent fiber product of the present embodiment will be described.

The water-repellent fiber product of the present embodiment is obtained by treating the fiber product with a treatment liquid containing the above-mentioned non-fluorine-based water-repellent composition. The material of such textile products is not particularly limited, and natural fibers such as cotton, linen, silk and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as nylon, polyester, polyurethane and polypropylene, and composite fibers thereof, Examples include blended fibers. The form of the textile product may be any form such as fiber, thread, cloth, woven fabric, knitted fabric, cloth in the form of clothing, carpet, non-woven fabric, and paper.

Examples of the method for treating the textile product with the above-mentioned treatment liquid include a processing method such as dipping, spraying, and coating, a processing method by a cleaning method, and the like. When the non-fluorine-based water repellent composition contains water, it is preferable to dry the composition after adhering it to the textile product in order to remove the water.

Further, after treating the textile product with the non-fluorine-based water repellent composition of the present embodiment, it is preferable to appropriately heat-treat it. The temperature condition is not particularly limited, but when the non-fluorine-based water repellent composition of the present embodiment is used, sufficiently good water repellency can be exhibited in the textile product under mild conditions of 100 to 130 ° C. The temperature condition may be high temperature treatment of 130 ° C. or higher (preferably up to 200 ° C.), but in such a case, the treatment time can be shortened as compared with the conventional case using a fluorine-based water repellent. .. Therefore, according to the water-repellent fiber product of the present embodiment, deterioration of the fiber product due to heat is suppressed, the texture of the fiber product during the water-repellent treatment becomes flexible, and under mild heat treatment conditions, that is, low-temperature cure conditions. Sufficient water repellency can be imparted to textile products.

In particular, when it is desired to improve the durable water repellency, the above-mentioned step of treating a textile product with a treatment liquid containing a non-fluorine-based water repellent composition and one methylol melamine, isocyanate group or blocked isocyanate group are used. It is preferable to make the textile product water-repellent by a method including a step of adhering a cross-linking agent typified by the above compound to the textile product and heating the cross-linking agent. Further, if it is desired to further improve the durable water repellency, the non-fluorine-based water-repellent composition comprises a non-fluorine-based polymer copolymerized with a monomer having a functional group capable of reacting with the above-mentioned cross-linking agent. Is preferable.

Compounds having one or more isocyanate groups include monoisocyanates such as butyl isocyanate, phenylisocyanate, tolyl isocyanate, and naphthalene isocyanate, diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate, and these. Examples thereof include a trimer which is an isocyanurate ring and a trimethylolpropane adduct. Examples of the compound having one or more blocked isocyanate groups include compounds in which the above-mentioned compound having an isocyanate group is protected with an isocyanate group by a blocking agent. Examples of the blocking agent used at this time include organic blocking agents such as secondary or tertiary alcohols, active methylene compounds, phenols, oximes and lactams, and bisulfites such as sodium bisulfite and potassium bisulfite. Salt is mentioned. The above-mentioned cross-linking agent may be used alone or in combination of two or more.

The cross-linking agent can be obtained, for example, by dissolving the cross-linking agent in an organic solvent or immersing the material to be treated (textile product) in a treatment liquid emulsified and dispersed in water and drying the treatment liquid adhering to the material to be treated. It can be attached to the object to be treated. Then, by heating the cross-linking agent adhering to the object to be treated, the reaction between the cross-linking agent and the object to be treated and the non-fluorine-based polymer can be allowed to proceed. In order to sufficiently proceed the reaction of the cross-linking agent and more effectively improve the washing durability, the heating at this time is preferably performed at 110 to 180 ° C. for 1 to 5 minutes. The step of adhering the cross-linking agent and heating may be performed at the same time as the step of treating with the treatment liquid containing the above-mentioned water repellent composition. When performed at the same time, for example, a treatment liquid containing a water repellent composition and a cross-linking agent is attached to the object to be treated, water is removed, and then the cross-linking agent adhering to the object to be treated is further heated. Considering simplification of the water-repellent processing step, reduction of heat quantity, and economy, it is preferable to perform the process at the same time as the treatment step of the water-repellent composition.

In addition, excessive use of the cross-linking agent may impair the texture. The cross-linking agent is preferably used in an amount of 0.1 to 50% by mass, particularly preferably 0.1 to 10% by mass, based on the object to be treated (textile product).

The water-repellent fiber product of the present embodiment thus obtained can sufficiently exhibit water repellency even when used outdoors for a long period of time, and the water-repellent fiber product uses a fluorine-based compound. Because it does not, it can be made environmentally friendly.

The water-repellent fiber product of the present embodiment can be coated on a predetermined portion. Examples of the coating process include moisture permeable and waterproof processing and windproof processing for sports and outdoor applications. As a processing method, for example, in the case of moisture permeable and waterproof processing, a coating liquid containing a urethane resin, an acrylic resin or the like and a medium can be applied to one side of a water-repellent treated textile product and dried. can.

Although the preferred embodiment of the present invention has been described above, the present invention is not limited to the above embodiment.

For example, in the case of producing a non-fluoropolymer, in the above embodiment, the polymerization reaction is carried out by radical polymerization, but the polymerization reaction is carried out by photopolymerization irradiating with ionizing radiation such as ultraviolet rays, electron beams and γ rays. May be done.

Further, in the present invention, the non-fluorine-based water repellent composition is treated into a textile product to obtain a water-repellent fiber product, but the product treated with the non-fluorine-based water repellent composition is used for textile products. Not limited to this, it may be an article such as metal, glass, or resin.

Further, in such a case, the method of adhering the non-fluorine-based water repellent composition to the article and the amount of the water repellent adhering can be arbitrarily determined according to the type of the object to be treated and the like.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited to these Examples.

<Preparation of water repellent aid>
(Synthesis Example 1)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, a nitrogen gas introduction tube and a dropping funnel, 63.2 g of methylhydrogen silicone having a SiH group equivalent of 63.2 g / mol and a degree of polymerization of 50 was added. It was added, nitrogen was allowed to flow, and the mixture was heated until the temperature reached 65 ° C. and mixed until uniform. As a hydrosilylation catalyst, an ethylene glycol monobutyl ether / toluene mixed solution of platinum (IV) chloride was added to the reaction product in the system so that the platinum concentration was 5 ppm. When the temperature of the reaction product reached 120 ° C., 168.3 g of 1 mol of 1-dodecene was added dropwise and reacted at 120 ° C. for 6 hours. The completion of the addition reaction was confirmed by performing an FT-IR analysis of the obtained organomodified silicone and confirming that the absorption spectrum derived from the SiH group of the methylhydrogen silicone disappeared. Thus, in the general formula (1), a is 0, b is 50, R ²² is a methyl group, R ²³ is a dodecyl group, R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are methyl groups. A certain organomodified silicone was obtained. Further, 3 parts by mass of an ethylene oxide 9 mol adduct of a branched higher alcohol having 12 to 14 carbon atoms was added to 20 parts by mass of the obtained organomodified silicone and mixed. Then, 77 parts by mass of water was added little by little while mixing and emulsified in water to obtain a silicone emulsion.

(Synthesis Example 2)
Organo-modified silicone and silicone emulsion were obtained in the same manner as in Synthesis Example 1 except that 84.2 g of 1 mol of 1-hexene was used instead of 168.3 g of 1 mol of 1-dodecene. In the organomodified silicone, a is 0, b is 50, R ²² is a methyl group, R ²³ is a hexyl group, R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R in the above general formula (1). An organomodified silicone having ³⁵ as a methyl group was obtained.

(Synthesis Example 3)
Organo-modified silicone and silicone emulsion were obtained in the same manner as in Synthesis Example 1 except that 252.5 g of 1 mol of 1-octadecene was used instead of 168.3 g of 1 mol of 1-dodecene. In the organomodified silicone, a in the general formula (1) is 0, b is 50, R ²² is a methyl group, R ²³ is an octadecyl group, R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ . An organomodified silicone having a methyl group was obtained.

(Synthesis Example 4)
Same as Synthesis Example 1 except that 0.5 mol of 1-dodecene 84.2 g and 0.5 mol of α-methylstyrene 59.1 g were used instead of 1 mol of 1-dodecene 168.3 g. To obtain organomodified silicone and silicone emulsion. In the organomodified silicone, a in the general formula (1) is 0, b is 50, R ²² is a methyl group, R ²³ is a dodecyl group or a methyl styrene group, R ³⁰ , R ³¹ , R ³² , R ³³ , R. Organo-modified silicones in which ³⁴ and ^R35 are methyl groups were obtained.

(Synthesis Example 5)
Same as Synthesis Example 1 except that 0.5 mol of 1-dodecene 84.2 g and 0.5 mol of 1-octadecene 126.2 g were used instead of 1 mol of 1-dodecene 168.3 g. Organo-modified silicone and silicone emulsion were obtained. In the organomodified silicone, a in the general formula (1) is 0, b is 50, R ²² is a methyl group, R ²³ is a dodecyl group or an octadecyl group, R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ . And an ^{organomodified} silicone having R35 as a methyl group was obtained.

(Synthesis Example 6)
Instead of 63.2 g of methylhydrogen silicone having a SiH group equivalent of 63.2 g / mol and a degree of polymerization of 50, dimethylsiloxane having a SiH group equivalent of 140.5 g / mol and a degree of polymerization of 50. Organo-modified silicone and silicone emulsion were obtained in the same manner as in Synthesis Example 1 except that 140.5 g of a copolymer of the above and methylhydrogensiloxane was used. In the organomodified silicone, a in the general formula (1) is 25, b is 25, R ²⁰ and R ²¹ are methyl groups, R ²² is a methyl group, R ²³ is a dodecyl group, R ³⁰ , R ³¹ , and R ³² . , R ³³ , R ³⁴ and R ³⁵ are methyl groups to give organomodified silicones.

(Synthesis Example 7)
Hydrogen Silicone (trade name: KF-99, manufactured by Shin-Etsu Chemical Co., Ltd.) was added with 3 parts by mass of a 9 mol adduct of a branched higher alcohol having 12 to 14 carbon atoms and mixed. Then, 77 parts by mass of water was added little by little while mixing and emulsified in water to obtain a silicone emulsion.

(Synthesis Example 8)
A silicone emulsion was obtained in the same manner as in Synthesis Example 7 except that dimethyl-modified silicone (trade name: KF-96H-300,000 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of hydrogen silicone.

<Preparation of polymer dispersion>
A mixture having the compositions shown in Tables 1 to 6 (in the table, the numerical value indicates (g)) was polymerized by the procedure shown below to obtain a polymer dispersion.

(Synthesis Example 9)
In a 500 mL flask, 60 g of stearyl acrylate, 2 g of Neugen XL-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7), Neugen XL-60 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 2 g of polyoxyalkylene branched decyl ether, HLB = 12.5), 3 g of stearyldimethylamine hydrochloride, 25 g of tripropylene glycol and 207.70 g of water were added, and the mixture was mixed and stirred at 45 ° C. to prepare a mixed solution. The mixed solution was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.3 g of azobis (isobutylamidine) dihydrochloride was added to the mixed solution and radically polymerized at 60 ° C. for 6 hours under a nitrogen atmosphere to obtain a non-fluorine polymer dispersion having a polymer concentration of 20% by mass. ..

(Synthesis Examples 10 to 36)
Polymerization was carried out in the same manner as in Synthesis Example 9 except that the materials shown in Tables 1 to 6 were used, and non-fluorine polymer dispersions having the polymer concentrations shown in Tables 7 to 10 were obtained.

In each of the polymers in the polymer dispersions obtained in Synthesis Examples 9 to 36, 98% or more of all the monomers were polymerized by a gas chromatograph (GC-15APTF, manufactured by Shimadzu Corporation). It was confirmed that there was.

The details of the materials shown in Tables 1 to 6 are as follows.
Latemul PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6)
Latemul PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 14.4)
12.5 mol adduct of ethylene oxide of cardanol (HLB = 12.9, indicated as "cardanol 12.5EO" in the table)
8.3 mol adduct of ethylene oxide of cardanol (HLB = 11.0, indicated as "cardanol 8.3EO" in the table)
42 mol of castor oil ethylene oxide adduct (HLB = 13.3, indicated as "castor oil 42EO" in the table)
30 mol of castor oil ethylene oxide adduct (HLB = 11.7, indicated as "castor oil 30EO" in the table)

で表され、ｎの平均値が８となる混合物（なお、当該混合物にはｎが６，８，１０，１２，１４の化合物が混合されている）である。 The "C8 fluorogroup-containing acrylate" in the table is the following general formula (III) :.

It is a mixture represented by and has an average value of n of 8 (note that a compound having n of 6, 8, 10, 12, and 14 is mixed in the mixture).

The polymer dispersion obtained above and the polymer obtained by the method shown below were evaluated.

(Evaluation of polymer properties)
The polymer and the emulsifier were separated by adding 500 mL of acetone to 50 g of the polymer dispersion obtained in Synthesis Examples 9 to 36, the polymer was collected by filtration, and the polymer was dried under reduced pressure at 25 ° C. for 24 hours. The obtained polymer was evaluated as follows. The results are shown in Tables 7-10.

(1) Method for measuring melt viscosity The polymer obtained above was used in a cylinder equipped with a die (length 10 mm, diameter 1 mm) using an elevated flow tester CFT-500 (manufactured by Shimadzu Corporation). Was added, and the mixture was held at 105 ° C. for 6 minutes, a load of 100 kg · f / cm ² was applied with a plunger, and the melt viscosity at 105 ° C. was measured.

(2) Method for measuring weight average molecular weight With respect to the polymer obtained above, a GPC apparatus (GPC "HLC-8020" manufactured by Toso Co., Ltd.) was used under the conditions of a column temperature of 40 ° C. and a flow rate of 1.0 ml / min. The eluent was measured using tetrahydrofuran, and the weight average molecular weight was measured in terms of standard polystyrene. In addition, three columns of trade names TSK-GEL G5000HHR, G4000HHR, and G3000HHR manufactured by Tosoh Corporation were connected and mounted.

<Adjustment of water repellent composition>
(Examples 1 to 37 and comparative examples 1 to 9)
The water repellent aids (silicone emulsions) obtained in Synthesis Examples 1 to 8 and the polymer dispersions obtained in Synthesis Examples 9 to 36 were mixed at the mass ratios shown in Tables 11 to 15 to form a water repellent composition. I made it a thing.

The water repellent composition obtained above was evaluated.

(Evaluation of water repellency of textile products)
The test was conducted with the shower water temperature set to 27 ° C. according to the spray method of JIS L 1092 (1998). In this test, a treated solution obtained by diluting a dyed 100% polyester cloth or 100% nylon cloth with water so that the water-repellent composition of Examples and Comparative Examples has a polymer content of 3% by mass. After being immersed in (pickup rate 60% by mass), dried at 130 ° C. for 2 minutes, and further heat-treated under the conditions shown in Tables 7 to 10, the water repellency of the obtained cloth was evaluated. The results were visually evaluated according to the following grades. When the characteristics were slightly good, "+" was added to the grade, and when the characteristics were slightly inferior, "-" was added to the grade. The results are shown in Tables 16-22.
Water repellency: Condition 5: No wetness adhered to the surface 4: Slightly adhered to the surface Wetness 3: Partial wetness on the surface 2: Wetness on the surface 1: Wetness on the entire surface Item 0: Both front and back sides are completely moist.

(Evaluation of texture of textile products)
For the texture, the dyed 100% polyester cloth was immersed in a treatment liquid obtained by diluting the water-repellent composition of Examples and Comparative Examples with water so that the polymer content was 3% by mass (pickup rate). After 60% by mass), the mixture was dried at 130 ° C. for 2 minutes and further heat-treated at 170 ° C. for 30 seconds for evaluation. The results were evaluated by handling in the following five stages. The results are shown in Tables 16-22.
1: Hard ~ 5: Soft

(Evaluation of durable water repellency of textile products)
The test was conducted with the shower water temperature set to 27 ° C. according to the spray method of JIS L 1092 (1998). In this test, the dyed 100% polyester cloth has a polymer content of 3% by mass and a UNIKA RESIN 380-K (bridge agent, Union Chemical Industry Co., Ltd., trimetylol melamine resin) content of 0. Water repellents of Examples and Comparative Examples so that the content of 3% by mass and UNIKA CATALYST 3-P (surface active agent, manufactured by Union Chemical Industry Co., Ltd., aminoalcohol hydrochloride) is 0.2% by mass. A cloth (L-) obtained by immersing the composition and each of the above chemicals in a treatment liquid diluted with water (pickup rate 60% by mass), drying at 130 ° C. for 2 minutes, and further heat-treating at 170 ° C. for 60 seconds. The water repellency of the cloth after washing by the 103 method of 0) and JIS L 0217 (1995) 10 times (L-10) was evaluated in the same manner as in the above water repellency evaluation method. The 100% nylon cloth was also evaluated in the same manner as the 100% polyester cloth, except that the heat treatment temperature was changed from 170 ° C to 160 ° C. The results are shown in Tables 16-22.

(Peeling strength against textile coating)
The test was conducted in accordance with JIS K 6404-5 (1999). In this test, the dyed 100% nylon cloth is immersed in a treatment liquid obtained by diluting the water-repellent composition of Examples and Comparative Examples with water so that the polymer content is 3% by mass (pickup). The base cloth was obtained by drying at 130 ° C. for 2 minutes and further heat-treating at 160 ° C. for 30 seconds. A hot melt adhesive tape (“MELCO tape” manufactured by Sun Kasei Co., Ltd.) was heat-bonded to the obtained base cloth at 150 ° C. for 1 minute using a thermocompression bonding device, and the layers between the base cloth and the seam tape were peeled off. The intensity was measured by an autograph (AG-IS, manufactured by Shimadzu Corporation). The moving speed of the grip was pulled at 100 mm / min, and the average value of stress was taken as the peel strength [N / inch]. The results are shown in Tables 16-22.

The textile products treated with the water repellent compositions of Examples 1 to 37 are the conventional fluorine-based water repellent (Comparative Example 7) and the organore represented by the above general formula (1) even when not heat-treated. It was confirmed that the water repellency was equal to or higher than that when only the modified silicone (Comparative Example 8) was used, the durability and water repellency were excellent, and the texture was also good.

Further, when the textile product treated with the water repellent composition of Examples 1 to 37 uses the water repellent composition (Comparative Example 9) containing no organomodified silicone represented by the above general formula (1). It was confirmed that the water repellency was equal to or higher than that of the resin coating, the durability and water repellency were excellent, and the peel strength against the resin coating was excellent.

The water repellent compositions of Comparative Examples 1 to 6 used silicones other than the organomodified silicone represented by the above general formula (1), and tended to be particularly inferior in durable water repellency.

Claims (10)

A water-repellent aid for non-fluorine-based water-repellent agents, which comprises an organomodified silicone represented by the following general formula (1).

[In the 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 is a carbon having an aromatic ring. Represents a hydrocarbon group of 8 to 40 or an alkyl group of 3 to 22 carbons, where R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independent hydrogen atoms, methyl groups and ethyls, respectively. A group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 3 to 22 carbon atoms, a represents an integer of 0 or more, and b represents 1. Representing the above integers, (a + b) is 10 to 200, and when a is 2 or more, a plurality of R ²⁰ and R ²¹ may be the same or different, and when b is 2 or more. , A plurality of R ²² and R ²³ may be the same or different from each other. ] A non-fluorine-based water-repellent composition comprising the water-repellent aid according to claim 1 and a non-fluorine-based water-repellent agent. Claimed that the non-fluorine-based water repellent agent contains a non-fluorine-based polymer containing a structural unit derived from the (meth) acrylic acid ester monomer (A) represented by the following general formula (A-1). 2. The non-fluorine-based water repellent composition according to 2.

[In the formula (A-1), R ¹ represents a hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent. ] The non-fluorinated polymer is (B1) a compound represented by the following general formula (I-1) having an HLB of 7 to 18, and (B2) a compound represented by the following general formula (II-1) having an HLB of 7 to 18. At least one selected from the compounds represented and compounds in which an alkylene oxide having 2 to 4 carbon atoms is added to a fat or oil having a (B3) HLB of 7 to 18 and having a hydroxyl group and a polymerizable unsaturated group. The non-fluorine-based water repellent composition according to claim 3, further containing a structural unit derived from the reactive emulsifier (B).

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

[In formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² contains an alkyleneoxy group having 2 to 4 carbon atoms. Represents a divalent group. ] The non-fluorine-based water repellent according to claim 3 or 4, wherein the non-fluorine-based polymer further contains a structural unit derived from at least one of vinyl chloride and vinylidene chloride, the monomer (E). Composition. The non-fluorine-based water repellent is a non-emulsion or dispersion obtained by emulsifying or dispersing a emulsion or dispersion containing a (meth) acrylic acid ester monomer (A) represented by the following general formula (A-1). The non-fluorine-based water repellent composition according to claim 2, which comprises a fluorine-based polymer.

[In the formula (A-1), R ¹ represents a hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent. ] The emulsion or dispersion is a compound represented by the following general formula (I-1) in which (B1) HLB is 7 to 18, and the following general formula (II-1) in which (B2) HLB is 7 to 18. ) And (B3) a compound having an HLB of 7 to 18 and having an alkylene oxide having 2 to 4 carbon atoms added to a fat or oil having a hydroxyl group and a polymerizable unsaturated group. The non-fluorinated water repellent composition according to claim 6, further comprising the reactive emulsifier (B) of the species.

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

[In formula (II-1), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² contains an alkyleneoxy group having 2 to 4 carbon atoms. Represents a divalent group. ] The non-fluorine-based water repellent composition according to claim 6 or 7, wherein the emulsion or the dispersion further contains a monomer (E) of at least one of vinyl chloride and vinylidene chloride. The non-fluorine-based water repellent composition according to any one of claims 3 to 8, wherein the content of the organomodified silicone is 1 to 50 parts by mass with respect to 100 parts by mass of the non-fluorine-based polymer. A method for producing a water-repellent textile product, comprising a step of treating the textile product with a treatment liquid containing the non-fluorine-based water repellent composition according to any one of claims 2 to 9.