JP6741442B2 - Water repellent aid, non-fluorine-based water repellent composition, and method for producing water repellent fiber product - Google Patents

Description

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

BACKGROUND ART Conventionally, a fluorine-based water repellent having a fluorine-containing group has been known, and a textile product having a surface thereof provided with water repellency by treating such a fluorine-based water repellent agent into a textile product or the like is known. .. Such a fluorine-based water repellent is generally produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group.

Textile products treated with a fluorine-based water repellent agent exhibit excellent water repellency, but in order to exhibit water repellency, it is necessary to adjust the orientation of the fluoroalkyl groups, so the fiber product has a fluorine-based water repellent property. After applying the agent, heat treatment must be performed at a temperature above 130°C. However, heat treatment at high temperature requires high energy, which is a problem in the international trend of energy saving.

Further, a monomer having a fluoroalkyl group is expensive and is not satisfactory in economic terms. Further, a monomer having a fluoroalkyl group is difficult to decompose, which causes environmental problems. There is.

On the other hand, in the field of water repellent finishing of textiles, a water repellent capable of imparting excellent water repellency to a textile even at a low concentration and a low heat treatment temperature is desired for stabilizing quality and reducing costs. ..

Therefore, in recent years, research has been conducted on a non-fluorine-based water repellent containing no fluorine. For example, Non-Patent Document 1 discloses a water repellent 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 obtained by emulsifying and dispersing a specific non-fluorine-based polymer for the purpose of imparting water repellency comparable to that of a conventional fluorine-based water repellent.

"Overall water-repellent treatment, new trends in processing agents and moisture-permeable waterproof materials," Osaka Chemical Marketing Center Co., Ltd., 1996, p. 7-9

JP, 2006-328624, A

However, conventional water repellents may not be able to obtain sufficient durable water repellency.

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, and a non-fluorine-based water repellent composition using the same. , And a method for producing a water-repellent fiber product.

The present invention provides a water repellent aid for a non-fluorine-based water repellent, which comprises an organo-modified 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 atom having an aromatic ring. Represents a hydrocarbon group having 8 to 40 carbon atoms or an alkyl group having 3 to 22 carbon atoms, and R ³⁰ , R ³¹ , R ³² , R ³³ , R ^34, and R ³⁵ each independently represent a hydrogen atom, a methyl group, or ethyl. 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 Represents the above integer, (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. ]

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

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

The non-fluorine-based water repellent may include 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 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-fluorine-based polymer is a compound represented by the following general formula (I-1) in which (B1) HLB is 7 to 18 and a general formula (II-1) in which (B2) HLB is 7 to 18 At least one compound selected from the compounds represented and (B3) HLB of 7 to 18 and 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. 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 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. It 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。］

Wherein (II-1), ^{R 4} represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, ^{Y 2} is includes an alkyleneoxy group having 2 to 4 carbon atoms Represents a divalent group. ]

The non-fluorine-based polymer may further contain a constituent unit derived from at least one monomer (E) selected from vinyl chloride and vinylidene chloride.

The non-fluorine-based water repellent is 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 emulsified product or the dispersion has the compound (B1) represented by the general formula (I-1) in which HLB is 7 to 18, and the general formula (II-1) in which (B2) HLB is 7 to 18. ) And a compound represented by (B3) HLB of 7 to 18 and a compound 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. A seed reactive emulsifier (B) may also be included.

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

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

The present invention also provides a method for producing a water-repellent fiber product, which comprises a step of treating the fiber 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, by using the non-fluorine-based water repellent composition containing the water repellent aid according to the present invention, a water-repellent fiber product excellent in durable water repellency can be stabilized. Can be manufactured. In addition, the method for producing a water-repellent fiber product of the present invention does not require heat treatment at high temperature, and therefore energy saving can be achieved, and since a non-fluorine-based water repellent is used, it is possible to improve the environment. 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 and a non-fluorine-based water repellent composition containing the same.

Further, the non-fluorine-based water repellent composition of the present invention shows excellent water repellency even though it is a water repellent composition containing no compound having a fluoroalkyl group or fluorine, and is an alternative to the fluorine-based water repellent. As a result, it is possible to eliminate the concern about the influence on the fluorine supply source and the environment. It should be noted that after the water repellent composition is attached to the textile product or the like, it is usually preferable to perform heat treatment, 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 of higher than 130° C. Can be shorter than. Therefore, deterioration of the object to be processed due to heat is suppressed, the texture becomes flexible, and the heat amount required for the heat treatment can be reduced.

Furthermore, according to the present invention, a water-repellent composition is obtained by using a specific reactive emulsifier instead of a general surfactant as an emulsifying dispersant used for emulsion or dispersion polymerization of a non-fluorine-based polymer. 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 that of the conventional non-fluorine-based water repellent.

The water repellent aid for the non-fluorine-based water repellent of the present embodiment contains an organo-modified silicone represented by the following general formula (1). In the general formula (1) below, each structural unit may be a block, may be 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 atom having an aromatic ring. Represents a hydrocarbon group having 8 to 40 carbon atoms or an alkyl group having 3 to 22 carbon atoms, and R ³⁰ , R ³¹ , R ³² , R ³³ , R ^34, and R ³⁵ each independently represent a hydrogen atom, a methyl group, or ethyl. 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 Represents the above integer, (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. ]

In the organo-modified silicone of the present embodiment, the alkoxy group having 1 to 4 carbon atoms may be linear or branched. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group and the like. It is preferable that R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group, and more preferably a methyl group, from the viewpoint of easy industrial production and easy availability.

Examples of the hydrocarbon group having 8 to 40 carbon atoms having the 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 ^{41 s} may be the same or different. ]

The 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 ^43's may be the same or different. ]

The alkylene group may be linear or branched.

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

In the group represented by the above general formula (2), R ⁴⁰ is preferably an alkylene group having 2 to 4 carbon atoms, and c is 0 or 1 from the viewpoints of easy industrial production and easy availability. Preferably, it is 0, more preferably 0.

In the group 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 from the viewpoints of easy industrial production and easy availability. Preferably, it is 0, more preferably 0.

The above-mentioned hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring is easily produced industrially and is easily available, and thus the aralkyl group having 8 to 40 carbon atoms and the above general formula ( The group represented by 2) is preferable, and the above aralkyl group having 8 to 40 carbon atoms is more preferable in that the water repellency of the obtained fiber product can be improved.

The alkyl group having 3 to 22 carbon atoms may be linear or branched. Examples of the alkyl group having 3 to 22 carbon atoms include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, myristyl group, cetyl group, stearyl group and the like. 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, from the viewpoint that the water repellency of the obtained fiber product can be improved.

In the organo-modified silicone of the present embodiment, 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, an alkoxy group having 1 to 4 carbon atoms, or an aroma. It is a C8-C40 hydrocarbon group having a group ring, or a C3-C22 alkyl group. 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, or a carbon number of 1 from the viewpoint of easy industrial production and easy availability. It is preferably an alkoxy group of 4 to 4, and more preferably a methyl group.

In the organo-modified silicone of the present embodiment, a is an integer of 0 or more. A is preferably 40 or less, and more preferably 30 or less from the viewpoints of easy industrial production, easy availability, and more excellent peeling strength of the obtained fiber product with respect to the resin coating.

In the organo-modified silicone of the present embodiment, (a+b) is 10 to 200. (A+b) is preferably 20 to 100, and more preferably 40 to 60 from the viewpoint of easy industrial production and easy availability. When (a+b) is within the above range, the production and handling of the silicone itself tend to be easy.

The organo-modified silicone of this embodiment can be synthesized by a conventionally known method. The organo-modified silicone of the present embodiment can be obtained, for example, by subjecting a silicone having a SiH group to a hydrosilylation reaction of an aromatic compound having a vinyl group and/or an α-olefin.

Examples of the SiH group-containing silicone include methyl hydrogen silicone having a polymerization degree of 10 to 200, a copolymer of dimethyl siloxane and methyl hydrogen siloxane, and the like. Among these, methylhydrogen silicone is preferable because it is easily industrially produced and easily available.

The 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 is derived from R ²³ in the general formula (1). Examples of the aromatic compound having a vinyl group include styrene, α-methylstyrene, vinylnaphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-cumyl phenyl ether, allyl-o-phenyl phenyl ether, allyl-triene. (Phenylethyl)-phenyl ether, allyl-tri(2-phenylpropyl)phenyl ether and the like can be mentioned.

The above α-olefin is a compound from which an alkyl group having 3 to 22 carbon atoms is derived in R ²³ in the above 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, Examples thereof include α-olefins having 3 to 22 carbon atoms such as 1-hexadecene and 1-octadecene.

The above hydrosilylation reaction is carried out by reacting the above SiH group-containing silicone with the above vinyl group-containing aromatic compound and the above α-olefin stepwise or all at once in the presence of a catalyst. Good.

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

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

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

In addition, the hydrosilylation reaction is preferably performed in an inert gas atmosphere. Examples of the inert gas include nitrogen and argon. Although the reaction proceeds even without 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 this embodiment will be described.

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

The non-fluorine-based water repellent is excellent in storage stability and can impart sufficient water repellency to a textile product even without heat treatment, and is a water repellent textile product excellent in texture and water repellency. 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 “(A) component”), in that It is preferable to include a non-fluorine-containing 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 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. is there.

The (meth)acrylic acid ester monomer (A) represented by the general formula (A-1) used in the present embodiment has 1 or more carbon atoms which may have a substituent. It has a valent hydrocarbon group. This 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, linear ones are preferable, and linear alkyl groups are more preferable. In this case, the water repellency will be more excellent. When the monovalent hydrocarbon group having 12 or more carbon atoms has a substituent, the substituent includes 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 the like. In the present embodiment, in the general formula (A-1), R ² is preferably an unsubstituted hydrocarbon group.

The hydrocarbon group preferably has 12 to 24 carbon atoms. When 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 fiber product tends to be coarse and hard when the non-fluorine-based polymer is attached to the fiber product or the like, as compared with the case where the carbon number is in the above range. ..

More preferably, the hydrocarbon group has 12 to 21 carbon atoms. When the carbon number is in this range, the water repellency and the feel become particularly excellent. Particularly preferable 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, Heptadecyl (meth)acrylate, Nonadecyl (meth)acrylate, Eicosyl (meth)acrylate, Heneicosyl (meth)acrylate, Behenyl (meth)acrylate, Ceryl (meth)acrylate, Melisyl (meth)acrylate Is 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, which can react with a crosslinking 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 resulting fiber 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) from the viewpoint of durable water repellency of the resulting fiber product. The ratio (a1)/(a2) of the mass of the (a1) component and the mass of the (a2) component to be blended is preferably 30/70 to 90/10, and 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) is more than 90/10 or less than 30/70, the durable water repellency of the obtained textile product tends to decrease.

From the viewpoint of water repellency and durable water repellency of the resulting fiber product, the total constituent ratio of the above-mentioned monomer of the component (A) in the non-fluorine-based polymer is based on the total amount of the monomer components constituting the non-fluorine-based polymer. It is preferably 50 to 100% by mass, more preferably 55 to 97% by mass, and further preferably 60 to 95% by mass.

The weight average molecular weight of the non-fluorine-based polymer is preferably 100,000 or more. When the weight average molecular weight is less than 100,000, the water repellency of the resulting fiber product tends to be insufficient. Further, the weight average molecular weight of the non-fluorine-based polymer is more preferably 500,000 or more. In this case, the obtained fiber product can exhibit water repellency more sufficiently. The upper limit of the weight average molecular weight of the non-fluorine-based polymer is preferably about 5,000,000.

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 fiber product tends to be coarse and hard. Further, if the melt viscosity of the non-fluorine-based polymer is too high, when the non-fluorine-based polymer is emulsified or dispersed into a water repellent composition, the non-fluorine-based polymer may be precipitated or settled, and The storage stability of the liquid preparation 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 and the like exhibit excellent water repellency and also have a better feeling.

“Melt viscosity at 105° C.” means that an elevated flow tester (for example, CFT-500 manufactured by Shimadzu Corporation) is used and 1 g of a non-fluorine-containing polymer is put in a cylinder equipped with a die (length 10 mm, diameter 1 mm). Viscosity when measured at a temperature of 105° C. for 6 minutes by 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 fiber product tends to be. Further, by copolymerizing a non-fluorine-based monomer that can be copolymerized, it is possible to improve the performance such as the durable water repellency and the feel of the attached fiber product.

The non-fluorine-based polymer is added to the component (A) in that it can improve the water repellency of the resulting fiber product and the emulsion stability of the non-fluorine-based polymer during or after emulsion polymerization or dispersion polymerization in the composition. And (B1) HLB is 7 to 18, a compound represented by the following general formula (I-1), (B2) HLB is 7 to 18, a compound represented by the following general formula (II-1), And (B3) at least one reactive emulsifier (B) selected from the compound in which an HLB is 7 to 18 and 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. ) (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 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. It 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。］

Wherein (II-1), ^{R 4} represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, ^{Y 2} is includes an alkyleneoxy group having 2 to 4 carbon atoms Represents a divalent group. ]

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

Further, "HLB" is an HLB value calculated by the Griffin method by regarding ethyleneoxy groups as hydrophilic groups and all other groups as lipophilic groups.

The HLB of the compounds (B1) to (B3) used in this embodiment is 7 to 18, and the emulsion stability of the non-fluorine-based polymer during emulsion polymerization or dispersion polymerization and in the composition after polymerization is stable. From the viewpoint of the property (hereinafter, simply referred to as emulsion stability), 9 to 15 is 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 from the viewpoint of storage stability of the non-fluorine-based water repellent.

In the reactive emulsifier (B1) represented by the general formula (I-1) used in the present embodiment, R ³ is hydrogen or a methyl group, and in view 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-fluorine-based 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 additions of the alkyleneoxy group in Y ¹ can be appropriately selected so as to fall within the above HLB range. When two or more alkyleneoxy groups are used, they can have a block addition structure or a random addition structure.

As the compound represented by the general formula (I-1), a 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 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 alkyleneoxy group having 2 to 4 carbon atoms. And m can be appropriately selected so as to fall 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. Or they may be different. ]

In the compound represented by the general formula (I-2), R ³ is hydrogen or a methyl group, and more preferably a methyl group from the viewpoint 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-fluorine-based polymer. A ¹ O is an alkyleneoxy 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 above HLB range. From the viewpoint of emulsion stability of the non-fluorine-based polymer, m is preferably an integer of 1 to 80, more preferably an integer of 1 to 60. When m is 2 or more, m A ¹ O may be the same or different. Further, when two or more kinds of A ¹ O are used, 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, they can be easily obtained from commercial products, and examples thereof include "Latemul PD-420", "Latemul PD-430", "Latemul PD-450" manufactured by Kao Corporation.

In the reactive emulsifier (B2) represented by the general formula (II-1) used in the present embodiment, R ⁴ is a monovalent unsaturated carbon atom having a polymerizable unsaturated group and having 13 to 17 carbon atoms. Hydrogen group, such as tridecenyl group, tridecadienyl group, tetradecenyl group, tetradienyl group, pentadecenyl group, pentadecadienyl group, pentadecatrienyl group, heptadecenyl group, heptadecadienyl group, heptadecatrienyl group and the like. .. From the viewpoint of emulsion stability of the non-fluorine-based polymer, R ⁴ 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 additions of the alkyleneoxy group in Y ² can be appropriately selected so as to fall within the above HLB range. When two or more alkyleneoxy groups are used, they can have a block addition structure or a random addition structure. From the viewpoint of emulsion stability of the non-fluorine-based polymer, the alkyleneoxy group is more preferably an ethyleneoxy group.

As the compound represented by the general formula (II-1), a 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), R ⁴ represents a C 13 to C 17 monovalent unsaturated hydrocarbon group having a polymerizable unsaturated group, and A ² O represents a C ^{2 to} C 4 alkyleneoxy group. , N can be appropriately selected so as to fall within the above HLB range. Specifically, an integer of 1 to 50 is preferable, and when n is 2 or more, n A ² O are the same. May also be different. ]

^{R 4} in the compound represented by the above Formula (II-2) are the same as those for ^{R 4} in the above-mentioned general formula (II-1).

A ² O is an alkyleneoxy group having 2 to 4 carbon atoms. From the viewpoint of emulsion stability of the non-fluorine-based polymer, the type and combination of A ² O and the number of n can be appropriately selected so as to fall within the above HLB range. From the viewpoint of emulsion stability of the non-fluorine-based 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 two or more kinds of A ² O are used, they can 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 is obtained by adding an alkylene oxide to a corresponding phenol having an 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 under pressure at 120 to 170° C. using an alkali catalyst such as caustic soda and caustic potassium.

The above-mentioned phenols having an unsaturated hydrocarbon group include not only industrially produced pure products or mixtures, but also those existing as purified products or mixtures extracted from plants and the like. For example, 3-[8(Z),11(Z),14-pentadecatrienyl]phenol and 3-[8(Z),11(Z), which are extracted from cashew nut shells and are collectively called cardanol. -Pentadecadienyl]phenol, 3-[8(Z)-pentadecenyl]phenol, 3-[11(Z)-pentadecenyl]phenol and the like.

The reactive emulsifier (B3) used in the present embodiment is a compound having an HLB of 7 to 18 and an alkylene oxide having 2 to 4 carbon atoms added to an oil or fat 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, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.). Examples thereof include mono- or diglycerides of fatty acids, and triglycerides of fatty acids containing at least one kind of hydroxy unsaturated fatty acid (ricinoleic acid, ricinoelaidic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of the emulsion stability of the non-fluorine-based polymer, an alkylene oxide adduct of a triglyceride of a fatty acid containing at least one hydroxyunsaturated fatty acid is preferable, and a castor oil (triglyceride of a fatty acid containing ricinoleic acid) has 2 to 4 carbon atoms. The alkylene oxide adduct of is more preferable, and the ethylene oxide adduct of castor oil is further preferable. Furthermore, the number of moles of alkylene oxide added can be appropriately selected so as to fall within the range of the above HLB, and from the viewpoint of emulsion stability of the non-fluorine-based polymer, 20 to 50 moles is more preferable, and 25 to 45 moles. Is more preferable. When two or more alkylene oxides are used, 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 not particularly limited. Not a thing. For example, triglyceride of fatty acid containing ricinoleic acid, that is, it can be synthesized by adding a predetermined amount of alkylene oxide to castor oil at 120 to 170° C. under pressure using an alkali catalyst such as caustic soda and potassium hydroxide. ..

The composition ratio of the above-mentioned component (B) monomer in the non-fluorine-based polymer is such that the water repellency of the obtained fiber product and the emulsion stability of the non-fluorine-based polymer during and after emulsion polymerization or dispersion polymerization are stable in the composition. From the viewpoint of improving the property, the amount is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and more preferably 3 to the total amount of the monomer components constituting the non-fluorine-based polymer. It is more preferably from 10 to 10% by mass.

The non-fluorine-based polymer contained in the non-fluorine-based water repellent is capable of improving the durable water repellency of the resulting fiber product, and in addition to the component (A), the following (C1), (C2), (C3), 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 Preferably.

［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。］ (Meth)acrylic acid ester monomer represented by the following general formula (C-1) other than (C1) and (C5)

[In the formula (C-1), R ⁵ represents hydrogen or a 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) (Meth)acrylic acid ester monomer represented by the following general formula (C-2)

[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 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 the 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) (Meth)acrylic acid ester monomer represented by the following general formula (C-4)

[In formula (C-4), R ¹⁰ represents hydrogen or a 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. 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) (Meth)acrylic acid ester monomer represented by the following general formula (C-5)

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

The monomer of (C1) has a carbon number having 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 portion. 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). From the viewpoint of reacting with a crosslinking agent, 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. It is preferable to have a functional group. When a non-fluorine-containing polymer containing a monomer of (C1) having a group capable of reacting with these cross-linking agents is treated with a cross-linking agent into a fiber product, while maintaining the texture of the resulting fiber product, The durable water repellency can be improved. The isocyanate group may be a blocked isocyanate group protected with 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, in terms of improving the durable water repellency of the obtained fiber product, it is preferably linear and/or saturated hydrocarbon group.

Specific examples of the monomer (C1) include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl. Isocyanate and the like can be mentioned. 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)ethylisocyanate are preferable because the durable water repellency of the obtained fiber product can be improved. Further, dimethylaminoethyl (meth)acrylate is preferable from the viewpoint of improving the feel of the obtained fiber product.

The composition ratio of the monomer (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 resulting fiber product. -30 mass% is preferred, 3-25 mass% is more preferred, and 5-20 mass% is even more preferred.

The monomer of (C2) is a (meth)acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester portion, and the cyclic hydrocarbon group includes an isobornyl group, Examples thereof include cyclohexyl group and 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 in which the total number of carbon atoms of the substituent and the cyclic hydrocarbon group is 11 or less is selected. Further, it is preferable that these cyclic hydrocarbon groups are directly bonded to an ester bond from the viewpoint of improving durable water repellency. The cyclic hydrocarbon group may be alicyclic or aromatic, and when it is alicyclic, it may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Specific monomers 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 these, isobornyl (meth)acrylate and cyclohexyl methacrylate are preferable, and isobornyl methacrylate is more preferable, from the viewpoint that the durable water repellency of the obtained fiber product can be improved.

The composition ratio of the monomer (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 resulting fiber product. -30 mass% is preferred, 3-25 mass% is more preferred, and 5-20 mass% is even more preferred.

The above-mentioned 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 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 preferable. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group and the like. Specific compounds 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. Of these, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferable, and methyl methacrylate is more preferable, from the viewpoint that the durable water repellency of the obtained fiber product can be improved.

From the viewpoint of water repellency and texture of the resulting fiber product, the composition ratio of the above-mentioned (C3) monomer in the non-fluorine-based polymer is 1 with respect to the total amount of the monomer components constituting the non-fluorine-based polymer. -30 mass% is preferred, 3-25 mass% is more preferred, and 5-20 mass% is even more preferred.

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

From the viewpoint of water repellency and texture of the resulting fiber product, the composition ratio of the above-mentioned (C4) monomer in the non-fluorine-based polymer is 1 with respect to the total amount of the monomer components constituting the non-fluorine-based polymer. -30 mass% is preferred, 3-25 mass% is more preferred, and 5-20 mass% is even more preferred.

The above-mentioned (C5) monomer has a monovalent chained 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 above (C5) monomer, R ¹¹ is hydrogen or a methyl group. From the viewpoint of durable water repellency of the resulting textile product, R ¹¹ is preferably a methyl group.

R ¹² is a monovalent chain saturated hydrocarbon group having 3 to 6 carbon atoms and having a hydroxyl group and at least one functional group selected from the group consisting of a chloro group and a bromo group. The chain saturated hydrocarbon group may be linear or branched. When the chain saturated hydrocarbon group is a straight chain, the resulting textile product has more excellent durable water repellency. The chain saturated hydrocarbon group preferably has 3 to 4 carbon atoms, more preferably 3 carbon atoms, from the viewpoint of durable water repellency of the resulting fiber product.

The chain saturated hydrocarbon group preferably has one or two chloro groups and one hydroxyl group in terms of durability and water repellency of the resulting fiber product, and one chloro group, It is more preferable to have one hydroxyl group. In addition, in terms of durable water repellency of the resulting fiber product, the chain saturated hydrocarbon group has a hydroxyl group at the β-position (the carbon atom adjacent 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 a 3-chloro-2-hydroxypropyl group, a 3-chloro-2-hydroxybutyl group, a 5-chloro-2-hydroxypentyl group, and a 3-chloro-2 group. -Hydroxy-2-methylpropyl group and 3-bromo-2-hydroxypropyl group.

Specific examples of the (C5) monomer include, for example, 3-chloro-2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxybutyl (meth)acrylate, and 5-(meth)acrylic acid. Examples include chloro-2-hydroxypentyl and 3-bromo-2-hydroxypropyl (meth)acrylate. Among these, 3-chloro-2-hydroxypropyl (meth)acrylate is preferable, and 3-chloro-2-hydroxypropyl methacrylate is more preferable, from the viewpoint that the durable water repellency of the obtained fiber product can be improved.

The composition ratio of the monomer (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 fiber product. It is preferably mass%, more preferably 3 to 25 mass%, and further preferably 5 to 20 mass%.

From the viewpoint of water repellency and texture of the obtained fiber product, the total constituent ratio of the above-mentioned monomer of the component (C) in the non-fluorine-based polymer is based on the total amount of the monomer components constituting the non-fluorine-based polymer. It is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and further preferably 5 to 20% by mass.

The non-fluorine-based polymer contained in the non-fluorine-based water repellent includes, in addition to the components (A), (B) and (C), a monofunctional monomer (D) (hereinafter referred to as a copolymerizable monomer). , (Also referred to as “(D) component”) can be contained within a range that does not impair the effects of the present invention.

Examples of the monomer (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. Ester, maleic acid ester, fumaric acid, maleic acid, (meth)acrylamide, N-methylol acrylamide, vinyl ethers, vinyl esters, ethylene, styrene and other vinyl monomers other than the fluorine-free (E) component, etc. Is mentioned. The (meth)acrylic acid ester having a hydrocarbon group other than the components (A) and (C) has a hydrocarbon group, a vinyl group, a hydroxyl group, an amino group, an epoxy group and an isocyanate group, a blocked isocyanate group. May have a substituent such as a quaternary ammonium group, and may have a substituent other than a group capable of reacting with a cross-linking agent such as a quaternary ammonium group, an ether bond, an ester bond, an amide bond, or a urethane bond. Etc. may be included. 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. Is mentioned. Among them, (meth)acryloylmorpholine is more preferable because it can improve the peel strength of the obtained fiber product with respect to the coating.

From the viewpoint of water repellency and feel of the obtained fiber product, 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 of the non-fluorine-based polymer. It is preferably 10% by mass or less.

The non-fluorine-based polymer contained in the non-fluorine-based 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, which is capable of reacting with a crosslinking agent. However, it is preferable since 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. In addition, it is preferable that the non-fluorine-based polymer has an amino group because the texture of the resulting fiber product is improved.

The non-fluorine-based polymer contained in the non-fluorine-based water repellent is capable of improving the water repellency of the resulting fiber product and the peeling strength to the coating, and in addition to the component (A), at least one of vinyl chloride and vinylidene chloride. It is preferable to contain one kind of monomer (E) (hereinafter, also referred to as “(E) component”) as a monomer component.

At least one monomer (E) selected from vinyl chloride and vinylidene chloride used in the present embodiment is preferably vinyl chloride from the viewpoint of water repellency of the resulting textile product and peeling strength against 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 of the non-fluorine-based polymer, from the viewpoint of improving the peel strength of the resulting fiber product with respect to the coating. , 1 to 45% by mass, more preferably 3 to 40% by mass, further preferably 5 to 35% by mass.

If necessary, additives and the like can be added to the water repellent composition of this embodiment. Examples of the additives include other water repellents, cross-linking agents, antibacterial deodorants, flame retardants, antistatic agents, softening agents, wrinkle-proofing agents and the like.

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

The non-fluorine-based water repellent 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 and environment of the water repellent obtained.

For example, a non-fluorine-based polymer can be obtained by emulsion-polymerizing or dispersion-polymerizing the (meth)acrylic acid ester monomer (A) represented by the 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 emulsification aid or dispersion in a medium. An auxiliary agent is added, and this mixed solution is emulsified or dispersed to obtain an emulsion or dispersion. By adding a polymerization initiator to the obtained emulsion or dispersion, the polymerization reaction is initiated, and the monomer and the reactive emulsifier can be polymerized. As a means for emulsifying or dispersing the above-mentioned mixed liquid, a homomixer, a high-pressure emulsifier, an ultrasonic wave or the like can be mentioned.

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

Water is preferable as a 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 a water-miscible organic solvent, for example, alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, diethyl. Examples thereof include ethers such as ether, and glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol. The ratio of water to organic solvent is not particularly limited.

As the polymerization initiator, a known polymerization initiator such as an azo type, a peroxide type, or a 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 all the monomers. 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 part by mass or less, and more preferably 0.1 part 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 to adjust the molecular weight. By adding the polymerization inhibitor, a non-fluorine-based 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. When the temperature is lower than 20°C, the polymerization tends to be insufficient as compared with the case where the temperature is in the above range, and when 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-fluorine-based polymer 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. In addition, when 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-fluorine-containing polymer in the polymer emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization is 10 to 50 relative to the total amount of the emulsion or dispersion from the viewpoint of storage stability and handling property of the composition. It is preferable to set it as mass %, and it is more preferable to set it as 20-40 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.

The content of the organo-modified silicone represented by the general formula (1) in the non-fluorine-based water repellent composition of the present embodiment is 1 to 10% by mass in terms of durable water repellency of the obtained textile product. It is preferable and it is more preferable that it is 3 to 7 mass %.

In addition, the blending amount of the organo-modified silicone represented by the general formula (1) in the non-fluorine-based water repellent composition of the present embodiment is 100% by weight of the non-fluorinated polymer in terms of durable water repellency of the obtained textile product. The amount 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. There is no particular limitation on the material of such fiber products, such as cotton, hemp, silk, natural fibers such as wool, rayon, semi-synthetic fibers such as acetate, synthetic fibers such as nylon, polyester, polyurethane, polypropylene and composite fibers thereof, Examples include mixed fibers. The form of the fiber product may be any form such as fiber, yarn, cloth, woven fabric, knitted fabric, cloth in the form of clothing, carpet, non-woven fabric, paper and the like.

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, and a processing method by a cleaning method. In addition, when the non-fluorine-based water repellent composition contains water, it is preferably dried to remove water after being attached to the fiber product.

In addition, after the textile product is treated with the non-fluorine-based water repellent composition of the present embodiment, it is preferable to appropriately perform heat treatment. The temperature condition is not particularly limited, but when the non-fluorine-based water repellent composition of the present embodiment is used, it is possible to cause the fiber product to exhibit sufficiently good water repellency under a mild condition of 100 to 130°C. The temperature condition may be a 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 textile product of the present embodiment, deterioration of the textile product due to heat is suppressed, the texture of the textile product during the water-repellent treatment becomes flexible, and under mild heat treatment conditions, that is, low-temperature curing 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 the textile with a treatment liquid containing a non-fluorine-based water repellent composition and one methylol melamine, isocyanate group or blocked isocyanate group It is preferable that the fiber product is subjected to a water-repellent treatment by a method including a step of attaching a crosslinking agent represented by the above compound to the fiber product and heating the same. Furthermore, in order to further improve the durable water repellency, the non-fluorine-based water repellent composition contains a non-fluorine-based polymer obtained by copolymerizing a monomer having a functional group capable of reacting with the above-mentioned crosslinking agent. Is preferred.

Examples of compounds having one or more isocyanate groups include monoisocyanates such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate, and naphthalene isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, and diisocyanates such as hydrogenated diphenylmethane diisocyanate. Examples include trimer which is an isocyanurate ring and trimethylolpropane adduct. Examples of the compound having one or more blocked isocyanate groups include compounds obtained by protecting the isocyanate group-containing compound with 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 bisulfite such as sodium bisulfite and potassium bisulfite. Examples include salt. The above-mentioned cross-linking agents may be used alone or in combination of two or more.

The cross-linking agent is, for example, by dissolving the cross-linking agent in an organic solvent or immersing the article to be treated (fiber product) in a treatment solution obtained by emulsifying and dispersing in water, and drying the treatment solution attached to the article to be treated. It can be attached to the object to be treated. Then, by heating the cross-linking agent attached 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 proceed. In order to sufficiently advance the reaction of the cross-linking agent and improve the washing durability more effectively, the heating at this time is preferably performed at 110 to 180°C for 1 to 5 minutes. The step of attaching the cross-linking agent and the step of heating may be performed simultaneously with the step of treating with the treatment liquid containing the water repellent composition. When simultaneously performed, for example, the treatment liquid containing the water repellent composition and the cross-linking agent is adhered to the object to be treated, water is removed, and then the cross-linking agent attached to the object is further heated. Considering the simplification of the water repellent processing step, the reduction of the amount of heat, and the economical efficiency, it is preferable to perform the step simultaneously with the step of treating the water repellent composition.

Further, excessive use of the crosslinking agent may impair the feeling. 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 material to be treated (textile product).

The water-repellent fiber product of the present embodiment thus obtained can exhibit sufficient water repellency even when used outdoors for a long time, and the water-repellent fiber product uses a fluorine-based compound. Because it doesn't, it can be environmentally friendly.

The water repellent textile product of the present embodiment can be coated on a predetermined portion. Examples of coating processing include moisture-permeable waterproofing and windproofing for sports and outdoor applications. As a processing method, for example, in the case of moisture-permeable waterproofing, a coating liquid containing a urethane resin, an acrylic resin or the like and a medium may be applied to one surface of a water-repellent treated textile product and then dried. it 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-fluorine-based polymer, in the above embodiment, the polymerization reaction is carried out by radical polymerization, but the polymerization reaction is carried out by photopolymerization by irradiation with ultraviolet rays, electron beams, ionizing radiation such as γ rays, or the like. You may go.

Further, in the present invention, the non-fluorine-based water repellent composition is treated into a fiber product to give a water-repellent fiber product. Not limited to this, it may be an article made of metal, glass, resin or the like.

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

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)
63.2 g of methyl hydrogen silicone having a SiH group equivalent of 63.2 g/mol and a degree of polymerization of 50 was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introducing pipe and a dropping funnel. The mixture was charged, flushed with nitrogen, and heated until the temperature reached 65° C., and mixed until uniform. As a hydrosilylation catalyst, a mixed solution of platinum(IV) chloride in ethylene glycol monobutyl ether/toluene was added so that the platinum concentration was 5 ppm with respect to the reaction product in the system. When the temperature of the reaction product reached 120°C, 168.3 g of 1-mol 1-dodecene was added dropwise and the reaction was carried out at 120°C for 6 hours. The completion of the addition reaction was confirmed by performing FT-IR analysis of the obtained organo-modified silicone and confirming that the absorption spectrum derived from the SiH group of methyl hydrogen 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. An organo-modified 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 and mixed with 20 parts by mass of the obtained organo-modified silicone. Next, 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-hexene was used instead of 168.3 g of 1-dodecene. The organo-modified silicone is a in the above general formula (1) in which 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 ^{34. An} organo-modified silicone in which ³⁵ is 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 12.5 mol of 1-octadecene was used instead of 168.3 g of 1-dodecene. In the organo-modified 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 organo-modified silicone having a methyl group was obtained.

(Synthesis example 4)
Similar to 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 an organo-modified silicone and a silicone emulsion. In the organo-modified 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 methylstyrene group, R ³⁰ , R ³¹ , R ³² , R ³³ , and R ³³ . ^An organo-modified silicone in which ³⁴ and R ³⁵ are methyl groups was obtained.

(Synthesis example 5)
The same procedure as in Synthesis Example 1 was repeated 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. To obtain organo-modified silicone and silicone emulsion. In the organo-modified 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 , and R ^34. And an organo-modified silicone in which R ³⁵ is a methyl group were obtained.

(Synthesis example 6)
A dimethylsiloxane having an SiH group equivalent of 140.5 g/mol and a degree of polymerization of 50 instead of 63.2 g of methyl hydrogen silicone having an SiH group equivalent of 63.2 g/mol and a degree of polymerization of 50. An organo-modified silicone and a silicone emulsion were obtained in the same manner as in Synthesis Example 1 except that 140.5 g of a copolymer of methyl hydrogen siloxane was used. In the organo-modified 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 obtain an organo-modified silicone.

(Synthesis example 7)
To 20 parts by mass of hydrogen silicone (trade name: KF-99, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts by mass of an ethylene oxide 9 mol adduct of a branched higher alcohol having 12 to 14 carbon atoms was added and mixed. Next, 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 the hydrogen silicone.

<Preparation of polymer dispersion>
A mixed liquid having the composition shown in Tables 1 to 6 (in the table, the numerical value shows (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 (Daiichi Kogyo Seiyaku Co., Ltd., 2 g of polyoxyalkylene branched decyl ether, HLB=12.5), 3 g of stearyl dimethylamine hydrochloride, 25 g of tripropylene glycol and 207.70 g of water were added and mixed and stirred at 45° C. to obtain a mixed solution. This mixed liquid 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 radical polymerization was carried out at 60° C. for 6 hours under a nitrogen atmosphere to obtain a non-fluorine-containing polymer dispersion having a polymer concentration of 20% by mass. ..

(Synthesis examples 10 to 36)
Polymerization was performed in the same manner as in Synthesis Example 9 except that the materials described in Tables 1 to 6 were used to obtain non-fluorine-containing polymer dispersions having the polymer concentrations shown in Tables 7 to 10.

Each of the polymers in the polymer dispersions obtained in Synthesis Examples 9 to 36 was polymerized by gas chromatography (GC-15APTF, manufactured by Shimadzu Corporation) in which 98% or more of all monomers were polymerized. Was confirmed.

Details of the materials shown in Tables 1 to 6 are as follows.
Latemur PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB=12.6)
Latemur PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB=14.4)
12.5 mol of ethylene oxide adduct of cardanol (HLB=12.9, shown as "cardanol 12.5EO" in the table)
8.3 mol of ethylene oxide adduct of cardanol (HLB=11.0, shown as "cardanol 8.3EO" in the table)
42 mol ethylene oxide adduct of castor oil (HLB=13.3, shown as "castor oil 42EO" in the table)
30 mol ethylene oxide adduct of castor oil (HLB=11.7, shown 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。 "C8 fluoro group-containing acrylate" in the table means the following general formula (III):

And a compound having an average value of n of 8 (the compound having n of 6, 8, 10, 12, 14 is mixed in the mixture).

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

(Evaluation of physical properties of polymer)
The polymer and the emulsifier were separated by adding 500 mL of acetone to 50 g of the polymer dispersions obtained in Synthesis Examples 9 to 36, and 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 placed in a cylinder equipped with a die (length 10 mm, diameter 1 mm) using an elevated flow tester CFT-500 (manufactured by Shimadzu Corporation). 1 g, was held for 6 minutes at 105° C., a load of 100 kg·f/cm ² was applied by a plunger, and the melt viscosity at 105° C. was measured.

(2) Method for measuring weight average molecular weight The polymer obtained above was analyzed with a GPC device (GPC "HLC-8020" manufactured by Tosoh Corporation) under a column temperature of 40°C and a flow rate of 1.0 ml/min. Tetrahydrofuran was used as an eluent, and the weight average molecular weight was measured in terms of standard polystyrene. In addition, the column was connected and equipped with three pieces of trade name TSK-GEL G5000HHR, G4000HHR, and G3000HHR manufactured by Tosoh Corporation.

<Preparation of water repellent composition>
(Examples 1-37 and Comparative Examples 1-9)
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 prepare a water repellent composition. It was a thing.

The water repellent composition obtained above was evaluated.

(Evaluation of water repellency of textile products)
Tests were carried out at a shower water temperature of 27° C. according to the spray method of JIS L 1092 (1998). In this test, a treated liquid prepared by diluting a dyed polyester 100% cloth or nylon 100% cloth with water so that the water repellent composition of each of Examples and Comparative Examples had a polymer content of 3% by mass. After the immersion treatment (pickup rate 60% by mass), it was dried at 130° C. for 2 minutes and further heat-treated under the conditions shown in Tables 7 to 10 to evaluate the water repellency of the obtained cloth. The results were visually evaluated according to the following grades. When the characteristics were slightly good, "+" was attached to the grade, and when the characteristics were slightly inferior, "-" was attached to the grade. The results are shown in Tables 16-22.
Water repellency: State 5: No adhesion and wetting on the surface 4: Slight adhesion and wetting on the surface 3: Partial wetting on the surface 2: Wetting on the surface 1: Wetting on the entire surface Thing 0: Those on which both front and back surfaces are completely wet

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

(Evaluation of durable water repellency of textile products)
Tests were carried out at a shower water temperature of 27° C. according to the spray method of JIS L 1092 (1998). In this test, the dyed polyester 100% cloth has a polymer content of 3% by mass and a content of UNIKA RESIN 380-K (crosslinking agent, trimethylolmelamine resin manufactured by Union Chemical Industry Co., Ltd.) of 0%. The water repellents of Examples and Comparative Examples so that the content of 0.3 mass% and UNIKA CATALLYST 3-P (surfactant, manufactured by Union Chemical Industry Co., Ltd., amino alcohol hydrochloride) is 0.2 mass %. The composition and the above chemicals were immersed in a treatment solution diluted with water (pickup rate 60% by mass), dried at 130° C. for 2 minutes, and further heat-treated at 170° C. for 60 seconds to obtain a cloth (L- 0), and the water repellency of the cloth after washing 10 times (L-10) according to the method 103 of JIS L 0217 (1995) were evaluated in the same manner as the water repellency evaluation method. Also, in the case of 100% nylon cloth, the evaluation was performed in the same manner as in the case of 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.

(Peel strength against coating of textile products)
The test was conducted according to JIS K 6404-5 (1999). In this test, a dyed nylon 100% cloth was dipped (picked up) in a treatment liquid prepared by diluting the water repellent compositions of Examples and Comparative Examples with water so that the polymer content was 3% by mass. (60% by weight), dried at 130° C. for 2 minutes, and further heat-treated at 160° C. for 30 seconds to obtain a base fabric. 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 by using a thermocompression bonding apparatus, and the base cloth and the seam tape were separated from each other. The strength was measured with an autograph (AG-IS, manufactured by Shimadzu Corporation). The moving speed of the gripping tool 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 fiber products treated with the water repellent compositions of Examples 1 to 37 were the conventional fluorine-based water repellents (Comparative Example 7) and the organo-organic compounds represented by the above general formula (1) even when not heat-treated. It was confirmed that the modified silicone alone exhibited water repellency equal to or higher than that of the case of using only (Comparative Example 8), was excellent in durable water repellency, and had good texture.

When the water repellent compositions treated with the water repellent compositions of Examples 1 to 37 were the water repellent compositions containing no organo-modified silicone represented by the general formula (1) (Comparative Example 9). It was confirmed that it exhibited a water repellency equal to or higher than that, was excellent in durable water repellency, and was excellent in peel strength against the resin coating.

The water repellent compositions of Comparative Examples 1 to 6 used silicones other than the organo-modified silicone represented by the general formula (1), and tended to have particularly poor durable water repellency.

Claims (11)

Including a water repellent aid and a non-fluorine-based water repellent,
The water repellent aid contains an organo-modified silicone represented by the following general formula (1),
The non-fluorine-based water repellent, see contains the non-fluorine-based polymer containing a constitutional unit derived from represented by the following general formula (A-1) (meth) acrylic acid ester monomer (A),
The total constituent ratio of the (meth)acrylic acid ester monomer (A) represented by the general formula (A-1) in the non-fluorine-based polymer is the same as that of the monomer components constituting the non-fluorine-based polymer. A non-fluorine-based water repellent composition for fibers containing 100% of polyester, which is 56% by mass to 100% by mass with respect to the total amount .

[In the formula (1), R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group, and R ²³ is a hydrocarbon group having an aromatic ring and having 8 to 40 carbon atoms, or Represents an alkyl group of 3 to 22, R ³⁰ , R ³¹ , R ³² , R ³³ , R ^34, and R ³⁵ each independently represent a hydrogen atom or a methyl group, a represents an integer of 0 or more, and b represents Represents an integer of 1 or more, (a+b) is 20 to 100, and when a is 2 or more, a plurality of R ²⁰ and R ²¹ may be the same or different, and b is 2 or more. In this case, a plurality of R ²² and R ²³ may be the same or different. ]

[In the formula (A-1), R ¹ represents 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-fluorine-based polymer is a compound represented by the following general formula (I-1) in which (B1) HLB is 7 to 18, and a general formula (II-1) in which (B2) HLB is 7 to 18 At least one compound selected from the compounds represented and (B3) HLB of 7 to 18 and a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a fat or oil having a hydroxyl group and a polymerizable unsaturated group. The non-fluorine-based water repellent composition according to claim 1, further comprising a constituent unit derived from the reactive emulsifier (B).

[In the formula (I-1), R ³ represents 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. It represents a divalent group containing. ]

Wherein (II-1), ^{R 4} represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, ^{Y 2} is includes an alkyleneoxy group having 2 to 4 carbon atoms Represents a divalent group. ] The non-fluorine-based water repellent according to claim 1 or 2, wherein the non-fluorine-based polymer further contains a structural unit derived from at least one monomer (E) selected from vinyl chloride and vinylidene chloride. Composition. (C1) a (meth)acrylic acid ester monomer represented by the following general formula (C-1), (C2) a (meth)acrylic acid ester monomer represented by the following general formula (C-2), (C3) a methacrylic acid ester monomer represented by the following general formula (C-3), (C4) a (meth)acrylic acid ester monomer represented by the following general formula (C-4), and (C5) ) Derived from at least one second (meth)acrylic acid ester monomer (C) selected from the group consisting of (meth)acrylic acid ester monomers represented by the following general formula (C-5). The non-fluorine-based water repellent composition according to any one of claims 1 to 3, further comprising a structural unit.

[In the formula (C-1), R ⁵ represents hydrogen or a 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. However, the (meth)acrylic acid ester monomer represented by the following general formula (C-5) (C5) is not included. ]

[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 which may have a substituent. ]

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

[In formula (C-4), R ¹⁰ represents hydrogen or a 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. Represents a valent organic group. ]

[In the formula (C-5), R ¹¹ represents hydrogen or a methyl group, and R ¹² has 3 to 6 carbon atoms having a hydroxyl group and at least one functional group selected from the group consisting of a chloro group and a bromo group. Represents a monovalent chain saturated hydrocarbon group. ] Including a water repellent aid and a non-fluorine-based water repellent,
The water repellent aid contains an organo-modified silicone represented by the following general formula (1),
The non-fluorine-based water repellent is obtained by emulsion polymerization or dispersion polymerization of an emulsion or dispersion containing the (meth)acrylic acid ester monomer (A) represented by the following general formula (A-1). a fluorine-based polymer seen including,
The total constituent ratio of the (meth)acrylic acid ester monomer (A) represented by the general formula (A-1) in the non-fluorine-based polymer is the same as that of the monomer components constituting the non-fluorine-based polymer. A non-fluorine-based water repellent composition for fibers containing 100% of polyester, which is 56% by mass to 100% by mass with respect to the total amount .

[In the formula (1), R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group, and R ²³ is a hydrocarbon group having an aromatic ring and having 8 to 40 carbon atoms, or Represents an alkyl group of 3 to 22, R ³⁰ , R ³¹ , R ³² , R ³³ , R ^34, and R ³⁵ each independently represent a hydrogen atom or a methyl group, a represents an integer of 0 or more, and b represents Represents an integer of 1 or more, (a+b) is 20 to 100, and when a is 2 or more, a plurality of R ²⁰ and R ²¹ may be the same or different, and b is 2 or more. In this case, a plurality of R ²² and R ²³ may be the same or different. ]

[In the formula (A-1), R ¹ represents 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 the 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 a compound represented by (B3) HLB of 7 to 18 and a compound 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-fluorine-based water repellent composition according to claim 5, further comprising a reactive emulsifier (B).

[In the formula (I-1), R ³ represents 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. It represents a divalent group containing. ]

Wherein (II-1), ^{R 4} represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, ^{Y 2} is includes an alkyleneoxy group having 2 to 4 carbon atoms Represents a divalent group. ] The non-fluorine-based water repellent composition according to claim 5 or 6, wherein the emulsion or the dispersion further contains at least one monomer (E) selected from vinyl chloride and vinylidene chloride. The emulsion or the dispersion is represented by (C1) a (meth)acrylic acid ester monomer represented by the following general formula (C-1), (C2) represented by the following general formula (C-2) ( (Meth)acrylic acid ester monomer, (C3) methacrylic acid ester monomer represented by the following general formula (C-3), (C4) (meth)acrylic represented by the following general formula (C-4) Acid ester monomer and (C5) at least one second (meth)acrylic acid ester selected from the group consisting of (meth)acrylic acid ester monomers represented by the following general formula (C-5) The non-fluorine-based water repellent composition according to any one of claims 5 to 7, which further comprises a monomer (C).

[In the formula (C-1), R ⁵ represents hydrogen or a 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. However, the (meth)acrylic acid ester monomer represented by the following general formula (C-5) (C5) is not included. ]

[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 which may have a substituent. ]

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

[In formula (C-4), R ¹⁰ represents hydrogen or a 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. Represents a valent organic group. ]

[In the formula (C-5), R ¹¹ represents hydrogen or a methyl group, and R ¹² has 3 to 6 carbon atoms having a hydroxyl group and at least one functional group selected from the group consisting of a chloro group and a bromo group. Represents a monovalent chain saturated hydrocarbon group. ] The (meth)acrylic acid ester monomer (A) represented by the general formula (A-1) is an acrylic acid ester monomer (a1) in which R ¹ is hydrogen, and R ¹ is a methyl group. The non-fluorine-based water repellent composition according to any one of claims 1 to 9 , which contains a methacrylic acid ester monomer (a2). The content of the organo-modified silicone, wherein 1 to 50 parts by weight with respect to the non-fluorine type polymer 100 parts by weight, the non-fluorine type water repellent composition according to any one of claims 1-9. A method for producing a water-repellent fiber product, comprising the step of treating the fiber product with a treatment liquid containing the non-fluorine-based water repellent composition according to any one of claims 1 to 10 .