JP2017155095A - Water repellent assistant, non-fluorine-based water repellent composition and manufacturing method of water repellent fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water repellent assistant capable of enhancing durable water repellency of a non-fluorine-based water repellent.SOLUTION: A water repellent assistant for non-fluorine-based water repellent contains organo modified silicone represented by the following general formula (1), where R, Rand Rrepresent each independently a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms, Rrepresents a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring or an alkyl group having 3 to 22 carbon atoms, R, R, R, R, Rand Rrepresent each independently a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon groups, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring or an alkoxy group having 3 to 22 carbon atoms, a represents an integer of 0 or more, b represents an integer of 1 or more and (a+b) is 10 to 200.SELECTED DRAWING: None

Description

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

  Conventionally, a fluorine-based water repellent having a fluorine-containing group is known, and a fiber product having water repellency on its surface by treating such a fluorine-based water repellent on a fiber 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 fluorine-based water repellents exhibit excellent water repellency, but in order to develop water repellency, it is necessary to align the orientation of the fluoroalkyl group. After depositing the agent, heat treatment must be performed at a temperature exceeding 130 ° C. However, high-temperature heat treatment requires high energy, and there is a problem in the international trend of energy saving.

  In addition, a monomer having a fluoroalkyl group is not economically satisfactory because it is expensive, and a monomer having a fluoroalkyl group is difficult to decompose because it is difficult to decompose. There is.

  On the other hand, in the field of water repellent finishing of textiles, water repellents that can give textiles excellent water repellency even at low concentrations and low heat treatment temperatures are desired to stabilize quality and reduce costs. .

  In recent years, therefore, research has been conducted on non-fluorinated water repellents that do not contain fluorine. For example, Non-Patent Document 1 discloses a water repellent in which a hydrocarbon compound such as paraffin or wax, a fatty acid metal salt, or an alkyl urea is emulsified and dispersed.

  Further, Patent Document 1 proposes a water repellent in which a specific non-fluorine polymer is emulsified and dispersed for the purpose of providing water repellency comparable to that of a conventional fluorine water repellent.

“Super-water-repellent finishing, the whole of processing agents and new trends in moisture-permeable and waterproof materials”, published by Osaka Chemical Marketing Center, 1996, p. 7-9

JP 2006-328624 A

  However, conventional water repellents sometimes fail to provide sufficient 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-fluorinated water repellent, and a non-fluorinated water repellent composition using the same. And a method for producing a water-repellent fiber product.

  The present invention provides a water repellent auxiliary agent for a non-fluorinated water repellent agent, 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 represents a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms, and R ²³ represents carbon 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 are each independently a hydrogen atom, a methyl group, ethyl Represents a group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 3 to 22 carbon atoms, a represents an integer of 0 or more, and b represents 1 The above integers are represented, (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 b is 2 or more. A plurality of R ²² and R ²³ are the same. Or different. ]

  According to the water repellent aid of the present invention, the durability and water repellency of the non-fluorinated water repellent can be improved by using it together with the non-fluorinated water repellent.

  The present invention also provides a non-fluorinated water repellent composition comprising the water repellent auxiliary according to the present invention and a non-fluorinated water repellent.

  The non-fluorine water repellent may include a non-fluorine 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 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 (B1) a compound represented by the following general formula (I-1) having an HLB of 7 to 18, and (B2) a following general formula (II-1) having an HLB of 7 to 18. And (B3) at least one selected from a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to an oil and fat having a hydroxyl group and a polymerizable unsaturated group, wherein HB is 7 to 18. A structural unit derived from the reactive emulsifier (B) may be further contained.

［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 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. Represents a divalent group. ]

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

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

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

  The non-fluorine-based water repellent is non-polymerized 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). A fluorine-based polymer may be included.

  The emulsion or the dispersion includes (B1) a compound represented by the general formula (I-1) having an HLB of 7 to 18, and (B2) the general formula (II-1) having an HLB of 7 to 18. ) And (B3) at least one selected from compounds having an HLB of 7 to 18 and having a hydroxyl group and a polymerizable unsaturated group added with an alkylene oxide having 2 to 4 carbon atoms. A seed reactive emulsifier (B) may further be contained.

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

  In the non-fluorinated 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-fluorinated polymer.

  The present invention also provides a method for producing a water-repellent fiber product comprising a step of treating a fiber product with a treatment liquid containing the non-fluorinated 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-fluorinated water repellent composition containing the water-repellent auxiliary agent 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 a high temperature, so that it can save energy and uses a non-fluorine-based water repellent. The load can be reduced.

  ADVANTAGE OF THE INVENTION According to this invention, the water-repellent auxiliary agent which can improve the durable water-repellent property of a non-fluorine-type water repellent, and the non-fluorine-type water-repellent composition containing the same can be provided.

  Further, the non-fluorinated water repellent composition of the present invention is a water repellent composition that does not contain a fluoroalkyl group or a compound having fluorine, but exhibits excellent water repellency and replaces the fluorine-based water repellent. And the concern about the influence on the fluorine supply source and the environment can be eliminated. In addition, after attaching the water repellent composition to a textile product or the like, it is usually preferable to perform heat treatment, but the non-fluorinated water repellent composition of the present invention does not use a monomer having a fluoroalkyl group. Even when heat-treated under mild conditions of 130 ° C. or less, high water repellency can be exhibited. Also, when heat-treated at a high temperature exceeding 130 ° C., the heat treatment time is the case of a fluorine-based water repellent. Can be shorter. Therefore, since the alteration of the object to be processed due to heat is suppressed, the texture is flexible, and the heat quantity 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 polymer. The amount of the surfactant contained in can be reduced. As a result, it is possible to suppress a decrease in water repellency of the obtained fiber product or the like, and it is possible to realize water repellency higher than that of a conventional non-fluorinated water repellent.

  The water repellent aid for a non-fluorinated water repellent of this embodiment contains an organo-modified silicone represented by the following general formula (1). In the following general formula (1), each structural unit may be a block, random, or alternately arranged.

［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 represents a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms, and R ²³ represents carbon 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 are each independently a hydrogen atom, a methyl group, ethyl Represents a group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 3 to 22 carbon atoms, a represents an integer of 0 or more, and b represents 1 The above integers are represented, (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 b is 2 or more. A plurality of R ²² and R ²³ are 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. As a C1-C4 alkoxyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example. R ²⁰ , R ²¹ and R ²² are each independently preferably a hydrogen atom or a methyl group, 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 and a group represented by the following general formula (2) or (3).

［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。］

Wherein ^{(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, c is an integer of 0 to 3. When c is 2 or 3, a plurality of R ⁴¹ 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。］

Wherein ^{(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, d represents an integer of 0 to 3. When d is 2 or 3, a plurality of R ⁴³ 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 easily manufactured industrially and are easily available.

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

  As said C8-C40 hydrocarbon group which has said aromatic ring, it is easy to manufacture industrially and it is easy to acquire, The said C8-C40 aralkyl group and said general formula ( The group represented by 2) is preferable, and the aralkyl group having 8 to 40 carbon atoms is more preferable in terms of improving the water repellency of the resulting fiber product.

  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 and stearyl group. As a C3-C22 alkyl group, the C8-C20 alkyl group is preferable and the C12-C18 alkyl group is more preferable at the point which can improve the water repellency of the textiles obtained.

In the organo-modified silicone of this 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, an aromatic It is a C8-C40 hydrocarbon group which has a group ring, or a C3-C22 alkyl group. 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, or a carbon number 1 in terms of easy industrial production and easy availability. It is preferably a ˜4 alkoxy group, and more preferably a methyl group.

  In the organo-modified silicone of this embodiment, a is an integer of 0 or more. A is preferably 40 or less, and more preferably 30 or less, in that it is easy to produce industrially, is easily available, and the peel strength of the resulting fiber product to the resin coating is more excellent.

  In the organo-modified silicone of this embodiment, (a + b) is 10-200. (A + b) is preferably from 20 to 100, more preferably from 40 to 60, in terms of easy industrial production and easy availability. When (a + b) is within the above range, the silicone itself tends to be easily produced and handled.

  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 silicone having SiH group include methyl hydrogen silicone having a polymerization degree of 10 to 200, or a copolymer of dimethyl siloxane and methyl hydrogen siloxane. Among these, methyl hydrogen silicone is preferable because it is easy to produce industrially and is easily available.

The aromatic compound having a vinyl group is a compound derived from a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring in R ²³ in the general formula (1). Examples of the aromatic compound having a vinyl group include styrene, α-methylstyrene, vinyl naphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-cumyl phenyl ether, allyl-o-phenyl phenyl ether, allyl-tri. (Phenylethyl) -phenyl ether, allyl-tri (2-phenylpropyl) phenyl ether and the like can be mentioned.

The above α- olefins, in R ²³ in formula (1) is a compound from which it is derived alkyl group having 3 to 22 carbon atoms. 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, C3-C22 alpha olefins, such as 1-hexadecene and 1-octadecene, are mentioned.

  The hydrosilylation reaction is performed by reacting the aromatic compound having the vinyl group and the α-olefin stepwise or at once with the silicone having the SiH group in the presence of a catalyst as necessary. Also good.

  The amounts of 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 or the number average molecular weight of the silicone having a SiH group. obtain.

  Examples of the catalyst used for the hydrosilylation reaction include compounds such as platinum and palladium. Of these, platinum compounds are preferred. As a platinum compound, platinum (IV) chloride etc. are mentioned, for example.

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

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

  The non-fluorinated water repellent composition of this embodiment will be described.

  The non-fluorinated water repellent composition of the present embodiment includes the water repellent assistant of the present embodiment and a non-fluorinated water repellent.

  The non-fluorine-based water repellent has excellent storage stability and can impart sufficient water repellency to textiles and the like even without heat treatment, and is excellent in texture and water repellency. Is a structural unit derived from a (meth) acrylic acid ester monomer (A) represented by the following general formula (A-1) (hereinafter also referred to as “component (A)”). It is preferable that the non-fluorine-type polymer containing is contained.

［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 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 also synonymous in “(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 that may have a substituent. Having a valent hydrocarbon group. The hydrocarbon group may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and further an alicyclic or aromatic cyclic group. You may have. Among these, those that are linear are preferable, and those that are linear alkyl groups are more preferable. In this case, the water repellency is 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. 1 or more types of etc. are mentioned. 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 a non-fluorine polymer is adhered to a fiber product or the like. On the other hand, when the number of carbons exceeds 24, compared to the case where the number of carbons is in the above range, when a non-fluorine polymer is attached to a fiber product or the like, the texture of the fiber product tends to be coarse. .

  As for the carbon number of the said hydrocarbon group, it is more preferable that it is 12-21. When the carbon number is within this range, the water repellency and texture are particularly excellent. Particularly preferred as the hydrocarbon group is a linear alkyl group having 12 to 18 carbon atoms.

  Examples of the component (A) include stearyl (meth) acrylate, cetyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, and (meth) acrylic acid. Pentadecyl, heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, henecosyl (meth) acrylate, behenyl (meth) acrylate, ceryl (meth) acrylate, melyl (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 that can react with the crosslinking agent. In this case, the durable water repellency of the resulting fiber product can be further improved. The isocyanate group may form a blocked isocyanate group protected with a blocking agent. Moreover, when the said (A) component has an amino group, the feel of the fiber product obtained can be improved further.

  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 used in combination with the acrylic ester monomer (a1) and the methacrylic ester monomer (a2) from the viewpoint of durable water repellency of the resulting fiber product. The ratio (a1) / (a2) of the mass of the component (a1) and the mass of the component (a2) to be blended is preferably 30/70 to 90/10, and 40/60 to 85/15. Is more preferable, and it is further more preferable that it is 50 / 50-80 / 20. When (a1) / (a2) is within the above range, the durable water repellency of the resulting fiber product becomes better. When (a1) / (a2) exceeds 90/10 or less than 30/70, the durable water repellency of the resulting fiber product tends to decrease.

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

  The non-fluorinated polymer preferably has a weight average molecular weight of 100,000 or more. If the weight average molecular weight is less than 100,000, the resulting fiber product tends to have insufficient water repellency. Further, the weight average molecular weight of the non-fluorinated 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-fluorinated polymer is preferably about 5 million.

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

“Melt viscosity at 105 ° C.” means using an elevated flow tester (for example, CFT-500 manufactured by Shimadzu Corporation) and putting 1 g of a non-fluorinated polymer in a cylinder attached with a die (length 10 mm, diameter 1 mm) The viscosity is measured when held at 105 ° C. for 6 minutes and a load of 100 kg · f / cm ² is applied with a plunger.

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

  A non-fluorine polymer is added to the component (A) in that it can improve the water repellency of the resulting fiber product and the emulsion stability in the emulsion polymerization or dispersion polymerization of the non-fluorine polymer and in the composition after polymerization. (B1) a compound represented by the following general formula (I-1) having an HLB of 7 to 18, (B2) a compound represented by the following general formula (II-1) having an HLB of 7 to 18, And (B3) at least one reactive emulsifier selected from a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to an oil and fat having a hydroxyl group and a polymerizable unsaturated group, wherein HLB is 7 to 18 (B ) (Hereinafter also referred to as “component (B)”) 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 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. Represents a divalent group. ]

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

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

  “Reactive emulsifier” means 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 the monomer.

  “HLB” is an HLB value calculated by the Griffin method, assuming that the ethyleneoxy group is a hydrophilic group and all other groups are lipophilic groups.

  The HLB of the compounds (B1) to (B3) used in the present embodiment is 7 to 18, and the emulsion stability in the composition during and after the emulsion polymerization or dispersion polymerization of the non-fluorinated polymer. From the point of property (henceforth only emulsion stability), 9-15 are preferable. Furthermore, it is more preferable to use two or more reactive emulsifiers (B) having different HLBs within the above range in view of storage stability of the non-fluorinated 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 is copolymerizable with the component (A). More preferred is a methyl group. X is a linear or branched alkylene group having 1 to 6 carbon atoms, and a linear alkylene group having 2 to 3 carbon atoms is more preferable from the viewpoint of emulsion stability of the non-fluorinated polymer of the present embodiment. Y ¹ is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. The type, combination, and number of additions of the alkyleneoxy group in Y ¹ can be appropriately selected so as to be within the above HLB range. Moreover, when an alkyleneoxy group is 2 or more types, 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 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. M can be appropriately selected such that it falls within the above HLB range. Specifically, an integer of 1 to 80 is preferable, and when m is 2 or more, m A ¹ Os are the same. Or 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 in terms of copolymerization with the component (A). X is a linear or branched alkylene group having 1 to 6 carbon atoms, and a linear alkylene group having 2 to 3 carbon atoms is more preferable from the viewpoint of emulsion stability of the non-fluorinated polymer. A ¹ O is an alkyleneoxy group having 2 to 4 carbon atoms. A 1 ^O type and combination, as well as the number of m can be appropriately selected to be in the range of the HLB. From the viewpoint of emulsion stability of the non-fluorine polymer, m is preferably an integer of 1 to 80, and more preferably an integer of 1 to 60. When m is 2 or more, m A ¹ Os may be the same or different. Further, when A 1 ^O is two or more, they may have a block addition structure or 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. Moreover, it can obtain easily from a commercial item, for example, "Latemul PD-420", "Latemul PD-430", "Latemul PD-450" etc. by Kao Corporation can be mentioned.

In the reactive emulsifier (B2) represented by the general formula (II-1) used in the present embodiment, R ⁴ is a monovalent unsaturated carbonization having 13 to 17 carbon atoms having a polymerizable unsaturated group. A hydrogen group, such as tridecenyl, tridecadienyl, tetradecenyl, tetradienyl, pentadecenyl, pentadecadienyl, pentadecatrienyl, heptadecenyl, heptadecadienyl, heptadecatrienyl, etc. . From the viewpoint of emulsion stability of the non-fluorinated 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 be within the above HLB range. Moreover, when an alkyleneoxy group is 2 or more types, they can have a block addition structure or a random addition structure. From the viewpoint of emulsion stability of the non-fluorinated 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 Formula (II-2), R ⁴ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and A ² O represents an alkyleneoxy group having 2 to 4 carbon atoms. N can be appropriately selected so as to be within the range of the HLB. Specifically, an integer of 1 to 50 is preferable, and when n is 2 or more, n A ² Os are the same. May 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-fluorinated polymer, the type and combination of A ² O and the number of n can be appropriately selected so as to be within the above HLB range. From the viewpoint of emulsion stability of the non-fluorine 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 further preferably an integer of 8 to 14. . When n is 2 or more, n A ² Os may be the same or different. Further, when A 2 ^O is more than two, they may have a block addition structure or random addition structure.

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

  The corresponding phenol having an unsaturated hydrocarbon group includes not only a pure product or a mixture produced industrially but also a pure product or a mixture extracted and purified from plants or the like. For example, 3- [8 (Z), 11 (Z), 14-pentadecatrienyl] phenol, 3- [8 (Z), 11 (Z), which is extracted from cashew nut shells, etc. and is 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 in which an alkylene oxide having 2 to 4 carbon atoms is added to an oil and fat having a hydroxyl group and a polymerizable unsaturated group having an HLB of 7 to 18. . The 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 good fatty acids and triglycerides of fatty acids including at least one hydroxy unsaturated fatty acid (such as ricinoleic acid, ricinoelaidic acid, 2-hydroxytetracosenoic acid). From the viewpoint of emulsion stability of the non-fluorinated polymer, an alkylene oxide adduct of a triglyceride of a fatty acid containing at least one hydroxy unsaturated fatty acid is preferable, and the carbon number of castor oil (triglyceride of a fatty acid containing ricinoleic acid) is 2 to 4 carbon atoms. More preferred is an alkylene oxide adduct, and more preferred is an ethylene oxide adduct of castor oil. Furthermore, the number of added moles of alkylene oxide can be appropriately selected so as to be within the range of the above HLB. From the viewpoint of the emulsion stability of the non-fluorinated polymer, it is more preferably 20 to 50 mol, and 25 to 45 mol. Is more preferable. Moreover, when alkylene oxide is 2 or more types, they can have a block addition structure or a random addition structure.

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

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

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

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

[In 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. 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 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) Methacrylate monomer represented by the following general formula (C-3)

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

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

[In the 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 has a polymerizable unsaturated group 1 Represents a valent organic group. ]

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

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

  The monomer (C1) has at least one functional group selected from the group consisting of hydroxyl group, amino group, carboxyl group, epoxy group, isocyanate group and (meth) acryloyloxy group in the ester moiety. It is a (meth) acrylic acid ester monomer having a monovalent chain hydrocarbon group of 1 to 11, and is a (meth) acrylic acid ester monomer other than the above (C5). From the viewpoint of being capable 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 preferably has a functional group. When the non-fluorinated polymer containing the monomer (C1) having a group capable of reacting with these crosslinking agents is processed into a fiber product together with the crosslinking agent, the texture of the resulting fiber product is maintained, 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. The chain hydrocarbon group may further have a substituent in addition to the functional group. Among these, it is preferable that the fiber product is linear and / or a saturated hydrocarbon group in terms of improving the durable water repellency of the obtained fiber product.

  Specific examples of the monomer (C1) include 2-hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, and 1,1-bis (acryloyloxymethyl) ethyl. An isocyanate etc. are mentioned. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type. Among them, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate are preferable because the durable water repellency of the obtained fiber product can be improved. Furthermore, dimethylaminoethyl (meth) acrylate is preferable in terms of improving the texture of the resulting fiber product.

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

  The monomer (C2) is a (meth) acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester moiety, and the cyclic hydrocarbon group includes an isobornyl group, Examples include a cyclohexyl group and a dicyclopentanyl group. These cyclic hydrocarbon groups may have a substituent such as an alkyl group. However, when the substituent is a hydrocarbon group, a hydrocarbon group in which the total number of carbon atoms of the substituent and the cyclic hydrocarbon group is 11 or less is selected. In addition, these cyclic hydrocarbon groups are preferably directly bonded to an ester bond from the viewpoint of improving durable water repellency. The cyclic hydrocarbon group may be alicyclic or aromatic, and in the case of alicyclic, it may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Specific examples of the monomer include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type. Among them, isobornyl (meth) acrylate and cyclohexyl methacrylate are preferable, and isobornyl methacrylate is more preferable in that the durable water repellency of the obtained fiber product can be improved.

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

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

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

  The monomer (C4) is a (meth) acrylic acid ester monomer having 3 or more polymerizable unsaturated groups in one molecule. In this embodiment, T in the general formula (C-4) is a (meth) acryloyloxy group, and a polyfunctional (meth) acrylic acid ester having 3 or more (meth) acryloyloxy groups in one molecule. A monomer is preferred. In formula (C-4), p pieces of T 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 include dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type. Among them, tetramethylolmethane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferable in terms of improving the durable water repellency of the obtained fiber product.

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

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

R ¹² is a C 3-6 monovalent chain saturated hydrocarbon group having at least one functional group selected from the group consisting of a chloro group and a bromo group and a hydroxyl group. The chain saturated hydrocarbon group may be linear or branched. When the chain saturated hydrocarbon group is linear, the durable water repellency of the resulting fiber product is more excellent. The number of carbon atoms of the chain saturated hydrocarbon group is preferably 3 to 4 and more preferably 3 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 durable water repellency of the resulting fiber product, and one chloro group, More preferably, it has one hydroxyl group. Further, in terms of durable water repellency of the resulting fiber product, the chain saturated hydrocarbon group is a hydroxyl group at the β position (the carbon atom adjacent to the carbon atom bonded to CH ₂ = CR ¹¹ (CO) O—). More preferably, Specific examples of the chain saturated hydrocarbon group include 3-chloro-2-hydroxylpropyl group, 3-chloro-2-hydroxybutyl group, 5-chloro-2-hydroxypentyl group, and 3-chloro-2. -Hydroxy-2-methylpropyl group and 3-bromo-2-hydroxypropyl group are mentioned.

  Specific examples of the monomer (C5) include 3-chloro-2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxybutyl (meth) acrylate, and 5- (meth) acrylic acid 5- Examples include chloro-2-hydroxypentyl and 3-bromo-2-hydroxypropyl (meth) acrylate. Among them, 3-chloro-2-hydroxypropyl (meth) acrylate is preferable, and 3-chloro-2-hydroxypropyl methacrylate is more preferable in terms of improving the durable water repellency of the obtained fiber product.

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

  The total component ratio of the monomer (C) in the non-fluorine polymer is based on the total amount of the monomer components constituting the non-fluorine polymer from the viewpoint of water repellency and texture of the resulting fiber product. The content is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass.

  In addition to the (A) component, the (B) component and the (C) component, the non-fluorinated polymer contained in the non-fluorinated water repellent is a monofunctional monomer (D) (hereinafter referred to as “copolymerizable with these”). , (Also referred to as “component (D)”) 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. Esters, maleic acid esters, fumaric acid, maleic acid, (meth) acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, vinyl monomers other than component (E) that do not contain fluorine such as ethylene, styrene, etc. Is mentioned. In addition, the (meth) acrylic acid ester having a hydrocarbon group other than the component (A) and the component (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 other than a group capable of reacting with a crosslinking 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 these, (meth) acryloylmorpholine is more preferable because it can improve the peel strength of the resulting textile product coating.

  From the viewpoint of water repellency and texture of the resulting fiber product, the component ratio of the component (D) in the non-fluorine polymer is based on the total amount of the monomer components constituting the non-fluorine polymer. It is preferable that it is 10 mass% or less.

  The non-fluorinated polymer contained in the non-fluorinated 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 that can react with the crosslinking agent. Is preferable because it improves the durable water repellency of the resulting fiber product. The isocyanate group may form a blocked isocyanate group protected with a blocking agent. Moreover, it is preferable that a non-fluorine-type polymer has an amino group from the viewpoint of improving the feel of the resulting fiber product.

  In addition to the component (A), the non-fluorinated polymer contained in the non-fluorinated water repellent can improve the water repellency of the resulting fiber product and the peel strength against the coating. One type of monomer (E) (hereinafter also referred to as “component (E)”) is preferably contained as a monomer component.

  Of the vinyl chloride and vinylidene chloride used in the present embodiment, at least one monomer (E) is preferably vinyl chloride in terms of the water repellency of the resulting fiber product and the peel strength against the coating.

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

  Additives and the like can be added to the water repellent composition of the present embodiment as necessary. Examples of the additive include other water repellents, crosslinking agents, antibacterial deodorants, flame retardants, antistatic agents, softeners, antifungal agents and the like.

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

  A non-fluorinated water repellent containing a non-fluorinated polymer can be produced by a radical polymerization method. Among these radical polymerization methods, it is preferable to perform polymerization by an emulsion polymerization method or a dispersion polymerization method from the viewpoint of performance and environment of the obtained water repellent.

  For example, a non-fluorine polymer can be obtained by emulsion polymerization or dispersion polymerization of 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 the 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. In addition, as a means for emulsifying or dispersing the above-described mixed liquid, a homomixer, a high-pressure emulsifier, an ultrasonic wave, or the like can be given.

  Examples of the emulsification aid or dispersion aid (hereinafter also referred to as “emulsification aid”) include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoterics other than the reactive emulsifier (B). 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 with respect to 100 parts by mass of all monomers, and 1 to 10 parts by mass. More preferably. When the content of the emulsification aid is less than 0.5 parts by mass, the dispersion stability of the mixed solution tends to be lower than when the content of the emulsification aid is in the above range, When the content of the emulsification aid exceeds 30 parts by mass, the water repellency of the obtained non-fluorinated polymer tends to be lower than when the content of the emulsification aid is in the above range.

  As a medium for emulsion polymerization or dispersion polymerization, water is preferable, and water and an organic solvent may be mixed as necessary. The organic solvent is not particularly limited as long as it is miscible with water. For example, alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, diethyl Examples include ethers such as ether, and glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol. In addition, the ratio of water and an organic solvent is not specifically limited.

  As said polymerization initiator, well-known polymerization initiators, such as an azo type | system | group, a peroxide type | system | group, or a redox type | system | group, can be used suitably. It is preferable that content of a polymerization initiator is 0.01-2 mass parts of polymerization initiators with respect to 100 mass parts of all the monomers. When the content of the polymerization initiator is within the above range, a non-fluorine polymer having a weight average molecular weight of 100,000 or more can be produced efficiently.

  In the polymerization reaction, a chain transfer agent such as dodecyl mercaptan or t-butyl alcohol may be used for the purpose of adjusting the molecular weight. The content of the chain transfer agent is preferably 0.3 parts by mass or less, more preferably 0.1 parts by mass or less with respect to 100 parts by mass of all monomers. When 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-fluorinated polymer having a weight average molecular weight of 100,000 or more.

  In order to adjust the molecular weight, a polymerization inhibitor may be used. By adding a polymerization inhibitor, a non-fluorinated polymer having a desired weight average molecular weight can be easily obtained.

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

  In the polymerization reaction, the weight average molecular weight of the obtained non-fluorinated polymer can be adjusted by increasing / decreasing the contents of the polymerization initiator, chain transfer agent and polymerization inhibitor described above, and the melt viscosity at 105 ° C. is polyfunctional. It can adjust by increase / decrease in content of a monomer and content of a polymerization initiator. In order to lower the melt viscosity at 105 ° C., the content of the monomer having two or more polymerizable functional groups may be reduced, or the content of the polymerization initiator may be increased.

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

  The non-fluorinated water repellent composition of the present embodiment can be produced by mixing the water repellent aid of the present embodiment and the non-fluorinated water repellent.

  The compounding amount of the organo-modified silicone represented by the general formula (1) in the non-fluorinated water repellent composition of the present embodiment is 1 to 10% by mass in terms of durable water repellency of the resulting fiber product. It is preferably 3 to 7% by mass.

  In addition, the amount of the organo-modified silicone represented by the general formula (1) in the non-fluorine water repellent composition of the present embodiment is 100 masses of the non-fluorine polymer in terms of the durable water repellency of the resulting fiber product. The amount is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and still more preferably 10 to 25 parts by mass with respect to parts.

  A method for producing the water-repellent fiber product of this embodiment will be described.

  The water-repellent fiber product of this embodiment is obtained by treating a fiber product with a treatment liquid containing the above-described non-fluorinated water repellent composition. There are no particular restrictions on the material of such textile products, natural fibers such as cotton, hemp, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as nylon, polyester, polyurethane, and polypropylene, and composite fibers thereof. A blended fiber etc. are mentioned. The form of the textile product may be any form such as fiber, yarn, cloth, woven fabric, knitted fabric, cloth in the form of clothing, carpet, non-woven fabric, and paper.

  Examples of a method for treating a textile product with the treatment liquid include a processing method such as dipping, spraying, and coating, or a processing method using a cleaning method. Moreover, when a non-fluorine type water repellent composition contains water, it is preferable to make it dry in order to remove water, after making it adhere to textiles.

  Moreover, after processing a textile product with the non-fluorine-type water repellent composition of this embodiment, it is preferable to heat-process suitably. The temperature condition is not particularly limited, but when the non-fluorinated water repellent composition of the present embodiment is used, sufficiently good water repellency can be expressed in the textile under mild conditions 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 compared to the conventional case using a fluorine-based water repellent. . Therefore, according to the water-repellent fiber product of this embodiment, alteration of the fiber product due to heat is suppressed, the texture of the fiber product at the time of water-repellent treatment is 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 process of treating a textile product with a treatment liquid containing a non-fluorinated water repellent composition and one methylol melamine, isocyanate group or blocked isocyanate group The fiber product is preferably water-repellent processed by a method comprising a step of adhering a crosslinking agent typified by the above-mentioned compound to the fiber product and heating it. Further, when it is desired to further improve the durable water repellency, the non-fluorinated water repellent composition contains a non-fluorinated polymer obtained by copolymerizing a monomer having a functional group capable of reacting with the above-mentioned crosslinking agent. Is preferred.

  Examples of the compound having at least one isocyanate group include monoisocyanates such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate, and naphthalene isocyanate, diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like. Examples include trimers that are isocyanurate rings and trimethylolpropane adducts. Moreover, as a compound which has 1 or more of blocked isocyanate groups, the compound which protected the isocyanate group with the blocking agent for the compound which has the said isocyanate group is mentioned. Blocking agents used at this time include organic blocking agents such as secondary or tertiary alcohols, active methylene compounds, phenols, oximes, and lactams, and bisulfites such as sodium bisulfite and potassium bisulfite. Salt. The above crosslinking 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 object to be processed (fiber product) in a processing liquid emulsified and dispersed in water, and drying the processing liquid attached to the object to be processed. It can be attached to the workpiece. And the reaction of a crosslinking agent, a to-be-processed object, and a non-fluorine-type polymer can be advanced by heating the crosslinking agent adhering to to-be-processed object. In order to sufficiently advance the reaction of the crosslinking agent and more effectively improve the washing durability, the heating at this time is preferably performed at 110 to 180 ° C. for 1 to 5 minutes. The step of attaching and heating the cross-linking agent may be performed simultaneously with the step of treating with the treatment liquid containing the above-described water repellent composition. In the case of carrying out simultaneously, for example, after the treatment liquid containing the water repellent composition and the crosslinking agent is adhered to the object to be treated and water is removed, the crosslinking agent adhered to the object to be treated is further heated. In view of simplification of the water repellent process, reduction of heat, and economy, it is preferable to perform the process simultaneously with the process of treating the water repellent composition.

  Moreover, when a crosslinking agent is used excessively, there exists a possibility that a feeling may be spoiled. The crosslinking agent is preferably used in an amount of 0.1 to 50% by mass, particularly preferably 0.1 to 10% by mass with respect to the object to be treated (textile product).

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

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

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

  For example, in the case of producing a non-fluorine polymer, in the above embodiment, the polymerization reaction is performed by radical polymerization, but the polymerization reaction is performed by photopolymerization that irradiates ionizing radiation such as ultraviolet rays, electron beams, and γ rays. May be performed.

  In the present invention, the non-fluorinated water repellent composition is treated with a fiber product to obtain a water-repellent fiber product. However, the product treated with the non-fluorinated water repellent composition is suitable for textile products. The article is not limited to metal, glass, resin, or the like.

  In such a case, the method of attaching the non-fluorinated 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.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

<Preparation of water repellent aid>
(Synthesis Example 1)
Into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel, 63.2 g of methyl hydrogen silicone having an SiH group equivalent of 63.2 g / mol and a polymerization degree of 50 was added. Then, the mixture was flushed with nitrogen and heated until the temperature reached 65 ° C. and mixed until uniform. As a hydrosilylation catalyst, an ethylene glycol monobutyl ether / toluene mixed solution of platinum (IV) chloride was added to the reaction product in the system so that the platinum concentration was 5 ppm. When the temperature of the reaction product reached 120 ° C., 168.3 g of 1 mol of 1-dodecene was added dropwise and reacted at 120 ° C. for 6 hours. The completion of the addition reaction was confirmed by conducting an 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 above 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 adduct of 9 moles of ethylene oxide of a branched higher alcohol having 12 to 14 carbon atoms was added to and mixed with 20 parts by mass of the obtained organo-modified silicone. Next, 77 parts by mass of water was added while being mixed little by little and emulsified in water to obtain a silicone emulsion.

(Synthesis Example 2)
An organo-modified silicone and a silicone emulsion were obtained in the same manner as in Synthesis Example 1 except that 84.2 g of 1 mol of 1-hexene was used instead of 168.3 g of 1 mol of 1-dodecene. In the organo-modified silicone, a in the general formula (1) 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 ^An organo-modified silicone in which ³⁵ is a methyl group was obtained.

(Synthesis Example 3)
An organo-modified silicone and a silicone emulsion were obtained in the same manner as in Synthesis Example 1 except that 252.5 g of 1 mol of 1-octadecene was used instead of 168.3 g of 1 mol of 1-dodecene. In the organo-modified silicone, a in 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)
The same as Synthesis Example 1 except that instead of 168.3 g of 1 mol of 1-dodecene, 84.2 g of 0.5 mol of 1-dodecene and 59.1 g of 0.5 mol of α-methylstyrene were used. Thus, an organo-modified silicone and a silicone emulsion were obtained. 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 , R ^An organo-modified silicone in which ³⁴ and R ³⁵ are methyl groups was obtained.

(Synthesis Example 5)
Instead of 168.3 g of 1 mol of 1-dodecene, the same procedure as in Synthesis Example 1 was carried out except that 84.2 g of 0.5 mol of 1-dodecene and 126.2 g of 0.5 mol of 1-octadecene were used. Thus, an organo-modified silicone and a silicone emulsion were obtained. In the organo-modified silicone, a in general formula (1) is 0, b is 50, R ²² is a methyl group, R ²³ is a dodecyl group or octadecyl group, R ³⁰ , R ³¹ , R ³² , R ³³ , R ^34. And an organo-modified silicone in which R ³⁵ is a methyl group.

(Synthesis Example 6)
A dimethylsiloxane having an SiH group equivalent of 140.5 g / mol and a polymerization degree of 50 instead of 63.2 g of methylhydrogen silicone having an SiH group equivalent of 63.2 g / mol and a polymerization degree 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 methylhydrogensiloxane was used. In the organo-modified silicone, a in formula (1) is 25, b is 25, R ²⁰ and R ²¹ are methyl groups, R ²² is methyl group, R ²³ is dodecyl group, R ³⁰ , R ³¹ , R ^32. An organo-modified silicone in which R ³³ , R ³⁴ and R ³⁵ are methyl groups was obtained.

(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 adduct of 9 moles of ethylene oxide of a branched higher alcohol having 12 to 14 carbon atoms was added and mixed. Next, 77 parts by mass of water was added while being mixed little by little and emulsified in water to obtain a silicone emulsion.

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

<Preparation of polymer dispersion>
Polymer mixtures having the compositions shown in Tables 1 to 6 (in the tables, the numerical values indicate (g)) were polymerized by the following procedure to obtain polymer dispersions.

(Synthesis Example 9)
In a 500 mL flask, stearyl acrylate 60 g, Neugen XL-100 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7) 2 g, Neugen XL-60 (Daiichi Kogyo Seiyaku Co., Ltd., 2 g of polyoxyalkylene branched decyl ether, HLB = 12.5), 3 g of stearyldimethylamine hydrochloride, 25 g of tripropylene glycol and 207.70 g of water were mixed and stirred at 45 ° C. to obtain a mixed solution. This mixture 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 performed at 60 ° C. for 6 hours under a nitrogen atmosphere to obtain a non-fluorine polymer dispersion having a polymer concentration of 20% by mass. .

(Synthesis Examples 10 to 36)
Except having used the material of Tables 1-6, superposition | polymerization was performed similarly to the synthesis example 9, and the non-fluorine-type polymer dispersion liquid of the polymer concentration shown to Tables 7-10 was obtained, respectively.

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

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

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

In which the average value of n is 8 (wherein n is 6, 8, 10, 12, or 14).

  Evaluation was performed about the polymer dispersion liquid obtained above and the polymer obtained by the method shown below.

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

(2) Measuring method of weight average molecular weight About the polymer obtained above, by GPC apparatus (Tosoh Co., Ltd. product GPC "HLC-8020"), column temperature of 40 degreeC, flow rate of 1.0 ml / min conditions, The measurement was performed using tetrahydrofuran as an eluent, and the weight average molecular weight was measured in terms of standard polystyrene. In addition, three columns of TOS-GEL G5000HHR, G4000HHR, and G3000HHR manufactured by Tosoh Corporation were connected and attached to the column.

<Adjustment of water repellent composition>
(Examples 1-37 and Comparative Examples 1-9)
The water repellent auxiliary agent (silicone emulsion) obtained in Synthesis Examples 1 to 8 and the polymer dispersion obtained in Synthesis Examples 9 to 36 were mixed at the mass ratios shown in Tables 11 to 15 to obtain a water repellent composition. It was a thing.

  The water repellent composition obtained above was evaluated.

(Evaluation of water repellency of textile products)
In accordance with the spray method of JIS L 1092 (1998), the shower water temperature was set to 27 ° C. and the test was performed. In this test, a treated liquid obtained by diluting a dyed 100% polyester cloth or 100% nylon cloth with water so that the water repellent composition of Examples and Comparative Examples was 3% by mass of the polymer. After being immersed in the film (pickup rate 60 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 resulting fabric. The results were visually evaluated according to the following grade. When the characteristics were slightly good, “+” was assigned to the grade, and when the characteristics were slightly inferior, “−” was assigned to the grade. The results are shown in Tables 16-22.
Water repellency: State 5: No adhesion or wetness on the surface 4: A slight adhesion or wetness on the surface 3: A partial wetness on the surface 2: A wetness on the surface 1: A wetness on the entire surface Things 0: Both front and back surfaces are completely wet

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

(Durable water repellency evaluation of textile products)
In accordance with the spray method of JIS L 1092 (1998), the shower water temperature was set to 27 ° C. and the test was performed. In this test, the dyed 100% polyester cloth has a polymer content of 3% by mass and a UNIKA RESIN 380-K (crosslinking agent, manufactured by Union Chemical Industries, Ltd., trimethylol melamine resin) of 0%. .3% by mass and UNIKA CATALYST 3-P (surfactant, manufactured by Union Chemical Industries, Ltd., amino alcohol hydrochloride) so that the content is 0.2% by mass. A cloth (L-) obtained by immersing the composition and each of the above chemicals in a treatment solution diluted with water (pickup rate 60 mass%), drying at 130 ° C. for 2 minutes, and further heat-treating at 170 ° C. for 60 seconds. 0) and the water repellency of the fabric after washing 10 times (L-10) according to the method 103 of JIS L 0217 (1995) was evaluated in the same manner as the above water repellency evaluation method. Further, in the case of 100% nylon cloth, 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 for textile coating)
The test was conducted according to JIS K 6404-5 (1999). In this test, a dyed 100% nylon cloth was immersed in a treatment solution in which the water repellent compositions of Examples and Comparative Examples were diluted with water so that the polymer content was 3% by mass (pickup). 60 mass%), 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 San Kasei Co., Ltd.) is thermally bonded to the obtained base fabric at 150 ° C. for 1 minute using a thermocompression bonding apparatus, and the interlayer between the base fabric and the seam tape is peeled off. 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 defined as peel strength [N / inch]. The results are shown in Tables 16-22.

  Even if the fiber product which processed the water repellent composition of Examples 1-37 is a case where it does not heat-process, the conventional fluorine-type water repellent (Comparative Example 7) and the organo represented by the said General formula (1) It was confirmed that the water repellency equivalent to or better than that obtained when only the modified silicone (Comparative Example 8) was used was excellent in durability and water repellency.

  Moreover, the textiles which processed the water repellent composition of Examples 1-37 use the water repellent composition (comparative example 9) which does not contain the organo modified silicone represented by the said General formula (1). It was confirmed that the water repellency was equal to or better than that of the resin, excellent in durable water repellency, and excellent in peel strength against the resin coating.

  The water repellent compositions of Comparative Examples 1 to 6 use silicones other than the organo-modified silicone represented by the general formula (1), and the durability and water repellency tend to be particularly poor.

Claims (10)

A water repellent auxiliary agent for non-fluorinated water repellent agents, comprising an organo-modified silicone represented by the following general formula (1).

[In the formula (1), R ²⁰ , R ²¹ and R ²² each independently represents a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms, and R ²³ represents carbon 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 are each independently a hydrogen atom, a methyl group, ethyl Represents a group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 3 to 22 carbon atoms, a represents an integer of 0 or more, and b represents 1 The above integers are represented, (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 b is 2 or more. A plurality of R ²² and R ²³ are the same. Or different. ]   A non-fluorinated water repellent composition comprising the water-repellent auxiliary agent according to claim 1 and a non-fluorinated water repellent. The said non-fluorine-type water repellent contains the non-fluorine-type polymer containing the structural unit derived from the (meth) acrylic acid ester monomer (A) represented by the following general formula (A-1). 2. A non-fluorinated water repellent composition according to 2.

[In 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 (B1) a compound represented by the following general formula (I-1) having an HLB of 7 to 18, and (B2) the following general formula (II-1) having an HLB of 7 to 18. And (B3) at least one selected from a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to an oil and fat having a hydroxyl group and a polymerizable unsaturated group, wherein HB is 7 to 18. The non-fluorinated water repellent composition according to claim 3, further comprising a structural unit derived from the reactive emulsifier (B).

[In 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. Represents a divalent group. ]

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

[In 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 (B1) a compound represented by the following general formula (I-1) having an HLB of 7 to 18, and (B2) the following general formula (II-1) having an HLB of 7 to 18. ) And (B3) at least one selected from compounds having an HLB of 7 to 18 and having a hydroxyl group and a polymerizable unsaturated group added with an alkylene oxide having 2 to 4 carbon atoms. The non-fluorinated water repellent composition according to claim 6, further comprising a seed reactive emulsifier (B).

[In 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. Represents a divalent group. ]

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