JP6209226B2 - Water repellent composition, water repellent fiber product and method for producing water repellent fiber product - Google Patents

Description

  The present invention relates to a water repellent composition, a water repellent fiber product, 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, with the non-fluorinated water repellent described in Non-Patent Document 1, it is difficult to obtain a fiber product having the same water repellency as when treated with a conventional fluorinated water repellent. Further, the treated textile product tends to be hard, and the texture is not sufficient.

  In the case of the non-fluorinated water repellent described in Patent Document 1, when a surfactant is added in such an amount that the non-fluorinated polymer is sufficiently emulsified and dispersed in order to ensure storage stability, the water repellency of the resulting fiber product is obtained. Therefore, it is difficult to achieve both storage stability and water repellency.

  The present invention has been made in view of the above circumstances, and is excellent in storage stability and can impart sufficient water repellency to a fiber product or the like even when heat treatment is not performed. It is an object of the present invention to provide a water repellent composition capable of obtaining an excellent water repellent fiber product, a water repellent fiber product using the same, and a method for producing a water repellent fiber product.

  The present invention includes a structural unit derived from the (meth) acrylic acid ester monomer (A) represented by the following general formula (A-1), and the following general formula (I) wherein (B1) HLB is 7 to 18: -1), (B2) a compound represented by the following general formula (II-1) in which HLB is 7 to 18, and (B3) a hydroxyl group and polymerizability in which HLB is 7 to 18 A repellent comprising a non-fluorinated polymer containing a structural unit derived from at least one reactive emulsifier (B) selected from compounds obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an oil and fat having an unsaturated group. A liquid composition is provided.

［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. ]

［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 is derived from at least one second (meth) acrylate monomer (C) selected from the group consisting of (C1), (C2), (C3) and (C4) below. It may further contain a constituent unit.

［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。］(C1) (meth) acrylic acid ester monomer represented by the following general formula (C-1)

[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. ]

  The present invention also provides a (meth) acrylic acid ester monomer (A) represented by the above general formula (A-1) and (B1) the above general formula (I-1) in which HLB is 7 to 18. A compound represented by formula (II-1) wherein (B2) HLB is 7-18, and (B3) a hydroxyl group and a polymerizable unsaturated group wherein HLB is 7-18. Non-fluorine system obtained by emulsion polymerization or dispersion polymerization of an emulsion or dispersion containing at least one reactive emulsifier (B) selected from compounds obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an oil or fat having A water repellent composition comprising a polymer is provided.

  The emulsion or dispersion is at least one second (meth) acrylate monomer (C) selected from the group consisting of (C1), (C2), (C3) and (C4). May further be included.

  According to the water repellent composition of the present invention, it has excellent storage stability and can impart sufficient water repellency to textiles and the like even without heat treatment, and has excellent texture and water repellency. An aqueous fiber product can be realized.

  The present invention also includes a structural unit derived from the (meth) acrylic acid ester monomer (A) represented by the general formula (A-1), and the general formula (B1) wherein the HLB is 7-18. A compound represented by I-1), (B2) a compound represented by the above general formula (II-1) in which HLB is 7 to 18, and (B3) a hydroxyl group and polymerization in which HLB is 7 to 18 A non-fluorinated polymer containing a structural unit derived from at least one reactive emulsifier (B) selected from compounds obtained by adding a C2-C4 alkylene oxide to an oil and fat having an unsaturated group A water-repellent fiber product comprising the above-described fiber product is provided.

  The non-fluorine polymer is derived from at least one second (meth) acrylate monomer (C) selected from the group consisting of (C1), (C2), (C3) and (C4). It may further contain a constituent unit.

  The present invention also provides a (meth) acrylic acid ester monomer (A) represented by the above general formula (A-1) and (B1) the above general formula (I-1) in which HLB is 7 to 18. A compound represented by formula (II-1) wherein (B2) HLB is 7-18, and (B3) a hydroxyl group and a polymerizable unsaturated group wherein HLB is 7-18. Non-fluorine system obtained by emulsion polymerization or dispersion polymerization of an emulsion or dispersion containing at least one reactive emulsifier (B) selected from compounds obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an oil or fat having A water-repellent fiber product comprising a fiber product to which a polymer is attached is provided.

  The emulsion or dispersion is at least one second (meth) acrylate monomer (C) selected from the group consisting of (C1), (C2), (C3) and (C4). May further be included.

  The water-repellent fiber product of the present invention can sufficiently maintain the texture and water repellency even when used outdoors for a long time.

  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 water repellent composition according to the present invention.

  According to the method for producing a water-repellent fiber product of the present invention, the water-repellent composition according to the present invention is excellent in storage stability and can impart sufficient water repellency to a fiber product or the like even without heat treatment. By using the product, a water-repellent fiber product excellent in texture and water repellency can be stably produced. 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.

  According to the present invention, it is excellent in storage stability and can impart sufficient water repellency to a fiber product or the like even without heat treatment, thereby obtaining a water repellent fiber product excellent in texture and water repellency. It is possible to provide a water repellent composition capable of

  The water repellent composition of the present invention exhibits excellent water repellency while being a water repellent composition that does not contain a compound having a fluoroalkyl group or fluorine, and can be used as a substitute for a fluorine-based water repellent. Thus, concerns about the influence on the fluorine supply source and the environment can be eliminated. In addition, after attaching the water repellent composition to a fiber product or the like, it is usually preferable to perform heat treatment. However, since the water repellent composition of the present invention does not use a monomer having a fluoroalkyl group, Even when heat-treated under the following mild conditions, high water repellency can be exhibited, and when heat-treated at a high temperature exceeding 130 ° C., the heat treatment time is shorter than in the case of a fluorine-based water repellent. Can do. 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. In addition, since the water repellent composition according to the present invention can improve the emulsifying dispersibility of the non-fluorinated polymer itself, it is easy to maintain a stable emulsified state even when added to a processing bath, and various fiber processing It becomes possible to cope with.

  The water repellent composition of the present embodiment is derived from a (meth) acrylic acid ester monomer (A) represented by the following general formula (A-1) (hereinafter also referred to as “component (A)”). (B1) a compound represented by the following general formula (I-1) having an HLB of 7 to 18, and (B2) a compound represented by the following general formula (II-1) having an HLB of 7 to 18. And (B3) at least one kind of reactivity 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 the HLB is 7 to 18. A non-fluorinated polymer containing a structural unit derived from the emulsifier (B) (hereinafter also referred to as “component (B)”) is included.

［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. ]

［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. ]

  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 “reactive emulsifier” is an emulsifying dispersant having radical reactivity, that is, a surfactant having one or more polymerizable unsaturated groups in the molecule. It can be copolymerized with such monomers.

  “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 (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 HLB of the compounds (B1) to (B3) used in the present embodiment is 7 to 18, and the non-fluorine polymer contained in the water repellent composition of the present embodiment (hereinafter referred to as the present embodiment). 9 to 15 are preferred from the viewpoint of emulsion stability (hereinafter simply referred to as emulsion stability) during and after emulsion polymerization or dispersion polymerization of the non-fluorinated polymer). Furthermore, it is more preferable to use two or more reactive emulsifiers (B) having different HLBs within the above range in view of the storage stability of the water repellent composition.

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 of the present embodiment. 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-fluorinated polymer of the present embodiment, m is preferably an integer of 1 to 80, and more preferably an integer of 1 to 60. When m is 2 or more, m A ¹ 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 group, tridecadienyl group, tetradecenyl group, tetradienyl group, pentadecenyl group, pentadecadienyl group, pentadecatrienyl group, heptadecenyl group, heptadecadienyl group, heptadecatrienyl group, etc. . From the viewpoint of emulsion stability of the non-fluorinated polymer of the present embodiment, R ⁴ is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

Y ² is a divalent group containing an 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 of the present embodiment, 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 of the present embodiment, the type and combination of A ² O and the number of n can be appropriately selected so as to be within the above HLB range. In terms of emulsion stability of the non-fluorine polymer of the present embodiment, 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 8 to 14 An integer is more preferred. 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 of this embodiment, an alkylene oxide adduct of a triglyceride of a fatty acid containing at least one hydroxy unsaturated fatty acid is preferable, and carbon of castor oil (a triglyceride of a fatty acid containing ricinoleic acid) An alkylene oxide adduct having a number of 2 to 4 is more preferable, and an ethylene oxide adduct of castor oil is more preferable. Furthermore, the number of added moles of alkylene oxide can be appropriately selected so as to be within the range of the above HLB, and is preferably 20 to 50 moles from the viewpoint of emulsion stability of the non-fluorinated polymer of the present embodiment, 25-45 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 content ratio of the structural unit derived from the component (A) and the structural unit derived from the component (B) in the non-fluorine polymer of the present embodiment is the water repellency of the resulting fiber product and the non-fluorine polymer of the present embodiment. In view of emulsion stability, the ratio (A) / (B) of the mass of the component (A) to be blended and the mass of the component (B) is preferably 85/15 to 99/1, 90 / More preferably, it is 10-97 / 3. When (A) / (B) is less than 85/15, the water repellency of the resulting fiber product tends to be insufficient. When (A) / (B) exceeds 99/1, the emulsification stability of the non-fluorinated polymer of this embodiment tends to be insufficient.

  Moreover, 80-100 mass% is preferable on the basis of the monomer component whole quantity which comprises a non-fluorine-type polymer, and the total mass of the mass of (A) component to mix | blend and the mass of (B) component is 85-99 mass. % Is more preferable, and 90-98 mass% is still more preferable.

  It is preferable that the weight average molecular weight of the non-fluorine polymer of this embodiment is 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-fluorine polymer of this embodiment are equal, the higher the blending ratio of the non-fluorine (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.

  In addition to the component (A) and the component (B), the non-fluorinated polymer contained in the water repellent composition of the present embodiment can improve the durable water repellency of the resulting fiber product. A single amount of at least one second (meth) acrylic acid ester monomer (C) (hereinafter also referred to as “C component”) selected from the group consisting of (C2), (C3) and (C4). It is preferably contained as a body component.

［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。］(C1) (meth) acrylic acid ester monomer represented by the following general formula (C-1)

[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. ]

  The content ratio of the structural unit derived from the component (A), the structural unit derived from the component (B), and the structural unit derived from the component (C) in the non-fluorine-based polymer of the present embodiment is blended with the component (A). The ratio (A) + (B) / (C) of the total mass of (B) and the total mass of component (B) to the mass of component (C) is preferably 70/30 to 99.9 / 0.1. 75/25 to 99/1 is more preferable.

  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. 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) is 0.1 to 30 mass 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. %, More preferably 1 to 25% by mass, and still more preferably 5 to 20% by mass.

  The monomer (C2) is a (meth) acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester moiety, and the cyclic hydrocarbon group includes an isobornyl group, Examples 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 composition ratio of the monomer (C2) is 0.1 to 30 mass with respect to the total amount of the monomer components constituting the non-fluorine polymer in terms of water repellency and texture of the resulting fiber product. %, More preferably 1 to 25% by mass, and still more preferably 5 to 20% by mass.

  The monomer (C3) is a methacrylic acid ester monomer in which an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms is directly bonded to the ester bond of the ester moiety. As the chain hydrocarbon group having 1 to 4 carbon atoms, a linear hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms are preferable. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, 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) is 0.1 to 30 mass with respect to the total amount of the monomer components constituting the non-fluorine polymer in terms of water repellency and texture of the resulting fiber product. %, More preferably 1 to 25% by mass, and still more preferably 5 to 20% by mass.

  The monomer (C4) is a (meth) acrylic acid ester monomer having 3 or more polymerizable unsaturated groups in one molecule. In 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, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, diethylene Examples include pentaerythritol 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 is more preferable because it can improve the durable water repellency of the obtained fiber product.

  The composition ratio of the monomer (C4) is 0.1 to 5 mass with respect to the total amount of monomer components constituting the non-fluorine polymer in terms of water repellency and texture of the resulting fiber product. % Is preferred.

  In addition to the component (A), the component (B) and the component (C), the non-fluorine polymer contained in the water repellent composition of the present embodiment is a monofunctional monomer (D ) Can be contained within a range not impairing the effects of the present invention.

  Examples of the monomer (D) include (meth) acrylic acid ester, (meth) acrylic acid, fumaric acid ester, maleic acid ester having a hydrocarbon group other than (A) component and (C) component, Examples include fumaric acid, maleic acid, (meth) acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, vinyl monomers not containing fluorine such as vinyl chloride, vinylidene chloride, ethylene, and styrene. 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.

  The composition ratio of the monomer (D) is 10% by mass or less 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 preferable.

  The non-fluorine-based polymer contained in the water repellent composition of the present embodiment is 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. It is preferable that the fiber product has durable water repellency. 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.

  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, the manufacturing method of the water repellent composition containing the non-fluorine-based polymer of this embodiment will be described.

  A water repellent composition containing a non-fluorine 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, (meth) represented by the above general formula (A-1) in the presence of at least one reactive emulsifier (B) selected from the compounds (B1) to (B3) in the medium. A non-fluorinated polymer can be obtained by emulsion polymerization or dispersion polymerization of the acrylate monomer (A). More specifically, for example, the component (A), the component (B), and, if necessary, an emulsification aid or dispersion aid are added to the medium, and this mixed solution is emulsified or dispersed to give an emulsion or dispersion. Get things. 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 etc.”) include nonionic surfactants other than the reactive emulsifier (B), cationic surfactants, anionic surfactants, and One or more selected from amphoteric 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 0.1 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 water-repellent fiber product of the present embodiment is made of a fiber product to which the above-described non-fluorine polymer of the present embodiment is attached.

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

  The water-repellent fiber product of the present embodiment is obtained by treating a fiber product with a treatment liquid containing the above-described water repellent composition, thereby attaching a non-fluorine polymer to the fiber product. 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 fiber product may be any form such as fiber, yarn, cloth, non-woven fabric, and paper.

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

  The amount of the water repellent composition attached to the fiber product can be appropriately adjusted according to the required degree of water repellency, but the non-fluorinated polymer contained in the water repellent composition with respect to 100 g of the fiber product. It is preferable to adjust so that the adhesion amount may become 0.01-10g, and it is more preferable to adjust so that it may become 0.05-5g. If the adhesion amount of the non-fluorine polymer is less than 0.01 g, the fiber product tends not to exhibit sufficient water repellency compared to the case where the adhesion amount of the non-fluorine polymer is in the above range. When it exceeds, compared with the case where the adhesion amount of a non-fluorine-type polymer exists in the said range, it exists in the tendency for the feel of a textile product to become coarse and hard.

  Moreover, after making the non-fluorine-type polymer of this embodiment adhere to textiles, it is preferable to heat-process suitably. The temperature condition is not particularly limited, but if the water repellent composition of the present embodiment is used, sufficiently good water repellency can be expressed in the fiber product 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 durable water repellency, the above-mentioned step of treating a textile product with a treatment liquid containing a water repellent composition, and a compound having one or more methylol melamine, isocyanate groups or blocked isocyanate groups It is preferable that the fiber product is water-repellent processed by a method including a step of attaching a cross-linking agent represented by the above to the fiber product and heating it. Furthermore, when it is desired to further improve the durable water repellency, the water repellent composition preferably contains a non-fluorinated polymer obtained by copolymerizing a monomer having a functional group capable of reacting with the above-mentioned crosslinking agent.

  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 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 the non-fluorine polymer contained in the water repellent composition of the present invention, in the above embodiment, the polymerization reaction is performed by radical polymerization, but ionization such as ultraviolet rays, electron beams, and γ rays is performed. The polymerization reaction may be performed by photopolymerization that irradiates with actinic radiation.

  In the present invention, the water repellent composition is treated with a fiber product to obtain a water-repellent fiber product. However, the product treated with the water repellent composition is not limited to the use of a fiber product, but is made of metal, glass. It may be an article such as a resin.

  In such a case, the method for adhering the 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 polymer dispersion>
Polymer mixtures having the compositions shown in Tables 1 to 5 (in the tables, the numerical values indicate (g)) were polymerized by the following procedure to obtain polymer dispersions.

Example 1
In a 500 mL flask, stearyl acrylate 60 g, Latem PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 2 g, Latem PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB) = 14.4) 2 g, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 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. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

(Example 2)
In a 500 mL flask, 55 g of stearyl acrylate, Latemu PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6), 2 g, Latemu PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB) = 14.4) 2 g, 2-hydroxyethyl acrylate 5 g, stearyldimethylamine hydrochloride 3 g, dodecyl mercaptan 0.15 g, tripropylene glycol 20 g and water 162.6 g were mixed and stirred at 45 ° C. did. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

(Example 3)
In a 500 mL flask, 55 g of stearyl methacrylate, Latemu PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6), 2 g, Latemu PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB) = 14.4) 2 g, 2-hydroxyethyl acrylate 5 g, stearyldimethylamine hydrochloride 3 g, dodecyl mercaptan 0.05 g, tripropylene glycol 20 g and water 162.7 g are mixed and stirred at 45 ° C. did. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

Example 4
In a 500 mL flask, 55 g of stearyl acrylate, Latemu PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6), 2 g, Latemu PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB) = 14.4) 2 g, 2-hydroxyethyl acrylate 5 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g and water 162.75 g were added and 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. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

(Example 5)
In a 500 mL flask, 55 g of cetyl acrylate, Latemu PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6), 2 g, Latemu PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB) = 14.4) 2 g, 2-hydroxyethyl acrylate 5 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g and water 162.75 g were added and 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. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

(Example 6)
In a 500 mL flask, 55 g of lauryl acrylate, Latemu PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6), 2 g, Latemu PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB) = 14.4) 2 g, 2-hydroxyethyl acrylate 5 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g and water 162.75 g were added and 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. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

(Example 7)
To a 500 mL flask was added 55 g of stearyl acrylate, 12.5 mol of cardanol ethylene oxide adduct (HLB = 12.9, indicated as “cardanol 12.5EO” in the table), and 8.3 mol of cardanol ethylene oxide. 2 g of product (HLB = 11.0, indicated in the table as “Cardanol 8.3 EO”), 5 g of 2-hydroxyethyl acrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water, The mixture was stirred at 45 ° C. to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

(Example 8)
In a 500 mL flask, stearyl acrylate 55 g, 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) 2 g, 5 g of 2-hydroxyethyl acrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water were added at 45 ° C. The mixture was stirred to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

Example 9
In a 500 mL flask, 57 g of stearyl acrylate, Latemu PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6), 2 g, Latemu PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB) = 14.4) 2 g, 3 g of tetramethylolmethane tetraacrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 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. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

(Example 10)
In a 500 mL flask, 55 g of stearyl acrylate, Latemu PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6), 2 g, Latemu PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB) = 14.4) 2 g, 5 g of dimethylaminoethyl methacrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 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. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

(Example 11)
In a 500 mL flask, 55 g of stearyl acrylate, Latemu PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6), 2 g, Latemu PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB) = 14.4) 2 g, 5 g of glycidyl methacrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 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. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

Example 12
In a 500 mL flask, 55 g of stearyl acrylate, Latemu PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6), 2 g, Latemu PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB) = 14.4) 2 g, methyl ethyl ketone oxime blocked product of 1,1-bis (acryloyloxymethyl) ethyl isocyanate 5 g, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water are mixed at 45 ° C. Stir to make a mixture. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

(Example 13)
In a 500 mL flask, stearyl acrylate 51 g, Latem PD-420 (Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 4 g, Latem PD-430 (Kao Corporation, polyoxyalkylene alkenyl ether, HLB) = 14.4) 4 g, 2 g of 2-hydroxyethyl acrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 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. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

(Example 14)
In a 500 mL flask, 56 g of stearyl acrylate, LATEMUL PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6) 0.5 g, LATEMUL PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether) HLB = 14.4) 0.5 g, polyoxyethylene (10 mol) lauryl ether 2 g, 2-hydroxyethyl acrylate 5 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g and water 162.75 g were added. 45 The mixture was stirred at 0 ° C. to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

(Example 15)
In a 500 mL flask, 45 g of stearyl acrylate, Latemul PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6), 2 g of latemul PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB) = 14.4) 2 g, 2-hydroxyethyl acrylate 5 g, isobornyl acrylate 10 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g and water 162.75 g 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. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

(Example 16)
In a 500 mL flask, 45 g of stearyl acrylate, Latemul PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6), 2 g of latemul PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB) = 14.4) 2 g, 2-hydroxyethyl acrylate 5 g, isobornyl methacrylate 10 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g and water 162.75 g 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. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

(Example 17)
In a 500 mL flask, 45 g of stearyl acrylate, Latemul PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6), 2 g of latemul PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB) = 14.4) 2 g, 2-hydroxyethyl acrylate 5 g, cyclohexyl methacrylate 10 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g and water 162.75 g 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. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

(Example 18)
In a 500 mL flask, 45 g of stearyl acrylate, Latemul PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6), 2 g of latemul PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB) = 14.4) 2 g, 2-hydroxyethyl acrylate 5 g, methyl methacrylate 10 g, stearyldimethylamine hydrochloride 3 g, tripropylene glycol 20 g and water 162.75 g 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. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 26% by mass. .

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）６０ｇ、ステアリルジメチルアミン塩酸塩３ｇ、ポリオキシエチレン（１０モル）ラウリルエーテル７ｇ、トリプロピレングリコール２０ｇ及び水１５８．５ｇを入れ、４５℃にて混合攪拌し混合液とした。この混合液に超音波を照射して上記混合物を乳化分散させた。次いで、アゾビス（イソブチルアミジン）二塩酸塩１．５ｇを混合液に添加し、窒素雰囲気下で６０℃にて６時間ラジカル重合させて、ポリマー濃度２４質量％のフッ素系ポリマー分散液を得た。(Comparative Example 1)
In a 500 mL flask, the following general formula (III):

60 g of a mixture in which the average value of n is 8 (wherein n is 6, 8, 10, 12, or 14), stearyldimethylamine hydrochloride 3 g, polyoxy 7 g of ethylene (10 mol) lauryl ether, 20 g of tripropylene glycol and 158.5 g of water were added and mixed and stirred at 45 ° C. to obtain a mixed solution. The mixture was emulsified and dispersed by irradiating the mixture with ultrasonic waves. Next, 1.5 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 fluorine-based polymer dispersion having a polymer concentration of 24 mass%.

(Comparative Example 2)
In a 500 mL flask, put 55 g of stearyl acrylate, 4 g of polyoxyethylene (10 mol) lauryl ether, 5 g of 2-hydroxyethyl acrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water, and bring the temperature to 45 ° C. The mixture was stirred to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 24% by mass. .

(Comparative Example 3)
In a 500 mL flask, put 55 g of stearyl acrylate, 4 g of polyoxyethylene (10 mol) lauryl ether, 5 g of 2-hydroxyethyl acrylate, 7 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol, and 158.75 g of water, and bring them to 45 ° C. The mixture was stirred to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 24% by mass. .

(Comparative Example 4)
In a 500 mL flask, 55 g of stearyl acrylate, 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), 5 g of 2-hydroxyethyl acrylate, 3 g of stearyldimethylamine hydrochloride, 20 g of tripropylene glycol and 162.75 g of water are mixed and stirred at 45 ° C. and mixed. Liquid. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Subsequently, 0.25 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-fluorinated polymer dispersion having a polymer concentration of 24% by mass. .

  In addition, as for each polymer in the polymer dispersion liquid obtained in Examples 1-18 and Comparative Examples 1-4, all are 98 of all monomers by gas chromatograph (GC-15APTF, the Shimadzu Corporation make). % Or more was confirmed to be polymerized.

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

(Physical property evaluation of non-fluorinated polymers)
By adding 500 mL of acetone to 50 g of the polymer dispersions obtained in Examples 1 to 18 and Comparative Examples 1 to 4, the polymer and the emulsifier were separated, the polymer was collected by filtration, and the polymer was dried under reduced pressure at 25 ° C. for 24 hours. It was. The obtained polymer was evaluated as follows. The results are shown in Tables 6-9.

(1) Method for measuring melt viscosity For the polymers of Examples 1 to 18 and Comparative Examples 2 to 4 obtained above, an elevated flow tester CFT-500 (manufactured by Shimadzu Corporation) was used and the die (length) was measured. 1 g of the polymer was put in a cylinder attached with a diameter of 10 mm and held at 105 ° C. for 6 minutes. A load of 100 kg · f / cm ² was applied with a plunger to measure the melt viscosity at 105 ° C.

(2) Measuring method of weight average molecular weight About the polymer of Examples 1-18 obtained above and Comparative Examples 2-4, column temperature 40 degreeC by GPC apparatus (Tosoh Co., Ltd. product GPC "HLC-8020"). The measurement was performed using tetrahydrofuran as an eluent under a flow rate of 1.0 ml / min, 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.

(Storage stability evaluation of water repellent composition)
The stability when the polymer dispersions obtained in Examples 1 to 18 or Comparative Examples 1 to 4 were stored at 45 ° C. for 2 weeks was evaluated according to the following criteria. The results are shown in Tables 6-9.
A: No change in appearance B: Oil near the liquid level and slight polymer deposits on the container wall C: Polymer precipitates, separation and gelation observed

(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, dyed 100% polyester cloth or 100% nylon cloth was added with water so that the polymer dispersion of Examples 1 to 18 or Comparative Examples 1 to 4 was 3% by mass. After the immersion treatment (pickup rate 60% by mass) in the diluted treatment liquid, it was dried at 130 ° C. for 2 minutes and further heat-treated under the conditions shown in Tables 6 to 9, and the water repellency of the obtained fabric was evaluated. . 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 6-9.
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 the dyed 100% polyester cloth in a treatment liquid obtained by diluting the polymer dispersion liquid of Examples 1 to 18 or Comparative Examples 1 to 4 with water so that the polymer content becomes 3% by mass. After the treatment (pickup rate 60 mass%), it was evaluated by using a product which was 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 five stages. The results are shown in Tables 6-9.
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%. Examples 1 to 18 or Comparative Example 1 so that the content of 3% by mass and UNIKA CATALYST 3-P (surfactant, manufactured by Union Chemical Industries, Ltd., amino alcohol hydrochloride) is 0.2% by mass. It was obtained by immersing the polymer dispersion liquid of -4 and the above-mentioned respective chemicals in a processing 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 The water repellency of the cloth (L-0) and JIS L 0217 (1995) after washing 10 times (L-10) is the same as the above water repellency evaluation method. It was evaluated. 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 6-9.

  Even when the fiber products treated with the water repellent compositions of Examples 1 to 18 are not heat-treated, the water repellency and durability are equal to or higher than those when the conventional fluorine-based water repellent (Comparative Example 1) is used. It was confirmed that water repellency was exhibited and the texture was good. Moreover, it was confirmed that the storage stability of the composition is also good.

  When Example 2 and Example 4 are compared, even if the composition of the non-fluorinated polymer is close, if the weight average molecular weight of the polymer is different, the higher the weight average molecular weight, the better the water repellency. Was confirmed.

  The water repellent composition of Comparative Example 2 uses a general surfactant that is not a reactive emulsifier. With the same amount of surfactant as in Example 4 using a reactive emulsifier, It was confirmed that the storage stability was lowered.

  In comparison with Comparative Example 2, the water repellent composition of Comparative Example 3 was obtained by increasing the amount of emulsification aid (general surfactant) for the purpose of improving the storage stability of the composition. There was a tendency for the water repellency of the textiles treated with the product to decrease.

  The water repellent composition of Comparative Example 4 was subjected to emulsion polymerization using a general surfactant having an HLB within the preferred range of the present invention instead of the reactive emulsifier, and the treated fiber product was repelled. It was confirmed that the aqueous property decreased.

  As described above, according to the present invention, the water-repellent fiber product is excellent in storage stability and can impart sufficient water repellency to a fiber product or the like even without heat treatment, and has excellent texture and water repellency. It was confirmed that a water repellent composition capable of providing

  The water repellent composition of the present invention is particularly effective for textile products. When the water repellent composition of the present invention is used for textile products, it is weak against heat because it can exhibit sufficiently excellent water repellency even after heat treatment at a low temperature after treating the fiber product with the water repellent composition. Water repellency can be sufficiently exhibited even in special fibers and natural fibers. Furthermore, durability water repellency and a feeling can be improved by using a crosslinking agent together or copolymerizing a reactive monomer. In addition, the water repellent composition of the present invention does not contain a fluorine-containing group, so that it is low in cost and useful as a water repellent composition having little adverse effect on the human body and the environment. In addition, the amount of the surfactant used can be reduced as compared with the conventional water repellent, and various fiber processing can be handled.

Claims (9)

A structural unit derived from the (meth) acrylic acid ester monomer (A) represented by the following general formula (A-1);
(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) To at least one reactive emulsifier (B) 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. Derived structural unit, and
A water repellent composition comprising a non-fluorine-based polymer containing

[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. ]

[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 polymer is derived from at least one second (meth) acrylate monomer (C) selected from the group consisting of (C1), (C2), (C3) and (C4) below. The water repellent composition according to claim 1, further comprising a constituent unit.
(C1) (meth) acrylic acid ester monomer represented by the following general formula (C-1)

[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. ]
(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. ]
(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. ]
(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. ] (Meth) acrylic acid ester monomer (A) represented by the following general formula (A-1);
(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 (B) 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 the HLB is 7 to 18. ,
A water repellent composition comprising a non-fluorinated polymer obtained by emulsion polymerization or dispersion polymerization of an emulsion or dispersion containing

[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. ]

[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 emulsion or dispersion is at least one second (meth) acrylic acid ester monomer (C) selected from the group consisting of (C1), (C2), (C3) and (C4) below. The water repellent composition according to claim 3, further comprising:
(C1) (meth) acrylic acid ester monomer represented by the following general formula (C-1)

[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. ]
(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. ]
(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. ]
(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. ] A structural unit derived from the (meth) acrylic acid ester monomer (A) represented by the following general formula (A-1);
(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) To at least one reactive emulsifier (B) 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. Derived structural unit, and
A water-repellent fiber product comprising a fiber product to which a non-fluorine-based polymer containing benzene is attached.

[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. ]

[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 polymer is derived from at least one second (meth) acrylate monomer (C) selected from the group consisting of (C1), (C2), (C3) and (C4) below. The water-repellent fiber product according to claim 5, further comprising a constituent unit.
(C1) (meth) acrylic acid ester monomer represented by the following general formula (C-1)

[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. ]
(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. ]
(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. ]
(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. ] (Meth) acrylic acid ester monomer (A) represented by the following general formula (A-1);
(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 (B) 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 the HLB is 7 to 18. ,
A water-repellent fiber product comprising a fiber product to which a non-fluorine polymer obtained by emulsion polymerization or dispersion polymerization of an emulsion or dispersion containing selenium is attached.

[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. ]

[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 emulsion or dispersion is at least one second (meth) acrylic acid ester monomer (C) selected from the group consisting of (C1), (C2), (C3) and (C4) below. The water-repellent fiber product according to claim 7, further comprising:
(C1) (meth) acrylic acid ester monomer represented by the following general formula (C-1)

[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. ]
(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. ]
(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. ]
(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. ]   A method for producing a water-repellent fiber product, comprising: treating the fiber product with a treatment liquid containing the water repellent composition according to any one of claims 1 to 4.