JP6529318B2 - Non-fluorinated polymer, water repellent composition, water repellent fiber product and method for producing water repellent fiber product - Google Patents

Description

  The present invention relates to a non-fluorinated polymer, 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 by treating such a fluorine-based water repellent onto a fiber product or the like, a fiber product having water repellency imparted to the surface thereof is known. . Such a fluorine-based water repellent is generally produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group.

  Although the textile treated with the fluorine-based water repellent exhibits excellent water repellency, it is necessary to adjust the orientation of the fluoroalkyl group in order to express the water repellency, therefore the fluorine-based water repellency of the textile Heat treatment must be performed at temperatures above 130 ° C. after depositing the agent. However, heat treatment at high temperatures requires high energy, and there is a problem in the international energy saving flow.

  In addition, monomers having a fluoroalkyl group are expensive and thus are not satisfactory in terms of economy, and furthermore, monomers having a fluoroalkyl group are difficult to be decomposed and thus are also problematic in terms of environment There is.

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

  Therefore, in recent years, research on non-fluorinated water repellents containing no fluorine has been advanced. For example, Non-Patent Document 1 discloses a water repellent agent 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-fluorinated polymer is emulsified and dispersed for the purpose of imparting water repellency not inferior to conventional fluorine-based water repellents.

"Super water repellent finish, the entire volume of processing agents and new trends in moisture permeable 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. In addition, the treated fiber products tend to be hard, and it can not be said that the feeling is sufficient.

  In the case of the non-fluorinated water repellent described in Patent Document 1, the water repellency of the resulting fiber product can be obtained by blending a surfactant in an amount sufficient to emulsify and disperse the non-fluorinated polymer in order to ensure storage stability. Tends to decrease, and it is difficult to achieve both storage stability and water repellency.

  In addition, when a plurality of untreated cloths are subjected to water repellent finish successively using the same treatment liquid containing the non-fluorine-based water repellent described in Patent Document 1, it is a fiber product processed every number of times. Water repellency tends to decrease.

  The present invention has been made in view of the above-mentioned circumstances, and is excellent in storage stability and adequate continuous processing, and can impart sufficient water repellency to textiles etc. even when not heat-treated, and it has a texture And a non-fluorinated polymer capable of obtaining a water repellent fiber product excellent in water repellency, and a method of producing a water repellent composition, a water repellent fiber product, and a water repellent fiber product using the same I assume.

  The present invention is derived from a structural unit derived from a (meth) acrylic acid ester monomer (A) represented by the following general formula (A-1), and a silicone oil (E) having a (meth) acryloyl group Provided is a non-fluorinated polymer containing a structural unit.

［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 that may have a substituent. ]

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

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

[In 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 containing. ]

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

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

  The non-fluorinated polymer is a structural unit derived from at least one second (meth) acrylic acid ester monomer (C) selected from the group consisting of (C1), (C2) and (C3) below: Furthermore, you may contain.

［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 the formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ represents at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group and a (meth) acryloyloxy group It represents a C1-C11 monovalent chain hydrocarbon group having one type 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。］
（Ｃ３）下記一般式（Ｃ−３）で表されるメタクリル酸エステル単量体 (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) Methacrylic acid ester monomer represented by the following general formula (C-3)

［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。］

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

  The present invention is also an emulsion or dispersion comprising (meth) acrylic acid ester monomer (A) represented by the above general formula (A-1) and silicone oil (E) having a (meth) acryloyl group. The present invention provides a non-fluorinated polymer obtained by emulsion polymerization or dispersion polymerization of a polymer.

［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 that may have a substituent. ]

  The emulsion or the dispersion is a compound represented by the following formula (I-1) having (B1) HLB of 7 to 18, (B2) a compound having the following formula (II-1) having an HLB of 7 to 18. And at least one compound selected from compounds obtained by adding an alkylene oxide of 2 to 4 carbon atoms to a fat and oil having a hydroxyl group and a polymerizable unsaturated group, and a compound represented by It may further contain a species of reactive emulsifier (B).

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

[In 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 containing. ]

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

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

  Further, the emulsion or the dispersion further comprises at least one second (meth) acrylic acid ester monomer (C) selected from the group consisting of (C1), (C2) and (C3) below: May be included.

［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。］
（Ｃ２）下記一般式（Ｃ−２）で表される（メタ）アクリル酸エステル単量体

[In the formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ represents at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group and a (meth) acryloyloxy group It represents a C1-C11 monovalent chain hydrocarbon group having one type 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)

［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。］
（Ｃ３）下記一般式（Ｃ−３）で表されるメタクリル酸エステル単量体

[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) Methacrylic acid ester monomer represented by the following general formula (C-3)

［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。］

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

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

  The present invention also provides a water repellent fiber product comprising a fiber product to which the non-fluorinated polymer according to the present invention is attached.

  The water repellent fiber product of the present invention can sufficiently maintain the feeling and the 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 the step of treating the 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 storage stability and the continuous processing suitability are excellent, and sufficient water-repellency can be imparted to a fiber product etc. even when no heat treatment is performed. By using a water repellent composition containing a non-fluorinated polymer, it is possible to stably manufacture a water repellent fiber product excellent in feeling and water repellency. In addition, since the method for producing a water-repellent fiber product of the present invention does not require heat treatment at a high temperature, energy saving can be achieved, and since a non-fluorinated water repellent is used, it is possible to the environment. The load can be reduced.

  According to the present invention, while being excellent in storage stability and continuous processing suitability, it is possible to impart sufficient water repellency to a fiber product etc. even when not subjected to heat treatment, and a water repellent fiber excellent in feeling and water repellency. It is possible to provide a non-fluorinated polymer from which a product can be obtained and a water repellent composition containing the same.

  According to the water repellent composition of the present invention, a fiber product having a certain level of water repellency can be stabilized even when a plurality of fiber products are continuously subjected to water repellent finish using the same treatment liquid. Can be obtained.

  In addition, the water repellent composition of the present invention is a water repellent composition which does not contain a compound having a fluoroalkyl group or a fluorine, but exhibits excellent water repellency and is used as a substitute for a fluorine-based water repellent. It is possible to eliminate the concern about the influence on the fluorine supply source, the environment, etc. After the water repellent composition is attached to the fiber product etc., it is usually preferable to carry out heat treatment, but since the water repellent composition of the present invention does not use a monomer having a fluoroalkyl group, it is 130.degree. 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 the fluorine-based water repellent It can be done. Therefore, the deterioration of the object to be treated due to the heat can be suppressed, so that the feeling becomes flexible, and the heat amount required for the heat treatment can be reduced.

  Furthermore, according to the present invention, a water repellent composition by using a specific reactive emulsifier instead of a general surfactant as an emulsifying dispersant used for emulsification or dispersion polymerization of a non-fluorinated polymer. The amount of surfactant contained in can be reduced. As a result, it is possible to suppress the decrease in the water repellency of the resulting fiber products and the like, and to realize higher water repellency than conventional non-fluorinated water repellents. Moreover, since the water repellent composition according to the present invention can improve the emulsification and dispersion of the non-fluorinated polymer itself, it is easy to maintain a stable emulsification state even when added to the processing bath, and various fiber processing It is possible to cope with

  The water repellent composition of the present embodiment is derived from a (meth) acrylic acid ester monomer (A) (hereinafter, also referred to as "component (A)") represented by the following general formula (A-1). Non-fluorinated polymer (hereinafter referred to as the embodiment of the present invention) containing a constituent unit derived from the constituent unit and a constituent unit derived from a silicone oil (E) having a (meth) acryloyl group (hereinafter, also referred to as “component (E)”) It is called non-fluorinated polymer).

［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 that may have a substituent. ]

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

The (meth) acrylic acid ester monomer (A) represented by the above general formula (A-1) used in this embodiment has 1 or more carbon atoms of 12 or more which may have a substituent. Have a valence hydrocarbon group. The hydrocarbon group may be linear or branched, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and further may be an alicyclic or aromatic cyclic group. May be included. Among these, linear ones are preferable, and 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, examples of the substituent include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group and a (meth) acryloyloxy group One or more of them may be mentioned. In the embodiment, in the above general formula (A-1), R ² is preferably a non-substituted hydrocarbon group.

  It is preferable that carbon number of the said hydrocarbon group is 12-24. When the non-fluorinated polymer is attached to a fiber product or the like with a carbon number of less than 12, sufficient water repellency can not be exhibited. On the other hand, when the number of carbons exceeds 24, when non-fluorinated polymers are attached to a fiber product or the like, the texture of the fiber product tends to be coarser than when the number of carbons is in the above range. .

  It is more preferable that carbon number of the said hydrocarbon group is 12-21. When the carbon number is in this range, the water repellency and the feel become particularly excellent. Particularly preferable as the hydrocarbon group is a linear alkyl group having 12 to 18 carbon atoms.

  Examples of the component (A) include stearyl (meth) acrylate, cetyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, and (meth) acrylic acid. Pentadecyl, heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, helicosyl (meth) acrylate, behenyl (meth) acrylate, seryl (meth) acrylate, melic (meth) acrylate Can be mentioned.

  The component (A) can have at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group capable of reacting with the crosslinking agent. In this case, the durable water repellency of the resulting textile can be further improved. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. Moreover, when the said (A) component has an amino group, the touch 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 silicone oil (E) having a (meth) acryloyl group used in the present embodiment is a silicone oil having at least one (meth) acryloyl group in one molecule, and it is possible to use (meth) silicone oil as the silicone oil. It can be obtained by introducing an acryloyl group. The silicone oil may be any polysiloxane having a main chain composed of a siloxane bond, for example, dimethyl silicone oil in which all side chains and ends are methyl groups, and part of side chains of dimethyl silicone substituted with phenyl groups Examples thereof include methylphenyl silicone oil and methyl hydrogen silicone oil in which the methyl group in the side chain of dimethyl silicone is partially hydrogen. Among them, dimethyl silicone oil is preferable.

  The introduction position of the (meth) acryloyl group in the component (E) is not particularly limited, and may be at both ends or one end of the main chain, or may be on the side chain. Furthermore, they may be present at both the terminal and side chains of the main chain. Among them, the (meth) acryloyl group at one end of the main chain as represented by the following general formula (E-1) from the viewpoint of having little influence on the water repellency of the obtained fiber product and preventing gelation at the time of polymerization Preferred are silicone oils having

［式（Ｅ−１）中、Ｒ^２１及びＲ^２２はそれぞれ独立に水素、メチル基又はフェニル基を表し、Ｒ^２３は、酸素原子、窒素原子又は硫黄原子を含んでいてもよい１価の炭化水素基を表し、Ｒ^２４は、酸素原子、窒素原子又は硫黄原子を含んでいてもよい２価の炭化水素基を表し、Ｒ^２５は水素又はメチル基を表し、ｓは０以上の整数である。］

[In formula (E-1), R ²¹ and R ²² each independently represent hydrogen, a methyl group or a phenyl group, and R ²³ represents a monovalent carbon which may contain an oxygen atom, a nitrogen atom or a sulfur atom] R ²⁴ represents a hydrogen group, R ²⁴ represents a divalent hydrocarbon group which may contain an oxygen atom, a nitrogen atom or a sulfur atom, R ²⁵ represents a hydrogen or methyl group, and s is an integer of 0 or more . ]

In the silicone oil represented by the above (E-1), R ²¹ and R ²² are preferably methyl groups from the viewpoint of suppressing troubles such as roll stains when water repellent finishing on textiles. ²³ is preferably a monovalent hydrocarbon group containing no oxygen atom, nitrogen atom and sulfur atom, and further, R ²⁴ is a divalent hydrocarbon containing no oxygen atom, nitrogen atom and sulfur atom It is preferably a group. Moreover, it is preferable that R ²⁵ is a methyl group from the viewpoint of the durable water repellency of the fiber product to be obtained. Furthermore, from the viewpoint of appropriate continuous processing, s is preferably 0 to 200, more preferably 1 to 100, and still more preferably 2 to 30.

  The functional group equivalent of the silicone oil represented by the above (E-1) is not particularly limited, but it is 200 to 16,000 g in terms of water repellency, feeling and continuous processing suitability of the obtained fiber product. / Mol is preferable, 250 to 8,000 g / mol is more preferable, and 300 to 2,500 g / mol is more preferable. Here, "functional group equivalent" means the mass of the main skeleton bonded to 1 mol of (meth) acryloyl group which is a functional group, for example, 1H-NMR obtained by nuclear magnetic resonance analyzer (NMR) It can be calculated from the spectral intensity of (proton NMR).

  Further, s in the silicone oil represented by (E-1) can be calculated from the functional group equivalent, and is preferably an integer satisfying the preferable range of the functional group equivalent.

  As a silicone oil represented by said (E-1), a commercial item can be used, For example, Shin-Etsu Silicone Co., Ltd. "X-22-2426", "X-22-174BX", "X-" 22-2475 "," KF-2012 "and" X-22-174 ASX "," Syraplane FM-0711 "," FM-0721 "," FM-0725 "," TM-0701 "and Chisso Corp. "TM-0701T", "AK-5" and "AK-30" manufactured by Toagosei Co., Ltd., and the like can be mentioned.

  The content ratio of the structural unit derived from the component (A) to the structural unit derived from the component (E) in the non-fluorinated polymer of the present embodiment is the water repellency, feel and continuous processing suitability of the obtained fiber product In terms of point, the ratio (A) / (E) of the mass of the component (A) to the mass of the component (E) is preferably 50/50 to 99.5 / 0.5, 80/20. It is more preferable that it is -99/1, and it is further more preferable that it is 90/10-98/2. When (A) / (E) is less than 50/50, the water repellency of the resulting fiber product tends to be insufficient. When (A) / (E) exceeds 99.5 / 0.5, the texture of the resulting fiber product is coarse-hardened, and continuous processing suitability tends to be poor.

  In addition, the total mass of the mass of the component (A) to be blended and the mass of the component (E) is preferably 80 to 100 mass%, based on the total amount of monomer components constituting the non-fluorinated polymer, 85 to 99 mass. % Is more preferable, and 90 to 98% by mass is further preferable.

  The weight average molecular weight of the non-fluorinated polymer of the present embodiment is preferably 100,000 or more. If the weight average molecular weight is less than 100,000, the water repellency of the resulting fiber product tends to be insufficient. Furthermore, the weight average molecular weight of the non-fluorinated polymer is more preferably 500,000 or more. In this case, the resulting 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 5,000,000.

  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 feeling of the resulting fiber product tends to be coarse and hard. In addition, when the melt viscosity of the non-fluorinated polymer is too high, when the non-fluorinated polymer is emulsified or dispersed to form the water repellent composition, the non-fluorinated polymer may be precipitated or precipitated, and the repellent The storage stability of the liquid preparation composition tends to decrease. The melt viscosity at 105 ° C. is more preferably 500 Pa · s or less. In this case, the obtained textile product etc. becomes more excellent in feeling while exhibiting sufficient water repellency.

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

  When the weight average molecular weights of the non-fluorinated polymers of this embodiment are equal, the higher the blending ratio of the non-fluorinated (meth) acrylic acid ester monomer, the higher the water repellency of the adhered fiber product tends to be higher. . In addition, by copolymerizing a non-fluorinated monomer that can be copolymerized, it is possible to improve the performance such as durability, water repellency and feeling of the adhered fiber product.

  The non-fluorinated polymer of the present embodiment can improve the water repellency of the obtained fiber product, and the emulsion stability in the composition after emulsion polymerization or dispersion polymerization of the non-fluorinated polymer of the present embodiment and after polymerization. And in addition to the (A) component and the (E) component, (B1) a compound represented by the following general formula (I-1) having an HLB of 7 to 18, (B2) a compound having an HLB of 7 to 18, The compound represented by the general formula (II-1), and (B3) a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a fat and oil having a hydroxyl group and a polymerizable unsaturated group having an HLB of 7 to 18 It is preferable to contain at least one reactive emulsifier (B) (hereinafter also referred to as "(B) component") selected from among them as a monomer component.

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

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

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

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

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

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

  The HLB of the compounds of the above (B1) to (B3) used in the present embodiment is 7 to 18, and it is in the composition at the time of emulsion polymerization or dispersion polymerization of the non-fluorinated polymer of the present embodiment and after polymerization. 9-15 are preferable at the point of the emulsion stability in (it is only hereafter called emulsion stability). Furthermore, it is more preferable to use together 2 or more types of reactive emulsifiers (B) which have different HLB within the said range in the storage stability of a water-repellent composition.

In the reactive emulsifier (B1) represented by the above general formula (I-1) used in the present embodiment, R ³ is hydrogen or a methyl group, and in terms of copolymerizability with the component (A) More preferably, it is a methyl group. X is a C1-C6 linear or branched alkylene group, and a C2-C3 linear alkylene group is more preferable at the emulsion stability of the non-fluorinated polymer of this embodiment. Y ¹ is a divalent group containing a C 2 to C 4 alkyleneoxy group. The type, combination and addition number of the alkyleneoxy group in Y ¹ can be appropriately selected so as to be within the above-mentioned HLB range. Moreover, when the alkyleneoxy group is 2 or more types, they can have a block addition structure or a random addition structure.

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

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

[In 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 is an alkyleneoxy group having 2 to 4 carbon atoms And m can be appropriately selected so as to fall within the range of the above HLB, and specifically, an integer of 1 to 80 is preferable, and when m is 2 or more, m A ¹ O are the same. Or they may be different. ]

In the compound represented by the above general formula (I-2), R ³ is hydrogen or a methyl group, and more preferably a methyl group in terms of copolymerizability with the component (A). X is a C1-C6 linear or branched alkylene group, and a C2-C3 linear alkylene group is more preferable at the emulsion stability of the non-fluorinated polymer of this embodiment. A ¹ O is an alkylene group having 2 to 4 carbon atoms. The type and combination of A ¹ O and the number of m can be appropriately selected so as to fall within the above-mentioned HLB range. In the 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 O 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 above 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, the "Lateml PD-420", "Latemul PD-430", "Latemul PD-450" etc. made by Kao Co., Ltd. can be mentioned.

In the reactive emulsifier (B2) represented by the above general formula (II-1) used in the present embodiment, R ⁴ is a monovalent unsaturated carbon 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 the 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 a C 2 to C 4 alkyleneoxy group. The type, combination and addition number of the alkyleneoxy group in Y ² can be appropriately selected so as to fall within the above-mentioned HLB range. Moreover, when the alkyleneoxy group is 2 or more types, they can have a block addition structure or a random addition structure. From the viewpoint of the emulsion stability of the non-fluorinated polymer of the present embodiment, the alkyleneoxy group is more preferably an ethyleneoxy group.

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

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

[In formula (II-2), R ⁴ represents a C 13-17 monovalent unsaturated hydrocarbon group having a polymerizable unsaturated group, and A ² O represents a C 2-4 alkyleneoxy group. N can be appropriately selected so as to fall within the above HLB range, and specifically, an integer of 1 to 50 is preferable, and when n is 2 or more, n A ² O are identical May also be different. ]

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

A ² O is an alkylene group having 2 to 4 carbon atoms. From the viewpoint of the 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 fall within the above HLB range. From the viewpoint of the emulsion stability of the non-fluorinated polymer of the present embodiment, A ² O is more preferably an ethyleneoxy group, n is preferably an integer of 1 to 50, and more preferably an integer of 5 to 20, An integer is more preferred. When n is 2 or more, n A ² O's 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 above general formula (II-2) used in the present embodiment adds an alkylene oxide to phenol having a corresponding unsaturated hydrocarbon group by a conventionally known method. Can be synthesized according to the present invention 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 potassium hydroxide.

  The phenol having the corresponding unsaturated hydrocarbon group includes, in addition to pure products or mixtures produced industrially, those present as pure products or mixtures extracted and purified from plants and the like. For example, 3- [8 (Z), 11 (Z), 14-pentadecatrienyl] phenol, 3- [8 (Z), 11 (Z), extracted from cashew nut shells etc. and collectively referred to as cardanol. -Pentadecadienyl] phenol, 3- [8 (Z) -pentadecenyl] phenol, 3- [11 (Z) -pentadecenyl] phenol and the like can be mentioned.

  The reactive emulsifier (B3) used in this embodiment is a compound having an HLB of 7 to 18 and having a hydroxyl group and a polymerizable unsaturated group and having a C 2-4 alkylene oxide added thereto. . As fats and oils having a hydroxyl group and a polymerizable unsaturated group, hydroxy unsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.) are included. Mention may also be made of triglycerides of fatty acids, including mono or diglycerides of fatty acids, and at least one hydroxy unsaturated fatty acid (such as ricinoleic acid, lisinoelliidic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of the emulsion stability of the non-fluorinated polymer of the present embodiment, an alkylene oxide adduct of triglyceride of fatty acid containing at least one kind of hydroxy unsaturated fatty acid is preferable, and carbon of castor oil (triglyceride of fatty acid containing ricinoleic acid) The alkylene oxide adduct of the number 2 to 4 is more preferable, and the ethylene oxide adduct of castor oil is further preferable. Furthermore, the addition mole number of the alkylene oxide can be appropriately selected so as to be within the above-mentioned HLB range, and in view of the emulsion stability of the non-fluorinated polymer of the present embodiment, 20 to 50 moles are more preferable. More preferably 25 to 45 moles. 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 a fat and 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 to a triglyceride of fatty acid containing ricinoleic acid, that is, castor oil using alkali catalyst such as caustic soda and potassium hydroxide under pressure at 120 to 170 ° C. .

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

  The non-fluorinated polymer of this embodiment can improve the durable water repellency of the resulting fiber product, and in addition to the components (A) and (E), the following (C1), (C2) and (C3) It is preferable to contain at least 1 type of 2nd (meth) acrylic acid ester monomer (C) (Hereinafter, it is also mentioned "C component".) Selected from the group which consists of as a monomer 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 the formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ represents at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group and a (meth) acryloyloxy group It represents a C1-C11 monovalent chain hydrocarbon group having one type 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) Methacrylic acid ester monomer represented by the following general formula (C-3)

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

  The monomer (C1) has a carbon number having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group and a (meth) acryloyloxy group in the ester portion It is a (meth) acrylic acid ester monomer having a monovalent chain hydrocarbon group of 1 to 11. The monovalent chain hydrocarbon group having 1 to 11 carbon atoms is at least one member selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group from the viewpoint of being capable of reacting with a crosslinking agent. It is preferable to have a functional group. When a non-fluorinated polymer containing a monomer (C1) having a group capable of reacting with the crosslinking agent is treated with the crosslinking agent into a fiber product, the feeling of the resulting fiber product is maintained, The durable water repellency can be improved. The isocyanate group may be a blocked isocyanate group protected by a blocking agent.

  The linear hydrocarbon group may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Moreover, the chain hydrocarbon group may further have a substituent in addition to the above functional group. Among them, from the viewpoint of being able to improve the durable water repellency of the fiber product to be obtained, it is preferably linear and / or a saturated hydrocarbon group.

  Specific examples of the monomer (C1) include 2-hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 1,1-bis (acryloyloxymethyl) ethyl An isocyanate etc. are mentioned. One of these monomers may be used alone, or two or more of these monomers may be used in combination. Among them, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate are preferable in that the durable water repellency of the obtained fiber product can be improved. Further, dimethylaminoethyl (meth) acrylate is preferable in terms of further improving the feel of the resulting fiber product.

  The constituent ratio of the above-mentioned (C1) monomer in the non-fluorinated polymer of the present embodiment is the total amount of the monomer components constituting the non-fluorinated polymer from the viewpoint of water repellency and feeling of the obtained fiber product. On the other hand, it is preferably 1 to 30% by mass, more preferably 3 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 portion, and the cyclic hydrocarbon group is an isobornyl group, A cyclohexyl group, a dicyclopentanyl group etc. are mentioned. These cyclic hydrocarbon groups may have a substituent such as an alkyl group. However, when the substituent is a hydrocarbon group, a hydrocarbon group is selected such that the total carbon number of the substituent and the cyclic hydrocarbon group is 11 or less. In addition, it is preferable that these cyclic hydrocarbon groups be directly bonded to an ester bond from the viewpoint of improving the 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, and dicyclopentanyl (meth) acrylate. One of these monomers may be used alone, or two or more of these monomers may be used in combination. Among them, isobornyl (meth) acrylate and cyclohexyl methacrylate are preferable, and isobornyl methacrylate is more preferable, from the viewpoint of improving the durable water repellency of the obtained fiber product.

  The constituent ratio of the above-mentioned (C2) monomer in the non-fluorinated polymer of the present embodiment is the total amount of monomer components constituting the non-fluorinated polymer from the viewpoint of water repellency and feeling of the obtained fiber product. On the other hand, it is preferably 1 to 30% by mass, more preferably 3 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 portion. As a C1-C4 chain hydrocarbon group, a C1-C2 linear hydrocarbon group and a C3-C4 branched hydrocarbon group are preferable. As a C1-C4 chain hydrocarbon group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group etc. are mentioned, for example. Specific examples of the compound include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and t-butyl methacrylate. One of these monomers may be used alone, or two or more of these monomers may be used in combination. Among them, methyl methacrylate, isopropyl methacrylate and t-butyl methacrylate are preferable, and methyl methacrylate is more preferable, from the viewpoint that the durable water repellency of the obtained fiber product can be improved.

  The constituent ratio of the above-mentioned (C3) monomer in the non-fluorinated polymer of the present embodiment is the total amount of monomer components constituting the non-fluorinated polymer from the viewpoint of water repellency and feeling of the obtained fiber product. On the other hand, it is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass.

  The total component ratio of the monomers of the component (C) in the non-fluorinated polymer of the present embodiment is a monomer component constituting the non-fluorinated polymer from the viewpoint of water repellency and texture of the obtained fiber product It is preferable that it is 1-30 mass% with respect to whole quantity of, it is more preferable that it is 3-25 mass%, and it is further more preferable that it is 5-20 mass%.

  The non-fluorinated polymer contained in the water repellent composition of the present embodiment is a monomer copolymerizable with the components (A), (E), (B) and (C) in addition to the components. (D) can be contained in the range which does not impair the effect of this invention.

  As a monomer of said (D), (meth) acrylic acid ester which has hydrocarbon groups other than (A) component and (C) component, (meth) acrylic acid, fumaric acid ester, maleic acid ester, Examples thereof include fumaric acid, maleic acid, (meth) acrylamide, N-methylol acrylamide, vinyl ethers, vinyl esters, vinyl chloride, vinylidene chloride, and vinyl monomers containing no fluorine such as 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 vinyl group, a hydroxyl group, an amino group, an epoxy group and an isocyanate group, a blocked isocyanate group as a hydrocarbon group. And the like, and may have a substituent other than a group capable of reacting with the crosslinking agent such as quaternary ammonium group, and may be an ether bond, an ester bond, an amide bond, or a urethane bond And the like. Examples of (meth) acrylic acid esters other than the component (A) and the component (C) include methyl acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, The (meth) acrylic acid ester monomer etc. which are represented by the following general formula (D-1) are mentioned.

［式（Ｄ−１）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。］

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

  The (meth) acrylic acid ester monomer represented by the above (D-1) is a (meth) acrylic acid ester monomer having three or more polymerizable unsaturated groups in one molecule. In the present embodiment, a multifunctional (meth) acrylic acid ester having three or more (meth) acryloyloxy groups in one molecule, in which T in the general formula (D-1) is a (meth) acryloyloxy group Preferred are mers. In formula (D-1), p T's 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, and dipentaerythritol hexaacrylate. Pentaerythritol hexamethacrylate and the like can be mentioned. One of these monomers may be used alone, or two or more of these monomers may be used in combination. Among these, tetramethylolmethane tetraacrylate is more preferable in that the durable water repellency of the obtained fiber product can be improved.

  The constituent ratio of the monomer (D) is 10% by mass or less based on the total amount of the monomer components constituting the non-fluorinated polymer from the viewpoint of water repellency and feeling of the obtained fiber product Is preferred.

  The non-fluorinated polymer contained in the water repellent composition of the present embodiment is at least one functional group selected from the group consisting of hydroxyl group, amino group, carboxyl group, epoxy group and isocyanate group capable of reacting with the crosslinking agent. It is preferable from the viewpoint of improving the durable water repellency of the resulting textile product. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. Moreover, it is preferable that a non-fluorinated polymer has an amino group from the viewpoint of also improving the feel of the obtained fiber product.

  It is also possible to add an additive etc. to the water repellent composition of this embodiment as needed. As the additives, other water repellents, crosslinking agents, antibacterial deodorants, flame retardants, antistatic agents, softeners, mildew proofing agents and the like can be mentioned.

  Next, a method of producing the water repellent composition containing the non-fluorinated polymer of the present embodiment will be described.

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

  For example, non-fluorine by emulsion polymerization or dispersion polymerization of the (meth) acrylic acid ester monomer (A) represented by the above general formula (A-1) in the presence of the above component (E) in a medium Based polymers can be obtained. More specifically, for example, (A) component, (E) component, and, if necessary, the above (B) component, the above (C) component and the above (D) component, and an emulsifying aid or dispersion in a medium An adjuvant is added and the mixture is emulsified or dispersed to obtain an emulsion or dispersion. By adding a polymerization initiator to the obtained emulsion or dispersion, the polymerization reaction can be initiated to polymerize the monomer and the reactive emulsifier. In addition, as a means to emulsify or disperse | distribute the mixed liquid mentioned above, a homomixer, a high-pressure emulsifying machine, an ultrasonic wave, etc. are mentioned.

  As the above-mentioned emulsification adjuvant or dispersion adjuvant (hereinafter, also referred to as "emulsion adjuvant etc."), nonionic surfactants other than the above-mentioned reactive emulsifier (B), cationic surfactants, anionic surfactants, and One or more selected from amphoteric surfactants can be used. It is preferable that it is 0.5-30 mass parts with respect to 100 mass parts of all monomers, as content of an emulsification adjuvant etc., it is more preferable that it is 1-20 mass parts, and 1-10 mass parts It is further preferred that When the content of the above-mentioned emulsification adjuvant etc. is less than 0.5 parts by mass, the dispersion stability of the mixed liquid tends to be reduced compared to the case where the content of the emulsification adjuvant etc. is in the above range, When the content of the emulsification aid or the like exceeds 30 parts by mass, the water repellency of the obtained non-fluorinated polymer tends to decrease as compared to the case where the content of the emulsification aid or the like 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 needed. The organic solvent at this time is not particularly limited as long as it is an organic solvent miscible with water, but, for example, alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, diethyl Ethers such as ethers, and glycols such as propylene glycol, dipropylene glycol and tripropylene glycol can be mentioned. The ratio of water to the organic solvent is not particularly limited.

  As said polymerization initiator, well-known polymerization initiators, such as an azo type, a peroxide type, or a redox type, can be used suitably. The content of the polymerization initiator is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of all the monomers. When the content of the polymerization initiator is in the above range, a non-fluorinated polymer having a weight average molecular weight of 100,000 or more can be efficiently produced.

  Further, in the polymerization reaction, a chain transfer agent such as dodecyl mercaptan and t-butyl alcohol may be used for the purpose of molecular weight adjustment. The content of the chain transfer agent is preferably 0.3 parts by mass or less and more preferably 0.1 parts by mass or less with respect to 100 parts by mass of all monomers. When the content of the chain transfer agent exceeds 0.1 parts by mass, the molecular weight decreases, 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 addition, you may use a polymerization inhibitor for molecular weight adjustment. By addition of 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., polymerization tends to be insufficient compared to the case where the temperature is in the above range, and when the temperature exceeds 150 ° C., control of the heat of reaction may be difficult. .

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

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

  The water-repellent fiber product of the present embodiment is a fiber product to which the non-fluorinated polymer of the present embodiment described above is attached.

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

  The water repellent fiber product of the present embodiment is obtained by adhering a non-fluorinated polymer to a fiber product by treating the fiber product with a treatment liquid containing the above-described water repellent composition. The material of such fiber products is not particularly limited, and 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 Blend fiber etc. are mentioned. The form of the fiber product may be any form of fiber, yarn, cloth, non-woven fabric, paper and the like.

  As a method of processing textiles with the above-mentioned processing solution, processing methods, such as immersion, spraying, application, are mentioned, for example. In addition, when the water repellent composition contains water, it is preferable to dry it in order to remove water after being attached to a fiber product.

  The adhesion amount of the water repellent composition to the fiber product can be appropriately adjusted according to the required degree of water repellency, but 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 of these may be 0.01-10 g, and it is more preferable to adjust so that it may be 0.05-5 g. If the adhesion amount of the non-fluorinated polymer is less than 0.01 g, the fiber product tends not to exhibit sufficient water repellency as compared to the case where the adhesion amount of the non-fluorinated polymer is in the above range, When it exceeds, compared with the case where the adhesion amount of a non-fluorinated polymer is in the above-mentioned range, the feeling of textiles tends to be coarse and hard.

  In addition, after the non-fluorinated polymer of the present embodiment is attached to the fiber product, it is preferable to carry out heat treatment appropriately. The temperature condition is not particularly limited, but when the water repellent composition of this embodiment is used, the fiber product can exhibit sufficiently good water repellency under mild conditions of 100 to 130 ° C. The temperature condition 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 the present embodiment, the deterioration of the fiber product due to heat is suppressed, and the texture of the fiber product at the time of water repellent treatment becomes soft, and under mild heat treatment conditions, ie, low temperature curing conditions. It is possible to impart sufficient water repellency to textiles.

  In particular, when it is desired to improve the durable water repellency, the above-mentioned process of treating a textile product with a treatment liquid containing a water repellent composition, and a compound having one or more methylolmelamine, isocyanate group or blocked isocyanate group And the step of attaching a cross-linking agent represented by to the fiber product and heating it, it is preferable to subject the fiber product to a water repellent finish. 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 compounds having one or more isocyanate groups include monoisocyanates such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate and naphthalene isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, tetramethyl xylylene diisocyanate, diisocyanates such as hydrogenated diphenylmethane diisocyanate, and the like Examples thereof include trimers which are isocyanurate rings and trimethylolpropane adducts. Moreover, as a compound which has one or more blocked isocyanate groups, the compound which protected the isocyanate group with the compound which has the said isocyanate group with a blocking agent is mentioned. As the blocking agent used at this time, an organic blocking agent such as secondary or tertiary alcohols, active methylene compounds, phenols, oximes, lactams, etc., and bisulfite such as sodium bisulfite and potassium bisulfite Salt is mentioned. The above-mentioned crosslinking agents may be used alone or in combination of two or more.

  The crosslinking agent may be, for example, a method of dissolving the crosslinking agent in an organic solvent or immersing the object to be treated (fiber product) in a treatment liquid obtained by emulsifying and dispersing in water, and drying the treatment liquid attached to the object It can be attached to an object to be treated. Then, by heating the crosslinking agent attached to the object to be treated, the reaction between the crosslinking agent and the object to be treated and the non-fluorinated polymer can be advanced. Heating at this time is preferably performed at 110 to 180 ° C. for 1 to 5 minutes in order to allow the reaction of the crosslinking agent to sufficiently advance and to improve the washing durability more effectively. The steps of adhesion of the crosslinking agent and heating may be performed simultaneously with the step of treating with the treatment liquid containing the water repellent composition described above. In the case of simultaneous treatment, for example, a treatment liquid containing a water repellent composition and a crosslinking agent is attached to an object to be treated, water is removed, and then the crosslinking agent attached to the object to be treated is heated. In consideration of simplification of the water repellent finishing process, reduction of heat quantity, and economy, it is preferable to carry out simultaneously with the water repellent composition treating process.

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

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

  As mentioned above, although the suitable embodiment of the present invention was described, the present invention is not limited to the above-mentioned embodiment.

  For example, in the case of producing the non-fluorinated polymer contained in the water repellent composition of the present invention, the polymerization reaction is carried out by radical polymerization in the above embodiment, but ionization such as ultraviolet light, electron beam, or γ-ray is performed. The polymerization reaction may be carried out by photopolymerization in which a chemical radiation or the like is irradiated.

  Further, in the present invention, the water repellent composition is treated to be a fiber product to make it a water repellent fiber product, but the product to be treated with the water repellent composition is not limited to the fiber product use, and metal, glass Or an article such as a resin.

  In such a case, the method of adhering the water repellent composition to the article or the adhesion amount of the water repellent can be arbitrarily determined according to the type of the object to be treated and the like.

  EXAMPLES The present invention will be further described by the following examples, but the present invention is not limited by these examples.

<Preparation of polymer dispersion>
The mixed solution having the composition shown in Tables 1 to 6 (in the table, the numerical value shows (g)) was polymerized by the procedure shown below to obtain a polymer dispersion.

Example 1
In a 500 mL flask, 60 g of stearyl acrylate, X-22-2475 (manufactured by Shin-Etsu Silicone Co., Ltd., dimethyl silicone having a methacryloyl group at one end, functional group equivalent = 420 g / mol), 5 g, Neugen XL-100 (1st Industry Pharmaceutical Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7 2 g, Neugen XL-60 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 12.5) 2 g, stearyl dimethyl 3 g of amine hydrochloride, 25 g of tripropylene glycol and 202.7 g of water were added, mixed and stirred at 45 ° C. to obtain a mixed solution. The mixed solution was irradiated with ultrasonic waves to emulsify and disperse all monomers. Next, 0.3 g of azobis (isobutylamidine) dihydrochloride was added to the mixture, and radical polymerization was carried out at 60 ° C. for 6 hours under a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion having a polymer concentration of 23 mass%. .

(Examples 2 to 23 and Comparative Examples 1 to 4)
The polymerization was performed in the same manner as in Example 1 except that the materials described in Tables 1 to 6 were used, to obtain non-fluorinated polymer dispersions with the polymer concentrations shown in Tables 7 to 10, respectively.

  Each polymer in the polymer dispersion obtained in each of Examples 1 to 23 and Comparative Examples 1 to 4 was 98% of the total monomer by gas chromatograph (GC-15APTF, manufactured by Shimadzu Corporation). It was confirmed that% or more was polymerized.

The details of the materials shown in Tables 1 to 6 are as follows.
KF-2012 (Shin-Etsu Silicone Co., Ltd., dimethyl silicone having a methacryloyl group at one end, functional group equivalent = 4,600 g / mol)
X-22-2426 (Shin-Etsu Silicone Co., Ltd., dimethyl silicone having a methacryloyl group at one end, functional group equivalent = 12,000 g / mol)
LATEML PD-420 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 12.6)
Latem PD-430 (manufactured by Kao Corporation, polyoxyalkylene alkenyl ether, HLB = 14.4)
Ethylene oxide 12.5 molar adduct of cardanol (HLB = 12.9, shown in the table as "cardanol 12.5 EO")
An ethylene oxide 8.3 molar adduct of cardanol (HLB = 11.0, indicated in the table as "cardanol 8.3 EO")
42 mol ethylene oxide adduct of castor oil (HLB = 13.3, shown as “castor oil 42 EO” in the table)
30 mol ethylene oxide adduct of castor oil (HLB = 11.7, shown as “castor oil 30EO” in the table)

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

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

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

(Evaluation of physical properties of non-fluorinated polymers)
The polymer and the emulsifier were separated by adding 500 mL of acetone to 50 g of the polymer dispersion obtained in Examples 1 to 23 and Comparative Examples 1 to 4, the polymer was separated by filtration, and the polymer was dried under reduced pressure at 25 ° C. for 24 hours. The The resulting polymer was evaluated as follows. The results are shown in Tables 7-10.

(1) Method of Measuring Melt Viscosity A die (length 10 mm, diameter 1 mm) was prepared using the elevated flow tester CFT-500 (manufactured by Shimadzu Corporation) for the polymers of the examples and comparative examples obtained above. 1 g of the polymer was put in the attached cylinder, held at 105 ° C. for 6 minutes, and a load of 100 kg · f / cm ² was applied by a plunger to measure the melt viscosity at 105 ° C.

(2) Measurement Method of Weight Average Molecular Weight The polymers of the examples and comparative examples obtained above were subjected to a column temperature of 40 ° C., a flow rate of 1.0 ml /, using a GPC apparatus (GPC “HLC-8020” manufactured by Tosoh Corp.). Under the conditions of the minute, it measured using tetrahydrofuran as an eluting solvent, and measured the weight average molecular weight in standard polystyrene conversion. In addition, three columns of brand names TSK-GEL G5000HHR, G4000HHR, and G3000HHR manufactured by Tosoh Corp. were connected and mounted.

(Evaluation of storage stability of water repellent composition)
The stability of the polymer dispersions obtained in Examples and Comparative Examples when stored at 45 ° C. for 2 weeks was evaluated based on the following criteria. The results are shown in Tables 7-10.
A: No change in appearance B: Oil near the liquid surface, slight polymer deposit on the container wall C: Precipitate, separation, gelation of polymer

(Water repellant evaluation and continuous processing appropriate evaluation of textile products)
According to the spray method of JIS L 1092 (1998), the test was conducted at a shower water temperature of 27 ° C. In this test, a dyed polyester 100% cloth or nylon 100% cloth is dipped in a treatment solution in which the polymer dispersions of Examples and Comparative Examples are diluted with water to a polymer content of 3% by mass. After the treatment (pickup rate 60 mass%), it was dried at 130 ° C. for 2 minutes and further heat-treated under the conditions as shown in Tables 7 to 10, and the water repellency of the obtained fabric was evaluated. Furthermore, after using the treatment liquid used for the above immersion treatment, 19 test cloths are dipped continuously, and then the 19th (20th continuous treatment) test cloth is dried at 130 ° C. for 2 minutes, and the table is further displayed. Heat treatment was performed under the conditions shown in 7 to 10, and the water repellency of the obtained cloth was also evaluated. The results were visually evaluated according to the following grades. In addition, when the property was slightly good, the grade was "+", and when the property was slightly inferior, the grade was "-". The results are shown in Tables 7-10.
Water Repellent: Condition 5: No adhesion on the surface 4: A slight adhesion on the surface 1: A partial wetting on the surface 2: A wetting on the surface 1: A wetting on the entire surface Thing 0: Both sides show complete wetting

(Evaluation of feeling of textile products)
The texture was treated by immersing a 100% dyed polyester fabric in a treatment solution obtained by diluting the polymer dispersions of Examples and Comparative Examples with water so that the content of the polymer was 3% by mass (pickup ratio 60 mass) %) And then dried at 130.degree. C. for 2 minutes and then heat-treated at 170.degree. C. for 30 seconds for evaluation. The results were evaluated in the following five stages in handling. The results are shown in Tables 7-10.
1: Hard ~ 5: Soft

(Durable water repellency evaluation of textile products)
According to the spray method of JIS L 1092 (1998), the test was conducted at a shower water temperature of 27 ° C. In this test, the 100% polyester dyed fabric has a polymer content of 3% by mass, and a content of UNIKA RESIN 380-K (crosslinking agent, trimethylolmelamine resin manufactured by Union Chemical Industry Co., Ltd.) is 0 .3% by mass and polymer dispersions of Examples and Comparative Examples such that the content of UNIKA CATALYST 3-P (surfactant, manufactured by Union Chemical Industries, Ltd., amino alcohol hydrochloride) is 0.2% by mass And the above-mentioned agents were dipped in a treatment solution diluted with water (pickup rate: 60% by mass), dried at 130 ° C. for 2 minutes, and heat treated at 170 ° C. for 60 seconds (L-0) The water repellency of the cloth after 10 washings (L-10) according to the method 103 of JIS L 0217 (1995) was evaluated in the same manner as the above water repellency evaluation method. Moreover, also in the case of 100% nylon cloth, it evaluated similarly to the case of 100% polyester cloth except having changed the heat processing temperature from 170 degreeC to 160 degreeC. The results are shown in Tables 7-10.

  The fiber products treated with the water repellent compositions of Examples 1 to 23 have water repellency equal to or higher than that obtained when the conventional fluorine-based water repellent (Comparative Example 1) is used, even without heat treatment. It was confirmed that it exhibited durable water repellency and that the texture was also good. Moreover, when Example 4 and Examples 9 to 11 are compared, even if the composition of the non-fluorinated polymer is close, the one having a larger weight average molecular weight is more water repellent when the weight average molecular weight of the polymer is different. It was confirmed to be excellent.

  Furthermore, the water repellent compositions of Examples 1 to 23 are suitable for continuous processing, that is, even when a plurality of fiber products are continuously subjected to water repellent finish using the same treatment agent, It was confirmed that the non-fluorinated water repellent composition which does not contain the component (E) of Comparative Examples 2 and 3 has better water repellency than the case of using the non-fluorinated water repellent composition.

  The water repellent composition of Comparative Example 2 is a non-fluorinated polymer consisting only of the component (A), and compared with the water repellent composition of Example 1, it is continuous because it does not contain the component (E). The processing suitability tends to be inferior. The water repellent composition of Comparative Example 3 is a non-fluorinated polymer consisting of the (A) component and the (B) component, and since the (B) component is contained, the obtained fiber product has good water repellency. Although it showed, since it did not contain (E) component, it was a tendency for continuous processing suitability to be inferior. The water repellent composition of Comparative Example 4 did not contain the component (A), and it was confirmed that the water repellency itself of the obtained fiber product was reduced. In addition, although the feel is improved because the proportion of the component (E) is too high, the storage stability tends to be greatly reduced.

Claims (12)

(Meth) acrylic acid ester monomer (A ) represented by the following general formula (A-1),
A silicone oil (E ) represented by the following general formula (E-1),
(B1) a compound represented by the following general formula (I-1) having a HLB of 7 to 18, (B2) a compound represented by the following general formula (II-1) having a HLB of 7 to 18, B3) At least one reactive emulsifier (B 1 ) selected from compounds obtained by adding an alkylene oxide of 2 to 4 carbon atoms to a fat and oil having a hydroxyl group and a polymerizable unsaturated group having a HLB of 7 to 18 ,
Emulsion polymerization or dispersion polymerization of a monomer composition containing
The ratio (A) / (E) of the mass of the component (A) to the mass of the component (E) in the monomer composition is 50/50 to 99.5 / 0.5,
The total mass of the mass of the component (A) and the mass of the component (E) is 80 to 99 mass% based on the total amount of the monomer components,
The non-fluorinated polymer whose mass of the said (B) component is 1-15 mass% on the basis of the monomer component whole quantity .

[In Formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 to 24 carbon atoms which may have a substituent. ]

Represents wherein ^{(E-1), R 21} and ^{R 22} are each independently hydrogen, a methyl group or a phenyl ^{group, R 23} represents a monovalent hydrocarbon ^{group, R 24} is a divalent hydrocarbon R ²⁵ represents a hydrogen or methyl group, and s is an integer of 0 or more. ]

Wherein (I-1), R ³ represents a methylation group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, Y ¹ comprises an alkyleneoxy group having 2 to 4 carbon atoms Represents a divalent group. ]

[In formula (II-1), R ⁴ represents a C 13-17 monovalent unsaturated hydrocarbon group having a polymerizable unsaturated group, and Y ² includes a C 2-4 alkyleneoxy group. Represents a divalent group. ] The monomer composition further contains at least one second (meth) acrylic acid ester monomer (C ) selected from the group consisting of the following (C1), (C2) and (C3): The non-fluorinated polymer according to claim 1 .
(C1) (Meth) acrylic acid ester monomer represented by the following general formula (C-1)

[In the formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ represents at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group and a (meth) acryloyloxy group It represents a C1-C11 monovalent chain hydrocarbon group having one type 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 3 to 11 carbon atoms which may have a substituent. ]
(C3) Methacrylic acid ester monomer represented by the following general formula (C-3)

[In Formula (C-3), R ⁹ represents an unsubstituted monovalent hydrocarbon chain hydrocarbon group having 1 to 4 carbon atoms. ] (Meth) acrylic acid ester monomer (A) represented by the following general formula (A-1),
A silicone oil (E) represented by the following general formula (E-1),
(B1) a compound represented by the following general formula (I-1) having a HLB of 7 to 18, (B2) a compound represented by the following general formula (II-1) having a HLB of 7 to 18, B3) At least one reactive emulsifier (B) selected from compounds obtained by adding an alkylene oxide of 2 to 4 carbon atoms to a fat and oil having a hydroxyl group and a polymerizable unsaturated group having a HLB of 7 to 18 and ,
A method for producing a non-fluorinated polymer , comprising emulsion polymerization or dispersion polymerization of an emulsion or dispersion containing
The mass ratio (A) / (E) of the compounding amount of the component (A) to the compounding amount of the component (E) is 50/50 to 99.5 / 0.5,
The total blending amount of the mass of the component (A) and the mass of the component (E) is 80 to 99 mass%, based on the total amount of the monomer components constituting the non-fluorinated polymer,
The manufacturing method of the non-fluorinated polymer whose compounding quantity of the said (B) component is 1-15 mass% on the basis of the monomer component whole quantity which comprises a non-fluorinated polymer.

[In Formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 to 24 carbon atoms which may have a substituent. ]

Represents wherein ^{(E-1), R 21} and ^{R 22} are each independently hydrogen, a methyl group or a phenyl ^{group, R 23} represents a monovalent hydrocarbon ^{group, R 24} is a divalent hydrocarbon R ²⁵ represents a hydrogen or methyl group, and s is an integer of 0 or more. ]

Wherein (I-1), R ³ represents a methylation group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, Y ¹ comprises an alkyleneoxy group having 2 to 4 carbon atoms Represents a divalent group. ]

[In formula (II-1), R ⁴ represents a C 13-17 monovalent unsaturated hydrocarbon group having a polymerizable unsaturated group, and Y ² includes a C 2-4 alkyleneoxy group. Represents a divalent group. ] The emulsion or the dispersion further contains at least one second (meth) acrylic acid ester monomer (C) selected from the group consisting of the following (C1), (C2) and (C3): The manufacturing method of the non-fluorinated polymer of Claim 3 .
(C1) (Meth) acrylic acid ester monomer represented by the following general formula (C-1)

[In the formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ represents at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group and a (meth) acryloyloxy group It represents a C1-C11 monovalent chain hydrocarbon group having one type 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 3 to 11 carbon atoms which may have a substituent. ]
(C3) Methacrylic acid ester monomer represented by the following general formula (C-3)

[In Formula (C-3), R ⁹ represents an unsubstituted monovalent hydrocarbon chain hydrocarbon group having 1 to 4 carbon atoms. ] A water repellent composition comprising the non-fluorinated polymer according to claim 1 or 2 . The water repellent composition according to claim 5 , which is for textiles. A water repellent fiber product comprising the fiber product to which the non-fluorinated polymer according to claim 1 or 2 is attached. Treating the fiber product with a treatment liquid containing the water repellent composition according to claim 5 or 6 , a method for producing a water repellent fiber product. A method of producing a water repellent composition containing a non-fluorinated polymer, comprising:
A process for producing a water repellent composition, comprising the step of obtaining the non-fluorinated polymer by the method according to claim 3 or 4 . The method for producing a water repellent composition according to claim 9 , wherein the water repellent composition is for textiles. Attaching the non-fluorinated polymer obtained by the method according to claim 3 to a fiber product, the method for producing a water-repellent fiber product. A process for producing a water repellent fiber product, comprising the step of treating the fiber product with a treatment liquid containing the water repellent composition obtained by the method for producing a water repellent composition according to claim 9 or 10 .