JP7431270B2 - Water repellent aid, non-fluorine water repellent composition, and method for producing water repellent textile products - Google Patents

Description

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

Conventionally, fluorine-based water repellents having fluorine-containing groups have been known, and textile products whose surfaces are made water repellent by treating such fluorine-based water repellents with such fluorine-based water repellents are known. . Such fluorine-based water repellents are generally produced by polymerizing or copolymerizing monomers having fluoroalkyl groups.

Textile products treated with fluorine-based water repellents exhibit excellent water repellency, but in order to develop water repellency, it is necessary to adjust the orientation of the fluoroalkyl groups. After the agent has been deposited, a heat treatment must be carried out at a temperature above 130°C. However, heat treatment at high temperatures requires high energy, which is a problem in the international trend toward energy conservation.

In addition, monomers having fluoroalkyl groups are expensive and are not economically satisfactory.Furthermore, monomers having fluoroalkyl groups are difficult to decompose and are therefore environmentally problematic. There is.

On the other hand, in the field of water repellent finishing of textile products, in order to stabilize quality and reduce costs, there is a need for water repellents that can provide textile products with excellent water repellency even at low concentrations and low heat treatment temperatures. .

Therefore, in recent years, research has been progressing on non-fluorine 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-based polymer is emulsified and dispersed, with the aim of providing water repellency comparable to that of conventional fluorine-based water repellents.

“Super Water Repellent Finishing, Full Details of Finishing Agents and New Trends in Breathable and Waterproof Materials”, Osaka Chemical Marketing Center Co., Ltd., 1996, p. 7-9

Japanese Patent Application Publication No. 2006-328624

However, with conventional water repellents, sufficient durable water repellency may not be obtained in some cases.

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

The present invention provides a water repellent aid for a non-fluorine water repellent, which contains an organo-modified silicone represented by the following general formula (1).

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

[In formula (1), R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and R ²³ is a carbon having an aromatic ring. Represents a hydrocarbon group having 8 to 40 carbon atoms or an alkyl group having 3 to 22 carbon atoms, and R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom, a methyl group, an ethyl group. group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 3 to 22 carbon atoms, a represents an integer of 0 or more, and b is 1 or more, (a+b) is 10 to 200, and when a is 2 or more, the plurality of R ²⁰ and R ²¹ may be the same or different, and when b is 2 or more, , a plurality of R ²² and R ²³ may be the same or different. ]

According to the water repellent aid of the present invention, when used in combination with a non-fluorine water repellent, the durable water repellency of the non-fluorine water repellent can be improved.

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

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

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

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

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

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

[In 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 monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms having a polymerizable unsaturated group, and Y ² includes an alkyleneoxy group having 2 to 4 carbon atoms. Represents a divalent group. ]

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

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

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

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

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

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

According to the method for producing a water-repellent textile product of the present invention, by using a non-fluorine water repellent composition containing the water-repellent aid according to the present invention, a water-repellent textile product with excellent durable water repellency can be stably produced. It can be manufactured using In addition, the method for producing water-repellent fiber products of the present invention does not require heat treatment at high temperatures, making it possible to save energy, and since it uses a non-fluorine-based water repellent, it is environmentally friendly. The load can be reduced.

According to the present invention, it is possible to provide a water repellent aid that can improve the durable water repellency of a non-fluorine water repellent, and a non-fluorine water repellent composition containing the same.

Furthermore, the non-fluorine-based water repellent composition of the present invention exhibits excellent water repellency even though it does not contain a fluoroalkyl group or a compound containing fluorine, and can be used as an alternative to fluorine-based water repellents. It can be used as a fluorine source, eliminating concerns about the impact on fluorine sources and the environment. Note that it is usually preferable to heat-treat the water repellent composition after attaching it to textile products, etc., but since the non-fluorine water repellent composition of the present invention does not use a monomer having a fluoroalkyl group, , high water repellency can be exhibited even when heat-treated under mild conditions of 130°C or less, and when heat-treated at a high temperature exceeding 130°C, the heat treatment time can be reduced in the case of fluorine-based water repellents. It can be made shorter than . Therefore, since deterioration of the treated object due to heat is suppressed, the texture becomes softer, and the amount of heat required for heat treatment can be reduced, which is advantageous in terms of cost.

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

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

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

[In formula (1), R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and R ²³ is a carbon having an aromatic ring. Represents a hydrocarbon group having 8 to 40 carbon atoms or an alkyl group having 3 to 22 carbon atoms, and R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom, a methyl group, an ethyl group. group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 3 to 22 carbon atoms, a represents an integer of 0 or more, and b is 1 or more, (a+b) is 10 to 200, and when a is 2 or more, the plurality of R ²⁰ and R ²¹ may be the same or different, and when b is 2 or more, , a plurality of R ²² and R ²³ may be the same or different. ]

In the organo-modified silicone of this embodiment, the alkoxyl group having 1 to 4 carbon atoms may be linear or branched. Examples of the alkoxyl group having 1 to 4 carbon atoms include methoxy group, ethoxy group, propoxy group, and butoxy group. In terms of easy industrial production and availability, R ²⁰ , R ²¹ and R ²² are each independently preferably a hydrogen atom or a methyl group, more preferably a methyl group.

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

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

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

The above alkylene group may be linear or branched.

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

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

The above alkylene group may be linear or branched.

Examples of the aralkyl group having 8 to 40 carbon atoms include phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group, naphthylethyl group, and the like. Among these, phenylethyl group and phenylpropyl group are preferred because they are easy to produce industrially and are easily available.

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

In the group represented by the above general formula (3), R ⁴² is preferably an alkylene group having 2 to 4 carbon atoms, and d is 0 or 1, in terms of easy industrial production and availability. It is preferably 0, and more preferably 0.

The above hydrocarbon group having 8 to 40 carbon atoms and having an aromatic ring is preferably the aralkyl group having 8 to 40 carbon atoms, and the above general formula ( Groups represented by 2) are preferred, and the above aralkyl groups having 8 to 40 carbon atoms are more preferred since they can improve the water repellency of the resulting fiber products.

The above alkyl group having 3 to 22 carbon atoms may be linear or branched. Examples of the alkyl group having 3 to 22 carbon atoms include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, myristyl group, cetyl group, stearyl group, and the like. As the alkyl group having 3 to 22 carbon atoms, an alkyl group having 8 to 20 carbon atoms is preferable, and an alkyl group having 12 to 18 carbon atoms is more preferable, from the viewpoint of improving the water repellency of the resulting fiber product.

In the organo-modified silicone of this embodiment, R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, an aromatic A hydrocarbon group having a group ring and having 8 to 40 carbon atoms, or an alkyl group having 3 to 22 carbon atoms. R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom, a methyl group, an ethyl group, or a carbon number 1 group in terms of easy industrial production and availability. -4 alkoxy groups are preferred, and methyl groups are particularly preferred.

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

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

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

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

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

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

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

The amounts of the silicone having an SiH group, the aromatic compound having a vinyl group, and the α-olefin used in the hydrosilylation reaction are appropriately selected depending on the SiH group equivalent or number average molecular weight of the silicone having an SiH group. obtain.

Examples of the catalyst used in the hydrosilylation reaction include compounds such as platinum and palladium, with platinum compounds being preferred. Examples of the platinum compound include platinum (IV) chloride.

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

Further, the hydrosilylation reaction is preferably carried out under an inert gas atmosphere. Examples of the inert gas include nitrogen, argon, and the like. Although the reaction proceeds without a solvent, a solvent may also be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

The non-fluorine water repellent composition of this embodiment will be explained.

The non-fluorine water repellent composition of the present embodiment includes the water repellent aid of the present embodiment and a non-fluorine water repellent.

The above-mentioned non-fluorine-based water repellent has excellent storage stability and can impart sufficient water repellency to textile products even without heat treatment, making it a water-repellent textile product with excellent texture and water repellency. A structural unit derived from a (meth)acrylic acid ester monomer (A) represented by the following general formula (A-1) (hereinafter also referred to as "component (A)") in that it can obtain It is preferable that a non-fluorine-based polymer containing .

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

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

Here, "(meth)acrylic ester" means "acrylic ester" or the corresponding "methacrylic ester", and has the same meaning as "(meth)acrylic acid", "(meth)acrylamide", etc. be.

The (meth)acrylic acid ester monomer (A) represented by the above general formula (A-1) used in this embodiment is a monomer having 12 or more carbon atoms that may have a substituent. It has a valent hydrocarbon group. This hydrocarbon group may be linear or branched, a saturated hydrocarbon group or an unsaturated hydrocarbon group, and even an alicyclic or aromatic cyclic group. It 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 will be even better. When a 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 the following may be mentioned. In the present embodiment, R ² in the above general formula (A-1) is preferably an unsubstituted hydrocarbon group.

The number of carbon atoms in the hydrocarbon group is preferably 12 to 24. When the number of carbon atoms is less than 12, sufficient water repellency cannot be exhibited when the non-fluorine-based polymer is attached to textile products or the like. On the other hand, when the carbon number exceeds 24, the texture of the textile product tends to become rougher and harder when a non-fluorine-based polymer is attached to the textile product, etc., compared to when the carbon number is within the above range. .

It is more preferable that the hydrocarbon group has 12 to 21 carbon atoms. When the number of carbon atoms is within this range, water repellency and texture will be particularly excellent. Particularly preferred as the hydrocarbon group are linear alkyl groups 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)acrylate. Pentadecyl, heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, behenyl (meth)acrylate, ceryl (meth)acrylate, merisyl (meth)acrylate can be mentioned.

The above component (A) can have at least one functional group selected from the group consisting of hydroxyl group, amino group, carboxyl group, epoxy group, and isocyanate group that can react with a crosslinking agent. In this case, the durable water repellency of the obtained textile product can be further improved. The isocyanate group may form a blocked isocyanate group protected with a blocking agent. Moreover, when the component (A) has an amino group, the texture of the obtained textile product can be further improved.

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

The above component (A) may be used alone or in combination of two or more.

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

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

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

In this embodiment, the melt viscosity of the non-fluorine-based polymer at 105° C. is preferably 1000 Pa·s or less. When the melt viscosity at 105° C. exceeds 1000 Pa·s, the texture of the obtained textile product tends to become rough and hard. In addition, if the melt viscosity of the non-fluorine-based polymer is too high, when the non-fluorine-based polymer is emulsified or dispersed to form a water repellent composition, the non-fluorine-based polymer may precipitate or settle, resulting in repellent The storage stability of the liquid formulation tends to decrease. Note that the melt viscosity at 105° C. is more preferably 500 Pa·s or less. In this case, the resulting textile products exhibit sufficient water repellency and also have a more excellent feel.

"Melt viscosity at 105°C" means that using an elevated flow tester (for example, CFT-500 manufactured by Shimadzu Corporation), 1 g of non-fluorine-based polymer is placed in a cylinder equipped 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-fluorine-based polymers are the same, the higher the blending ratio of the non-fluorine-based (meth)acrylic acid ester monomer, the higher the water repellency of the attached textile product tends to be. Furthermore, by copolymerizing a copolymerizable non-fluorine-based monomer, it is possible to improve the properties such as durable water repellency and texture of the attached textile product.

In addition to component (A), the non-fluorine-based polymer can improve the water repellency of the resulting textile product and the emulsion stability during and after the emulsion polymerization or dispersion polymerization of the non-fluorine-based polymer. (B1) a compound represented by the following general formula (I-1) whose HLB is 7 to 18; (B2) a compound represented by the following general formula (II-1) whose HLB is 7 to 18; and (B3) at least one reactive emulsifier (B ) (hereinafter also referred to as "component (B)") as a monomer component.

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

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

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

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

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

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

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

In the reactive emulsifier (B1) represented by the above general formula (I-1) used in this embodiment, R ³ is hydrogen or a methyl group, and from the viewpoint of copolymerizability with component (A). More preferably, it 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-fluorine-based polymer of the present embodiment. Y ¹ is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. The type, combination, and number of alkyleneoxy groups added in Y ¹ can be appropriately selected so as to fall within the above HLB range. Furthermore, when there are two or more types of alkyleneoxy groups, they can have a block addition structure or a random addition structure.

As the compound represented by the above 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 so as to fall within the above HLB range, and specifically, an integer of 1 to 80 is preferable, and when m is 2 or more, m A ¹ O are the same. may also be different. ]

In the compound represented by the above general formula (I-2), R ³ is hydrogen or a methyl group, and from the viewpoint of copolymerizability with component (A), a methyl group is more preferable. X is a straight chain or branched alkylene group having 1 to 6 carbon atoms, and from the viewpoint of emulsion stability of the non-fluorine polymer, a straight chain alkylene group having 2 to 3 carbon atoms is more preferable. A ¹ O is an alkyleneoxy group having 2 to 4 carbon atoms. The type and combination of A ¹ O and the number of m can be appropriately selected so as to fall within the above HLB range. In terms of emulsion stability of the non-fluorine-based polymer, m is preferably an integer of 1 to 80, more preferably an integer of 1 to 60. When m is 2 or more, m A ¹ O's may be the same or different. Furthermore, when there are two or more types of A ¹ O, they can have a block addition structure or a random addition structure.

The reactive emulsifier (B1) represented by the above general formula (I-2) can be obtained by a conventionally known method and is not particularly limited. Further, they can be easily obtained from commercial products, such as "Latemul PD-420", "Latemul PD-430", and "Latemul PD-450" manufactured by Kao Corporation.

In the reactive emulsifier (B2) represented by the above general formula (II-1) used in this embodiment, R ⁴ is a monovalent unsaturated carbonized carbon having 13 to 17 carbon atoms having a polymerizable unsaturated group. It is a hydrogen group, and examples include 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-fluorine-based polymer, R ⁴ is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

Y ² is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. The type, combination, and number of alkyleneoxy groups in Y ² can be appropriately selected so as to fall within the above HLB range. Furthermore, when there are two or more types of alkyleneoxy groups, they can have a block addition structure or a random addition structure. From the viewpoint of emulsion stability of the non-fluorine-based polymer, the alkyleneoxy group is more preferably an ethyleneoxy group.

As the compound represented by the above 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 and 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 that it falls within the range of the above HLB, specifically, an integer of 1 to 50 is preferable, and when n is 2 or more, n A ² O are the same and may also be different. ]

Examples of R ⁴ in the compound represented by the above general formula (II-2) include the same compounds as R ⁴ in the above general formula (II-1).

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

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

The above-mentioned phenols having corresponding unsaturated hydrocarbon groups include not only industrially produced pure products or mixtures, but also those existing as pure products or mixtures extracted and purified from plants and the like. For example, 3-[8(Z), 11(Z), 14-pentadecatrienyl]phenol, 3-[8(Z), 11(Z)], which is extracted from cashew nut shells 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 this embodiment is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an oil or fat having a hydroxyl group and a polymerizable unsaturated group and having an HLB of 7 to 18. . Fats and oils having hydroxyl groups and polymerizable unsaturated groups include hydroxy unsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.). Examples include mono- or diglycerides of fatty acids, triglycerides of fatty acids containing at least one hydroxyunsaturated fatty acid (ricinoleic acid, ricinoelaidic acid, 2-hydroxytetracosenoic acid, etc.). In terms of emulsion stability of the non-fluorine-based polymer, alkylene oxide adducts of fatty acid triglycerides containing at least one hydroxyunsaturated fatty acid are preferred, and castor oil (fatty acid triglycerides containing ricinoleic acid) having 2 to 4 carbon atoms is preferred. An alkylene oxide adduct of is more preferred, and an ethylene oxide adduct of castor oil is even more preferred. Further, the number of moles of alkylene oxide added can be appropriately selected so as to fall within the above HLB range, and from the viewpoint of emulsion stability of the non-fluorine polymer, 20 to 50 moles is more preferable, and 25 to 45 moles. is even more preferable. Furthermore, when there are two or more types of alkylene oxides, 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 or fat having a hydroxyl group and a polymerizable unsaturated group by a conventionally known method, and is not particularly limited. It's not a thing. For example, it can be synthesized by adding a predetermined amount of alkylene oxide to fatty acid triglyceride containing ricinoleic acid, that is, castor oil, using an alkali catalyst such as caustic soda or caustic potassium under pressure at 120 to 170°C. .

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

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

［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 monomers represented by the following general formula (C-1) other than (C5)

[In formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ is 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. Represents a monovalent chain hydrocarbon group having 1 to 11 carbon atoms and 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 chain hydrocarbon group having 1 to 4 carbon atoms. ]

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

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

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

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

The monomer (C1) above has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group in the ester moiety. A (meth)acrylic ester monomer having 1 to 11 monovalent chain hydrocarbon groups, and a (meth)acrylic ester monomer other than the above (C5). From the viewpoint of being able to react with a crosslinking agent, the monovalent chain hydrocarbon group having 1 to 11 carbon atoms is at least one type selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. Preferably, it has a functional group. When a non-fluorine-based polymer containing the monomer (C1) having a group capable of reacting with these crosslinking agents is processed into a textile product together with a crosslinking agent, while maintaining the texture of the resulting textile product, 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. Moreover, the chain hydrocarbon group may further have a substituent in addition to the above functional group. Among them, it is preferable that it is linear and/or that it is a saturated hydrocarbon group, since it can improve the durable water repellency of the obtained textile product.

Specific monomers of (C1) include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl. Examples include isocyanates. These monomers may be used alone or in combination of two or more. Among them, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are preferred in that they can improve the durable water repellency of the resulting textile product. Furthermore, dimethylaminoethyl (meth)acrylate is preferred in terms of improving the feel of the resulting textile product.

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

The monomer (C2) above 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 cyclohexyl group and dicyclopentanyl group. These cyclic hydrocarbon groups may have a substituent such as an alkyl group. However, when the substituent is a hydrocarbon group, a hydrocarbon group in which the total number of carbon atoms of the substituent and the cyclic hydrocarbon group is 11 or less is selected. Further, it is preferable that these cyclic hydrocarbon groups are directly bonded to the 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 monomers include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and the like. These monomers may be used alone or in combination of two or more. Among them, isobornyl (meth)acrylate and cyclohexyl methacrylate are preferred, and isobornyl methacrylate is more preferred, since they can improve the durable water repellency of the resulting textile products.

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

The monomer (C3) above 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 straight chain hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms are preferable. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and t-butyl group. Specific compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate. These monomers may be used alone or in combination of two or more. Among them, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferred, and methyl methacrylate is more preferred, since they can improve the durable water repellency of the resulting textile product.

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

The monomer (C4) above is a (meth)acrylic acid ester monomer having three or more polymerizable unsaturated groups in one molecule. In this embodiment, T in the above general formula (C-4) is a (meth)acryloyloxy group, and a polyfunctional (meth)acrylic acid ester monomer having three or more (meth)acryloyloxy groups in one molecule is used. mer is preferred. In formula (C-4), p T's may be the same or different. Specific compounds include, for example, ethoxylated isocyanuric acid triacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, Examples include dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate. These monomers may be used alone or in combination of two or more. Among them, tetramethylolmethanetetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferred since they can improve the durable water repellency of the resulting textile product.

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

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

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

The above-mentioned chain saturated hydrocarbon group preferably has one or two chloro groups and one hydroxyl group, and one chloro group, More preferably, it has one hydroxyl group. In addition, in terms of the durable water repellency of the resulting textile products, the chain saturated hydrocarbon group has a hydroxyl group at the β position (the carbon atom next to the carbon atom bonded to CH ₂ ═CR ¹¹ (CO)O-). It is further preferable that it has the following. Specific examples of the above-mentioned chain saturated hydrocarbon groups include 3-chloro-2-hydroxylpropyl group, 3-chloro-2-hydroxybutyl group, 5-chloro-2-hydroxypentyl group, 3-chloro-2 -hydroxy-2-methylpropyl group and 3-bromo-2-hydroxypropyl group.

Specific examples of the monomer (C5) include 3-chloro-2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxybutyl (meth)acrylate, and 5-chloro-(meth)acrylate. Examples include chloro-2-hydroxypentyl and 3-bromo-2-hydroxypropyl (meth)acrylate. Among them, 3-chloro-2-hydroxypropyl (meth)acrylate is preferred, and 3-chloro-2-hydroxypropyl methacrylate is more preferred, since it can improve the durable water repellency of the resulting textile product.

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

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

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

Examples of the monomer (D) include (meth)acryloylmorpholine, (meth)acrylic acid ester having a hydrocarbon group other than the components (A) and (C), (meth)acrylic acid, and fumaric acid. Vinyl monomers other than the fluorine-free component (E) such as esters, maleic esters, fumaric acid, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, ethylene, styrene, etc. can be mentioned. Note that (meth)acrylic acid esters having hydrocarbon groups other than components (A) and (C) include vinyl groups, hydroxyl groups, amino groups, epoxy groups, isocyanate groups, and blocked isocyanate groups in the hydrocarbon groups. It may have a substituent such as, or it 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 (meth)acrylic esters other than component (A) and component (C) include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and ethylene glycol di(meth)acrylate. can be mentioned. Among them, (meth)acryloylmorpholine is more preferred since it can improve the peel strength of the resulting textile product against coating.

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

The non-fluorine polymer contained in the non-fluorine water repellent has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group that can react with a crosslinking agent. is preferable because it improves the durable water repellency of the resulting textile product. The isocyanate group may form a blocked isocyanate group protected with a blocking agent. Further, it is preferable that the non-fluorine-based polymer has an amino group since this also improves the feel of the resulting textile product.

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

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

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

It is also possible to add additives and the like to the water repellent composition of this embodiment, if necessary. Examples of additives include other water repellents, crosslinking agents, antibacterial deodorants, flame retardants, antistatic agents, softeners, antiwrinkle agents, and the like.

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

A non-fluorine water repellent containing a non-fluorine polymer can be produced by a radical polymerization method. Among these radical polymerization methods, emulsion polymerization or dispersion polymerization is preferred from the viewpoint of the performance of the resulting water repellent and the environment.

For example, a non-fluorine-based polymer can be obtained by emulsion polymerization or dispersion polymerization of the (meth)acrylic acid ester monomer (A) represented by the above general formula (A-1) in a medium. More specifically, for example, component (A) and, if necessary, component (B), component (C), component (D), and component (E), as well as an emulsification aid or dispersion, are added to the medium. An auxiliary agent 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, a 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-mentioned liquid mixture, a homomixer, a high-pressure emulsifying machine, an ultrasonic wave, etc. can be mentioned.

The emulsification aids or dispersion aids, etc. (hereinafter also referred to as "emulsification aids, etc.") include nonionic surfactants other than the reactive emulsifier (B), cationic surfactants, anionic surfactants, and amphoteric surfactants. One or more types selected from surfactants can be used. The content of the emulsification aid, etc. is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, and 1 to 10 parts by weight based on 100 parts by weight of the total monomers. It is more preferable that When the content of the emulsification auxiliary agent, etc. is less than 0.5 parts by mass, the dispersion stability of the mixed liquid tends to decrease compared to when the content of the emulsification auxiliary agent, etc. is within the above range, When the content of the emulsification aid, etc. exceeds 30 parts by mass, the water repellency of the resulting non-fluorine-based polymer tends to be lower than when the content of the emulsification aid, etc. is within the above range.

Water is preferred as the medium for emulsion polymerization or dispersion polymerization, and water and an organic solvent may be mixed as necessary. The organic solvent at this time is not particularly limited as long as it is an organic solvent that is miscible with water, but examples include 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. Note that the ratio of water and organic solvent is not particularly limited.

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

Furthermore, in the polymerization reaction, a chain transfer agent such as dodecyl mercaptan or t-butyl alcohol may be used for the purpose of controlling 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, based on 100 parts by mass of the total monomers. When the content of the chain transfer agent exceeds 0.3 parts by mass, the molecular weight tends to decrease, making it difficult to efficiently produce a non-fluorine-based polymer having a weight average molecular weight of 100,000 or more.

Note that a polymerization inhibitor may be used to adjust the molecular weight. By adding a polymerization inhibitor, a fluorine-free polymer having a desired weight average molecular weight can be easily obtained.

The temperature of the polymerization reaction is preferably 20°C to 150°C. If the temperature is less than 20°C, polymerization tends to be insufficient compared to when the temperature is within the above range, and if 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 non-fluorine-based polymer obtained can be adjusted by increasing or decreasing the contents of the above-mentioned polymerization initiator, chain transfer agent, and polymerization inhibitor, and the melt viscosity at 105 ° C. It can be adjusted by increasing or decreasing the monomer content and the polymerization initiator content. In addition, if it is desired to lower the melt viscosity at 105° C., the content of a monomer having two or more polymerizable functional groups may be reduced or the content of a polymerization initiator may be increased.

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

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

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

In addition, the amount of the organo-modified silicone represented by the above general formula (1) in the non-fluorine water repellent composition of the present embodiment is determined to be 100% by mass of the non-fluorine-based polymer in terms of durable water repellency of the resulting textile product. The amount is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and even more preferably 10 to 25 parts by weight.

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

The water-repellent textile product of this embodiment is obtained by treating the textile product with a treatment liquid containing the above-mentioned non-fluorine water repellent composition. The materials for such textile products are not particularly limited, and include 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. Examples include blended fibers. The form of the textile product may be any form such as fiber, thread, cloth, woven fabric, knitted fabric, cloth in the form of clothing, carpet, nonwoven fabric, paper, etc.

Examples of methods for treating textile products with the above-mentioned treatment liquid include processing methods such as dipping, spraying, and coating, and processing methods using cleaning methods. Further, when the non-fluorine water repellent composition contains water, it is preferable to dry it to remove water after adhering it to a textile product.

Further, after treating a textile product with the non-fluorine water repellent composition of the present embodiment, it is preferable to perform appropriate heat treatment. There are no particular restrictions on the temperature conditions, but when the non-fluorine water repellent composition of the present embodiment is used, textile products can exhibit sufficiently good water repellency under mild conditions of 100 to 130°C. The temperature condition may be high temperature treatment of 130°C or higher (preferably up to 200°C), but in such a case, it is possible to shorten the treatment time compared to the conventional case using a fluorine-based water repellent. . Therefore, according to the water-repellent textile product of this embodiment, deterioration of the textile product due to heat is suppressed, the texture of the textile product becomes soft during water-repellent treatment, and moreover, under mild heat treatment conditions, that is, low-temperature curing conditions. Can impart sufficient water repellency to textile products.

In particular, when it is desired to improve durable water repellency, the above-mentioned process of treating the textile product with a treatment liquid containing a non-fluorine water repellent composition and the addition of one methylolmelamine, isocyanate group or blocked isocyanate group are recommended. It is preferable to water-repellent a textile product by a method that includes a step of attaching a crosslinking agent typified by the above-mentioned compounds to the textile product and heating it. Furthermore, if it is desired to further improve the durable water repellency, the non-fluorinated water repellent composition may contain a non-fluorinated polymer copolymerized with a monomer having a functional group capable of reacting with the above-mentioned crosslinking agent. is preferred.

Examples of compounds having one or more isocyanate groups include monoisocyanates such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate, and naphthalene isocyanate; diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; Examples include isocyanurate ring trimers and trimethylolpropane adducts. Furthermore, examples of the compound having one or more blocked isocyanate groups include compounds obtained by protecting the isocyanate group of the above-mentioned compound having an isocyanate group with a blocking agent. Blocking agents used at this time include organic blocking agents such as secondary or tertiary alcohols, active methylene compounds, phenols, oximes, and lactams, and bisulfite such as sodium bisulfite and potassium bisulfite. Salt is an example. The above-mentioned crosslinking agents may be used alone or in combination.

The crosslinking agent can be prepared by, for example, dissolving the crosslinking agent in an organic solvent or emulsifying and dispersing it in water, immersing the object to be treated (textile products) in the treatment liquid, and drying the treatment liquid that has adhered to the object. It can be attached to the object to be treated. By heating the crosslinking agent attached to the object to be processed, the reaction between the crosslinking agent, the object to be processed, and the non-fluorine-based polymer can proceed. In order to sufficiently advance the reaction of the crosslinking agent and more effectively improve washing durability, heating at this time is preferably carried out at 110 to 180° C. for 1 to 5 minutes. The steps of applying a crosslinking agent and heating may be performed simultaneously with the step of treating with a treatment liquid containing the above-mentioned water repellent composition. When carrying out simultaneously, for example, a treatment liquid containing a water repellent composition and a crosslinking agent is applied to the object to be treated, water is removed, and then the crosslinking agent adhering to the object to be treated is further heated. When considering the simplification of the water repellent treatment process, the reduction of the amount of heat, and the economic efficiency, it is preferable to carry out the treatment at the same time as the water repellent composition treatment process.

Moreover, if the crosslinking agent is used excessively, there is a risk that the texture may be impaired. 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 (textile product).

The water-repellent fiber product of this embodiment thus obtained can exhibit sufficient water repellency even when used outdoors for a long time, and the water-repellent fiber product is made of a fluorine-based compound. It can be made environmentally friendly because it does not contain any waste.

The water-repellent fiber product of this embodiment can be coated in predetermined portions. Examples of coating processing include moisture permeable waterproofing and windproof processing for sports and outdoor applications. For example, in the case of moisture-permeable waterproofing, a coating liquid containing a urethane resin, acrylic resin, etc. and a medium can be applied to one side of a water-repellent textile product and dried. can.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

For example, in the case of producing a non-fluorine-based polymer, the polymerization reaction is carried out by radical polymerization in the above embodiment, but the polymerization reaction is carried out by photopolymerization by irradiating ionizing radiation such as ultraviolet rays, electron beams, and gamma rays. You may do so.

In addition, in the present invention, textile products are treated with a non-fluorine water repellent composition to make them water-repellent textile products. However, the material may be made of metal, glass, resin, or the like.

Further, in such a case, the method of applying the non-fluorine water repellent composition to the article and the amount of the water repellent applied can be arbitrarily determined depending on the type of the object to be treated.

EXAMPLES The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples in any way.

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

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

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

(Synthesis example 4)
Same as Synthesis Example 1 except that 84.2 g of 0.5 mol of 1-dodecene and 59.1 g of α-methylstyrene of 0.5 mol were used instead of 168.3 g of 1 mol of 1-dodecene. An organo-modified silicone and a silicone emulsion were obtained. In addition, the organo-modified silicone has general formula (1) in which a is 0, b is 50, R ²² is a methyl group, R ²³ is a dodecyl group or a methylstyrene group, R ³⁰ , R ³¹ , R ³² , R ³³ , R An organo-modified silicone in which ³⁴ and R ³⁵ are methyl groups was obtained.

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

(Synthesis example 6)
Instead of 63.2 g of methyl hydrogen silicone with a SiH group equivalent of 63.2 g/mol and a polymerization degree of 50, dimethylsiloxane with a SiH group equivalent of 140.5 g/mol and a polymerization degree of 50. An organo-modified silicone and a silicone emulsion were obtained in the same manner as in Synthesis Example 1, except that 140.5 g of a copolymer of and methyl hydrogen siloxane was used. In addition, the organo-modified silicone has general formula (1) in which a is 25, b is 25, R ²⁰ and R ²¹ are a methyl group, R ²² is a methyl group, R ²³ is a dodecyl group, R ³⁰ , R ³¹ , R ³² An organo-modified silicone in which R ³³ , R ³⁴ and R ³⁵ are methyl groups was obtained.

(Synthesis example 7)
To 20 parts by mass of hydrogen silicone (trade name: KF-99, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts by mass of an adduct of 9 moles of ethylene oxide of a branched higher alcohol having 12 to 14 carbon atoms was added and mixed. Next, 77 parts by mass of water was added little by little while mixing, and the mixture was emulsified in water to obtain a silicone emulsion.

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

<Preparation of polymer dispersion>
Mixed liquids having the compositions shown in Tables 1 to 6 (in the tables, the numerical values indicate (g)) were polymerized according to the procedure shown below to obtain polymer dispersions.

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

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

It should be noted that each polymer in the polymer dispersions obtained in Synthesis Examples 9 to 36 was analyzed using a gas chromatograph (GC-15APTF, manufactured by Shimadzu Corporation) to confirm that 98% or more of the total monomers were polymerized. It was confirmed that there is.

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

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

It is a mixture represented by , and the average value of n is 8 (the mixture includes compounds in which n is 6, 8, 10, 12, and 14).

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

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

(1) Melt viscosity measurement method The polymer obtained above was tested using an elevated flow tester CFT-500 (manufactured by Shimadzu Corporation). 1 g of was added, held at 105°C for 6 minutes, and a load of 100 kg·f/cm ² was applied using a plunger to measure the melt viscosity at 105°C.

(2) Method for measuring weight average molecular weight The polymer obtained above was measured using a GPC device (GPC "HLC-8020" manufactured by Tosoh Corporation) under the conditions of a column temperature of 40 ° C. and a flow rate of 1.0 ml/min. The weight average molecular weight was measured using tetrahydrofuran as an eluent, and the weight average molecular weight was measured in terms of standard polystyrene. Note that three columns manufactured by Tosoh Corporation under the trade name TSK-GEL G5000HHR, G4000HHR, and G3000HHR were connected and installed.

<Adjustment of water repellent composition>
(Examples 1 to 37 and Comparative Examples 1 to 9)
The water repellent aids (silicone emulsions) obtained in Synthesis Examples 1 to 8 and the polymer dispersions obtained in Synthesis Examples 9 to 36 were mixed at the mass ratios listed in Tables 11 to 15 to form a water repellent composition. It became a thing.

The water repellent composition obtained above was evaluated.

(Evaluation of water repellency of textile products)
The test was conducted at a shower water temperature of 27° C. according to the spray method of JIS L 1092 (1998). In this test, dyed 100% polyester cloth or 100% nylon cloth was treated with a treatment solution prepared by diluting the water repellent compositions of Examples and Comparative Examples with water so that the polymer content was 3% by mass. After immersion treatment (pickup rate 60% by mass), the cloth was dried at 130° C. for 2 minutes, and further heat treated under the conditions shown in Tables 7 to 10, and the water repellency of the resulting cloth was evaluated. The results were visually evaluated using the following grades. In addition, when the characteristics were slightly good, a "+" was added to the grade, and when the characteristics were slightly inferior, a "-" was added to the grade. The results are shown in Tables 16-22.
Water repellency: Status 5: No moisture adhesion on the surface 4: Slight moisture adhesion on the surface 3: Partial moisture on the surface 2: Moisture on the surface 1: Moisture on the entire surface 0: Completely wet on both sides

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

(Durable water repellency evaluation of textile products)
The test was conducted at a shower water temperature of 27° C. according to the spray method of JIS L 1092 (1998). In this test, dyed 100% polyester cloth was used with a polymer content of 3% by mass and a UNIKA RESIN 380-K (crosslinking agent, trimethylolmelamine resin manufactured by Union Chemical Industry Co., Ltd.) content of 0. The water repellent of Examples and Comparative Examples was adjusted such that the content of UNIKA CATALYST 3-P (surfactant, manufactured by Union Chemical Industry Co., Ltd., amino alcohol hydrochloride) was 0.2% by mass. A fabric (L- The water repellency of the cloth was evaluated in the same manner as the water repellency evaluation method described above after washing the cloth 10 times (L-10) according to Method 103 of JIS L 0217 (1995). In addition, in the case of 100% nylon cloth, evaluation was performed in the same manner as in the case of 100% polyester cloth, except that the heat treatment temperature was changed from 170°C to 160°C. The results are shown in Tables 16-22.

(Peel strength against textile coating)
The test was conducted in accordance with JIS K 6404-5 (1999). In this test, dyed 100% nylon cloth was immersed in a treatment solution prepared by diluting the water repellent compositions of Examples and Comparative Examples with water so that the polymer content was 3% by mass. 60% by mass), dried at 130°C for 2 minutes, and further heat-treated at 160°C for 30 seconds to obtain a base fabric. A hot melt adhesive tape ("MELCO Tape" manufactured by Sun Kasei Co., Ltd.) was thermally bonded to the obtained base fabric at 150°C for 1 minute using a thermocompression bonding device, and the layer between the base fabric and the seam tape was peeled off. The strength was measured using an autograph (AG-IS, manufactured by Shimadzu Corporation). The grip was pulled at a moving speed of 100 mm/min, and the average value of the stress was defined as the peel strength [N/inch]. The results are shown in Tables 16-22.

The textile products treated with the water repellent compositions of Examples 1 to 37 were treated with the conventional fluorine-based water repellent (Comparative Example 7) and the organoleptic compound represented by the above general formula (1), even when not heat-treated. It was confirmed that it exhibited water repellency equivalent to or better than the case using only modified silicone (Comparative Example 8), had excellent durable water repellency, and had a good texture.

In addition, the textile products treated with the water repellent compositions of Examples 1 to 37 were treated with the water repellent composition (Comparative Example 9) that did not contain organo-modified silicone represented by the above general formula (1). It was confirmed that it exhibits water repellency equivalent to or better than that of 100%, has excellent durable water repellency, and has superior peel strength against resin coatings.

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

Claims (11)

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

[In formula (1), R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group, and R ²³ represents a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group. R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom or a methyl group . where a represents an integer of 0 or more, b represents an integer of 1 or more, (a+b) is 20 to 100, and when a is 2 or more, multiple R ²⁰ and R ²¹ are each the same. When b is 2 or more, a plurality of R ²² and R ²³ may be the same or different. ]

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

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

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

[In formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ is 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. Represents a monovalent chain hydrocarbon group having 1 to 11 carbon atoms and having one type of functional group. However, the number of (meth)acryloyloxy groups in the molecule is 2 or less. However, the (C5) (meth)acrylic acid ester monomer represented by the following general formula (C-5) is not included. ]

[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. ]

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

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

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

[In formula (1), R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group, and R ²³ represents a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group. R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom or a methyl group. where a represents an integer of 0 or more, b represents an integer of 1 or more, (a+b) is 20 to 100, and when a is 2 or more, multiple R ²⁰ and R ²¹ are each the same. When b is 2 or more, a plurality of R ²² and R ²³ may be the same or different. ]

[In formula (A-1), R ¹ represents hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent. ] The emulsion or the dispersion is (B1) a compound represented by the following general formula (I-1) having an HLB of 7 to 18, (B2) the following general formula (II-1) having an HLB of 7 to 18. ), and (B3) at least one compound selected from the group consisting of an alkylene oxide having 2 to 4 carbon atoms added to an oil or fat having a hydroxyl group and a polymerizable unsaturated group and having an HLB of 7 to 18. The non-fluorine water repellent composition according to claim 5, further comprising a reactive emulsifier (B).

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

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

[In formula (C-1), R ⁵ represents hydrogen or a methyl group, and R ⁶ is 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. Represents a monovalent chain hydrocarbon group having 1 to 11 carbon atoms and having one type of functional group. However, the number of (meth)acryloyloxy groups in the molecule is 2 or less. However, the (C5) (meth)acrylic acid ester monomer represented by the following general formula (C-5) is not included. ]

[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. ]

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

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

[In formula (C-5), R ¹¹ represents hydrogen or a methyl group, and R ¹² has 3 to 6 carbon atoms and has at least one functional group selected from the group consisting of a chloro group and a bromo group and a hydroxyl group. represents a monovalent chain saturated hydrocarbon group. ] The (meth)acrylic ester monomer (A) represented by the general formula (A-1) is an acrylic ester monomer (a1) in which R ¹ is hydrogen and R ¹ is a methyl group. The non-fluorine-based water repellent composition according to any one of claims 1 to 8, comprising a methacrylic acid ester monomer (a2). The non-fluorine water repellent composition according to any one of claims 1 to 9, wherein the content of the organo-modified silicone is 1 to 50 parts by mass based on 100 parts by mass of the non-fluorine polymer. A method for producing a water-repellent textile product, comprising the step of treating a textile product with a treatment liquid containing the non-fluorine water repellent composition according to any one of claims 1 to 10.