JP2021143292A - Water repellent agent composition, water repellent fiber product, and method for producing water repellent fiber product - Google Patents

Abstract

To provide: a water repellent agent composition which can manifest excellent water repellency and durable water repellency without being limited by the kind of a fiber product; a water repellent fiber product using the water repellent agent composition; and a method for producing the water repellent fiber product.SOLUTION: Provided is a water repellent agent composition, comprising a non-fluoropolymer (α) containing a constitutional unit derived from a (meth)acrylate monomer (A1) of a specific structure and a constitutional unit derived from a compound (A2) of a specific structure containing an ester group or an amide group, and a ureido group or a ketone group; an organo-modified silicone (β) of a specific structure, and a wax (γ).SELECTED DRAWING: None

Description

The present invention relates to a water repellent composition, a water repellent fiber product using the same, and a method for producing the same.

Conventionally, a fluorine-based water repellent containing a fluorine-based compound is known, and a textile product in which water repellency is imparted to the surface of the fiber product or the like by treating the fluorine-based water repellent is known. .. Such a fluorine-based water repellent is generally produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group. Although textile products treated with a fluorine-based water repellent exhibit excellent water repellency, since concerns about environmental load have become clear for monomers having a fluoroalkyl group, fluorine is not contained in fluorine-based compounds. There is an international demand for non-fluorine-based water repellents that exhibit high-performance water-repellent performance comparable to that of water-based water repellents.

Therefore, in recent years, research has been conducted on non-fluorine-based water repellents that do not contain fluorine-based compounds. Patent Document 1 describes a processing agent for fibers containing at least one of a silicon-based compound, a wax-based compound, and a wax-zirconium-based compound and a cross-linking agent as main components. Patent Document 2 includes a non-fluorine polymer having a repeating unit derived from a specific non-fluorine (meth) acrylate ester monomer, a wax having a melting point of 52 to 88 ° C., an aqueous medium, and a specific emulsifier. A water- and oil-repellent agent, which is an aqueous dispersion, is described.

Japanese Unexamined Patent Publication No. 2006-124866 JP-A-2018-104632

However, even if the conventional water repellent composition can satisfactorily exhibit water repellency (initial water repellency) (hereinafter, may be simply referred to as water repellency) in the initial state of the textile product, the textile product is used. Water repellency (hereinafter, also referred to as durable water repellency) after receiving a load of time (washing, rubbing, etc.) may be significantly reduced, and it is excellent not only in initial water repellency but also in durable water repellency. A liquid composition is desired.

Further, when manufacturing a textile product in which fibers are dyed, if an unfixed dye remains in the dyed fiber, color transfer occurs due to washing, rubbing, etc. during use of the textile product. After that, a process of fixing the dye to the fiber (that is, a fixing process) may be performed. The fixing treatment is usually carried out by attaching a fixing agent selected according to the type of fiber and dye to the dyed fiber. For example, anionic fixing agents (eg, polyhydric phenol derivatives, etc.) may be useful for acid dyes or gold-containing dyes, and cationic fixing agents (for example, polyamines, etc.) may be useful for direct dyes or reactive dyes. However, when the fixed fiber is further treated with a water repellent composition to produce a water repellent fiber product, it is not always easy to develop the desired water repellency in the water repellent fiber product, and it is particularly good. It is difficult to develop not only good water repellency but also good durable water repellency. In the fixed fiber, the surface of the fiber is smoothed by the presence of the fixing agent in a film form, so that the water repellent composition is hard to physically adhere to the fiber, and the fixing agent is used in the fiber. It is considered that one of the causes is that the water repellent composition is difficult to penetrate because it adheres to the amorphous region. In order to impart water repellency to the fixed fiber, it is necessary to use at least a water repellent composition specially formulated for the treatment of the fiber, which is a burden on process control and cost. It has become.

The present invention solves the above-mentioned problems, and a water-repellent composition capable of exhibiting excellent water repellency and durable water repellency without being restricted by the type of textile product, and a water-repellent fiber using the water-repellent composition. The purpose is to provide a product and a method for manufacturing the product.

［式（Ａ−１）中、Ｒ¹は水素又はメチル基を表し、Ｒ²は置換基を有していてもよい炭素数１２〜３０の１価の炭化水素基を表す。］

［式（Ａ−２）中、Ｒ¹¹は水素又はメチル基を表し、Ｒ¹²は炭素数１〜６の２価の炭化水素基を表し、Ｚはエステル基またはアミド基を表し、Ｗは−ＣＯ−Ｒ¹³（式中、Ｒ¹³は炭素数１〜４の１価の炭化水素基を表す）で表される基、−ＮＨ−ＣＯ−ＮＨ₂で表される基、又は下記式（Ａ−３）で表される基を表す。］

［式（１）中、Ｒ²⁰、Ｒ²¹及びＲ²²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、Ｒ²³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８〜２２のアルキル基を表し、Ｒ³⁰、Ｒ³¹、Ｒ³²、Ｒ³³、Ｒ³⁴及びＲ³⁵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８〜２２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Ｒ²⁰及びＲ²¹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Ｒ²²及びＲ²³はそれぞれ同一であっても異なっていてもよい。］
［２］ 前記非フッ素系ポリマー（α）が、塩化ビニル及び塩化ビニリデンのうち少なくとも１種の単量体（ＶＣ）に由来する構成単位を更に含有する、上記態様１に記載の撥水剤組成物。
［３］ 前記オルガノ変性シリコーン（β）の含有量が、非フッ素系ポリマー（α）１００質量部に対して、１〜５０質量部である、上記態様１又は２に記載の撥水剤組成物。
［４］ 前記ワックス（γ）の融点が、３５℃〜９０℃である、上記態様１〜３のいずれかに記載の撥水剤組成物。
［５］ 上記態様１〜４のいずれかに記載の撥水剤組成物が付着した繊維製品である、撥水性繊維製品。
［６］ 繊維製品を、上記態様１〜４のいずれかに記載の撥水剤組成物が含まれる処理液で処理する工程、を備える、撥水性繊維製品の製造方法。 The present disclosure includes the following aspects.
[1] The structural unit derived from the (meth) acrylic acid ester monomer (A1) represented by the following general formula (A-1) and the compound (A2) represented by the following general formula (A-2). Non-fluorinated polymer (α) containing the derived structural unit and
Organo-modified silicone (β) represented by the following general formula (1) and
A water repellent composition comprising wax (γ).

[In the formula (A-1), R ¹ represents a hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent. ]

[In formula (A-2), R ¹¹ represents a hydrogen or methyl group, R ¹² represents a divalent hydrocarbon group having 1 to 6 carbon atoms, Z represents an ester group or an amide group, and W represents a − A group represented by CO-R ¹³ (in the formula, R ¹³ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms), a group represented by -NH-CO-NH ₂ , or the following formula (A). Represents the group represented by -3). ]

[In formula (1), R ²⁰ , R ²¹ and R ²² 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 of number 8 to 40 or an alkyl group of number 8 to 22, and R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independent hydrogen atoms, methyl groups and ethyls, respectively. A group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 8 to 22 carbon atoms, a represents an integer of 0 or more, and b represents 1 Representing the above integers, (a + b) is 10 to 200, and when a is 2 or more, a plurality of R ²⁰ and R ²¹ may be the same or different, and when b is 2 or more. , A plurality of R ²² and R ²³ may be the same or different from each other. ]
[2] The water repellent composition according to the above aspect 1, wherein the non-fluorinated polymer (α) further contains a structural unit derived from at least one monomer (VC) of vinyl chloride and vinylidene chloride. thing.
[3] The water repellent composition according to the above aspect 1 or 2, wherein the content of the organomodified silicone (β) is 1 to 50 parts by mass with respect to 100 parts by mass of the non-fluorinated polymer (α). ..
[4] The water repellent composition according to any one of the above aspects 1 to 3, wherein the wax (γ) has a melting point of 35 ° C. to 90 ° C.
[5] A water-repellent textile product to which the water-repellent composition according to any one of the above aspects 1 to 4 is attached.
[6] A method for producing a water-repellent textile product, comprising a step of treating the textile product with a treatment liquid containing the water-repellent composition according to any one of the above aspects 1 to 4.

According to one aspect of the present disclosure, a water repellent composition capable of exhibiting excellent water repellency and durable water repellency (particularly washing durability and abrasion durability) without being restricted by the type of textile product, and the water repellency. A water-repellent fiber product using the agent composition and a method for producing the same can be provided.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following aspects.

［式（Ａ−１）中、Ｒ¹は水素又はメチル基を表し、Ｒ²は置換基を有していてもよい炭素数１２〜３０の１価の炭化水素基を表す。］

［式（Ａ−２）中、Ｒ¹¹は水素又はメチル基を表し、Ｒ¹²は炭素数１〜６の２価の炭化水素基を表し、Ｚはエステル基またはアミド基を表し、Ｗは−ＣＯ−Ｒ¹³（式中、Ｒ¹³は炭素数１〜４の１価の炭化水素基を表す）で表される基、−ＮＨ−ＣＯ−ＮＨ₂で表される基、又は下記式（Ａ−３）で表される基を表す。］

［式（１）中、Ｒ²⁰、Ｒ²¹及びＲ²²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、Ｒ²³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８〜２２のアルキル基を表し、Ｒ³⁰、Ｒ³¹、Ｒ³²、Ｒ³³、Ｒ³⁴及びＲ³⁵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８〜２２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Ｒ²⁰及びＲ²¹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Ｒ²²及びＲ²³はそれぞれ同一であっても異なっていてもよい。］ [Water repellent composition]
One aspect of the present invention is
A structural unit derived from the (meth) acrylic acid ester monomer (A1) represented by the following general formula (A-1) and a configuration derived from the compound (A2) represented by the following general formula (A-2). A non-fluorinated polymer (α) containing a unit and
Organo-modified silicone (β) represented by the following general formula (1) and
Provided is a water repellent composition containing wax (γ).

[In the formula (A-1), R ¹ represents a hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent. ]

[In formula (A-2), R ¹¹ represents a hydrogen or methyl group, R ¹² represents a divalent hydrocarbon group having 1 to 6 carbon atoms, Z represents an ester group or an amide group, and W represents a − A group represented by CO-R ¹³ (in the formula, R ¹³ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms), a group represented by -NH-CO-NH ₂ , or the following formula (A). Represents the group represented by -3). ]

[In formula (1), R ²⁰ , R ²¹ and R ²² 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 of number 8 to 40 or an alkyl group of number 8 to 22, and R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independent hydrogen atoms, methyl groups and ethyls, respectively. A group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 8 to 22 carbon atoms, a represents an integer of 0 or more, and b represents 1 Representing the above integers, (a + b) is 10 to 200, and when a is 2 or more, a plurality of R ²⁰ and R ²¹ may be the same or different, and when b is 2 or more. , A plurality of R ²² and R ²³ may be the same or different from each other. ]

The water repellent composition of the present embodiment is an unexpectedly fixed textile product by containing a specific combination of a non-fluorinated polymer (α), an organomodified silicone (β) and a wax (γ). It adheres well even to and can impart excellent water repellency. Further, since the water repellent composition can impart excellent durable water repellency regardless of the type of the textile product, including the above-mentioned fixed textile product, the textile product treated with the water repellent composition. Can still maintain good water repellency even after being subjected to physical loads such as washing and rubbing during use. A water repellent composition capable of imparting water repellency and durable water repellency at a satisfactory level even to a textile product to which the water repellent composition is inherently difficult to adhere, such as a fixed textile product, is available. It is unexpected that the water repellent composition of the present embodiment, which has not been provided conventionally, can exhibit such excellent performance.

Although not bound by theory, the non-fluoropolymer (α) aggregates by having an ester group or an amide group and a ureido group or a ketone group as a constituent unit derived from the compound (A2). It is considered to have easy characteristics. The water repellent composition of the present embodiment containing the non-fluoropolymer (α), the organomodified silicone (β) and the wax (γ) is disadvantageous for adhesion of the water repellent composition to the fibers such as fixing treatment. In addition to being able to adhere well to the treated fibers, it is easy to form an uneven structure on the surface of the fibers treated with the water repellent composition, so that not only good water repellency but also good water repellency is good. It can contribute to the development of durable water repellency.

Hereinafter, each component of the water repellent composition will be further described.

<Non-fluorine polymer (α)>
The non-fluorinated polymer (α) is a structural unit derived from the (meth) acrylic acid ester monomer (A1) represented by the following general formula (A-1) (hereinafter, also referred to as “(A1) component”). And a structural unit derived from the compound (A2) represented by the following general formula (A-2) (hereinafter, also referred to as “component (A2)”).

［式（Ａ−１）中、Ｒ¹は水素又はメチル基を表し、Ｒ²は置換基を有していてもよい炭素数１２〜３０の１価の炭化水素基を表す。］

[In the formula (A-1), R ¹ represents a hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent. ]

［式（Ａ−２）中、Ｒ¹¹は水素又はメチル基を表し、Ｒ¹²は炭素数１〜６の２価の炭化水素基を表し、Ｚはエステル基またはアミド基を表し、Ｗは−ＣＯ−Ｒ¹³（Ｒ¹³は炭素数１〜４の１価の炭化水素基を表す）で表される基、−ＮＨ−ＣＯ−ＮＨ₂で表される基、又は下記式（Ａ−３）で表される基を表す。］

[In formula (A-2), R ¹¹ represents a hydrogen or methyl group, R ¹² represents a divalent hydrocarbon group having 1 to 6 carbon atoms, Z represents an ester group or an amide group, and W represents a − A group represented by CO-R ¹³ (R ¹³ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms), a group represented by -NH-CO-NH ₂ , or the following formula (A-3). Represents a group represented by. ]

Here, "(meth) acrylic acid ester" means "acrylic acid ester" or its corresponding "methacrylic acid ester", and is synonymous with "(meth) acrylic acid", "(meth) acrylamide" and the like. be.

The component (A1) has a monovalent hydrocarbon group having 12 to 30 carbon atoms, which may have a substituent. The hydrocarbon group may be linear or branched, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be an alicyclic or aromatic cyclic group. May have. Among these, from the viewpoint of water repellency, durable water repellency and texture, a linear one is preferable, and a linear alkyl group is more preferable. In this case, the water repellency and the water repellency are more excellent. When a monovalent hydrocarbon group having 12 to 30 carbon atoms has a substituent, the substituents include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group and (meth) acryloyloxy. One or more of the groups and the like can be mentioned. In the present embodiment, in the above general formula (A-1), R ² is preferably an unsubstituted hydrocarbon group.

The number of carbon atoms of the hydrocarbon group is preferably 12 to 24 from the same viewpoint as above.

The number of carbon atoms of the hydrocarbon group is more preferably 12 to 22. When the number of carbon atoms is in this range, water repellency, durable water repellency and texture become particularly excellent. Particularly preferred as the hydrocarbon group is a linear alkyl group having 18 to 22 carbon atoms.

Examples of the (A1) component include stearyl (meth) acrylate, cetyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, and (meth) acrylic acid. Examples thereof include heptadecyl, nonadecil (meth) acrylate, eikosyl (meth) acrylate, heneikosyl (meth) acrylate and behenyl (meth) acrylate.

The component (A1) can have at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group capable of reacting with a cross-linking agent. In this case, by using the non-fluorine-based polymer (α) together with the cross-linking agent, the durable water repellency of the obtained textile product can be further improved. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. Further, when the component (A1) has an amino group, the texture of the obtained textile product can be further improved.

The component (A1) is preferably a monofunctional (meth) acrylic acid ester monomer having one polymerizable unsaturated group in one molecule.

The above component (A1) may be used alone or in combination of two or more.

In the above formula (A-2), R ¹² may be linear or branched, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be a fat. It may have a cyclic or aromatic ring. The presence of the component (A2) contributes to the development of good durable water repellency.

In the above formula (A-2), when Z is an ester group, R ¹² is a hydrocarbon group having 2 to 4 carbon atoms, and W is _{a group represented by -NH-CO-NH 2} or the above formula. It is preferably a group represented by (A-3). When Z is an amide group, R ¹² is a hydrocarbon group having 2 to 4 carbon atoms, W is a group represented by ^{−CO-R 13 , and R 13} has 1 to 2 carbon atoms. Is preferable.

The component (A2) is not particularly limited, but is, for example, diacetoneacrylamide, 2-methylpropenate [2- (2-oxo-2-imidazolidinyl) ethyl], N- [2- (2-oxoimidazolidine)]. -3-Il) Ethyl] Methacrylamide can be mentioned. Among these, from the viewpoint of durable water repellency of textile products, diacetone acrylamide and 2-methylpropene acid [2- (2-oxo-2-imidazolidinyl) ethyl] are preferable as the component (A2).

The above component (A2) may be used alone or in combination of two or more.

The content ratio of the structural unit derived from the component (A1) and the structural unit derived from the component (A2) in the non-fluorinated polymer (α) of the present embodiment is the mass of the component (A1) to be blended and the component (A2). The ratio (A1) / (A2) to the mass of (A1) / (A2) is preferably 99.9 / 0.1 to 70/30, more preferably 99.8 / 0.2 to 80/20, and 99. It is more preferably .7 / 0.3 to 90/10. When (A1) / (A2) is within the above range, the durable water repellency and water repellency of the obtained textile product become better.

The total mass of the mass of the component (A1) and the mass of the component (A2) to be blended is preferably 60 to 100% by mass, preferably 70% by mass, based on the total amount of the monomer components constituting the non-fluorinated polymer (α). ~ 99% by mass is more preferable, and 80 to 98% by mass is further preferable.

The non-fluorinated polymer (α) is a single amount of at least one of vinyl chloride and vinylidene chloride in addition to the components (A1) and (A2) from the viewpoint of water repellency, durable water repellency and peel strength. It is preferable that the body (VC) (hereinafter, also referred to as “(VC) component”) is contained as a monomer component.

The (VC) component is preferably vinyl chloride from the viewpoint of maintaining the texture of the textile product.

The mass of the (VC) component to be blended is 10 masses from the viewpoint of water repellency, durable water repellency and peel strength with respect to 100 parts by mass in total of the mass of the component (A1) and the mass of the component (A2) to be blended. The amount is preferably 20 parts by mass or more, and more preferably 20 parts by mass or more. The mass of the (VC) component to be blended is 100 parts by mass from the viewpoint of water repellency, durable water repellency and texture with respect to a total of 100 parts by mass of the mass of the (A1) component and the mass of the (A2) component to be blended. The amount is preferably 75 parts by mass or less, and more preferably 75 parts by mass or less.

The non-fluoropolymer (α) is a component (A1) and a component (A2) in that it can improve the emulsification stability of the non-fluorine polymer (α) at the time of emulsification polymerization or dispersion polymerization and in the composition after the polymerization. In addition, (B1) a compound represented by the following general formula (I-1) having an HLB of 7 to 18, and (B2) represented by the following general formula (II-1) having an HLB of 7 to 18. At least one reactive emulsifier selected from a compound and a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to a fat or oil having a hydroxyl group and a polymerizable unsaturated group having an HLB of 7 to 18 (B3). It is preferable that (B) (hereinafter, also referred to as “component (B)”) is contained as a monomer component.

［式（Ｉ−１）中、Ｒ³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、Ｙ¹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 a hydrogen or 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、Ｒ⁴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、Ｙ²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 contains an alkyleneoxy group having 2 to 4 carbon atoms. Represents a divalent group. ]

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

The "HLB" is an HLB value calculated by the Griffin method, with the ethyleneoxy group being regarded as a hydrophilic group and all other groups being regarded as lipophilic groups.

The HLBs of the compounds (B1) to (B3) used in the present embodiment are 7 to 18, and the non-fluoropolymer (α) of the present embodiment is emulsified or dispersedly polymerized during and after the polymerization. From the viewpoint of emulsion stability in the composition (hereinafter, simply referred to as emulsion stability), 9 to 15 are preferable. Furthermore, it is more preferable to use two or more kinds of reactive emulsifiers (B) having different HLBs within the above range in combination in terms of storage stability of the water repellent composition.

In the reactive emulsifier (B1) represented by the above general formula (I-1) used in the present embodiment, R ³ is a hydrogen or a methyl group, and the component (A1) and / or the component (A2) It is more preferable that it is a methyl group in terms of copolymerizability. X is a linear or branched alkylene group having 1 to 6 carbon atoms, and a linear alkylene group having 2 to 3 carbon atoms is more preferable from the viewpoint of emulsion stability of the non-fluorinated polymer (α) 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 be within the above HLB range. Moreover, when there are two or more kinds of alkyleneoxy groups, they can have a block addition structure or a random addition structure.

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

［式（Ｉ−２）中、Ｒ³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、Ａ¹Ｏ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Ａ¹Ｏは同一であっても異なっていてもよい。］

[In formula (I-2), R ³ represents a hydrogen or 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. Can be appropriately selected so that m is within the range of the above HLB. Specifically, an integer of 1 to 80 is preferable, and when m is 2 or more, m A ¹ O are the same. May be different. ]

In the compound represented by the general formula (I-2), R ³ is a hydrogen or a methyl group, and may be a methyl group in terms of copolymerizability with the component (A1) and / or the component (A2). More preferred. X is a linear or branched alkylene group having 1 to 6 carbon atoms, and a linear alkylene group having 2 to 3 carbon atoms is more preferable from the viewpoint of emulsion stability of the non-fluorinated polymer (α) of the present embodiment. .. A ¹ O is an alkyleneoxy group having 2 to 4 carbon atoms. The type and combination of A ¹ O and the number of m can be appropriately selected so as to be within the above HLB range. In terms of the emulsion stability of the non-fluorinated polymer (α) of the present embodiment, m is preferably an integer of 1 to 80, and more preferably an integer of 1 to 60. When m is 2 or more, m A ¹ O may be the same or different. Further, ^{when 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 general formula (I-2) can be obtained by a conventionally known method, and is not particularly limited. Further, it can be easily obtained from a commercially available product, and examples thereof include "Latemuru PD-420", "Latemuru PD-430", and "Latemuru PD-450" manufactured by Kao Corporation.

In the reactive emulsifier (B2) represented by the above general formula (II-1) used in the present embodiment, R ⁴ is a monovalent unsaturated hydrocarbon having 13 to 17 carbon atoms having a polymerizable unsaturated group. Examples of the hydrogen group include a tridecenyl group, a tridecadienyl group, a tetradecenyl group, a tetradienyl group, a pentadecenyl group, a pentadecadienyl group, a pentadecatrienyl group, a heptadecenyl group, a heptadecadienyl group, a heptadecatrienyl group and the like. .. In terms of the emulsion stability of the non-fluorinated polymer (α) of the present embodiment, R ⁴ is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

Y ² is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. The type, combination and number of alkyleneoxy groups added in Y ² can be appropriately selected so as to be within the above HLB range. Moreover, when there are two or more kinds of alkyleneoxy groups, they can have a block addition structure or a random addition structure. The ethyleneoxy group is more preferable as the alkyleneoxy group in terms of the emulsion stability of the non-fluorinated polymer (α) of the present embodiment.

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

［式（ＩＩ−２）中、Ｒ⁴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、Ａ²Ｏ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Ａ²Ｏは同一であっても異なっていてもよい。］

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

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

A ² O is an alkyleneoxy group having 2 to 4 carbon atoms. In terms of emulsion stability of the non-fluorine-containing polymer of the present embodiment (alpha), the type and combination of A ² O, and the number of n may be appropriately chosen to be within the scope of the HLB. In terms of the emulsion stability of the non-fluorinated polymer (α) of the present embodiment, A ² O is more preferably an ethyleneoxy group, n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, and 8 An integer of ~ 14 is even more preferred. When n is 2 or more, n A ² O may be the same or different. Further, ^{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 the present embodiment is to add an 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 at 120 to 170 ° C. under pressure using an alkaline catalyst such as caustic soda or caustic potassium.

The above-mentioned phenol having an unsaturated hydrocarbon group includes 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 can be mentioned.

The reactive emulsifier (B3) used in the present embodiment is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a fat or oil having a hydroxyl group and a polymerizable unsaturated group having an HLB of 7 to 18. .. The fats and oils having a hydroxyl group and a polymerizable unsaturated group include hydroxy unsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.). Examples include mono or diglyceride of fatty acids, and triglyceride of fatty acids containing at least one hydroxyunsaturated fatty acid (ricinoleic acid, ricinooleic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of emulsion stability of the non-fluoropolymer (α) of the present embodiment, an alkylene oxide adduct of triglyceride of a fatty acid containing at least one hydroxyunsaturated fatty acid is preferable, and castor oil (triglyceride of a fatty acid containing ricinoleic acid) is preferable. ), The alkylene oxide adduct having 2 to 4 carbon atoms is more preferable, and the ethylene oxide adduct of castor oil is further preferable. Further, the number of moles of alkylene oxide added can be appropriately selected so as to be within the above range of HLB, and 20 to 50 moles can be selected in terms of the emulsion stability of the non-fluorinated polymer (α) of the present embodiment. More preferably, 25 to 45 mol is even more preferable. Moreover, when there are two or more kinds of alkylene oxides, they can have a block addition structure or a random addition structure.

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

The composition ratio of the monomer of the component (B) in the non-fluorinated polymer (α) of the present embodiment is determined by the emulsion polymerization or dispersion polymerization of the non-fluorinated polymer (α) and the emulsification in the composition after the polymerization. From the viewpoint of improving stability and imparting good water repellency and durable water repellency to textile products, 0.5 to 20% by mass with respect to the total amount of the monomer components constituting the non-fluoropolymer (α). It is preferably 1 to 15% by mass, more preferably 3 to 10% by mass, and even more preferably 3 to 10% by mass.

The non-fluorine-based polymer (α) contained in the water-repellent composition of the present embodiment can improve the durable water repellency of the obtained textile product, and in addition to the components (A1) and (A2), the following ( At least one second (meth) acrylic acid ester monomer (C) (hereinafter, also referred to as “C component”) selected from the group consisting of C1), (C2), (C3) and (C4). It is preferably contained as a monomer component.

［式（Ｃ−１）中、Ｒ⁵は水素又はメチル基を表し、Ｒ⁶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) (Meta) acrylic acid ester monomer represented by the following general formula (C-1)

[In formula (C-1), R ⁵ represents a hydrogen or methyl group, and R ⁶ is at least selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group and a (meth) acryloyloxy group. It represents a monovalent chain hydrocarbon group having 1 to 11 carbon atoms and having one kind of functional group. However, the number of (meth) acryloyloxy groups in the molecule is 2 or less. ]

［式（Ｃ−２）中、Ｒ⁷は水素又はメチル基を表し、Ｒ⁸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) (Meta) acrylic acid ester monomer represented by the following general formula (C-2)

[In formula (C-2), R ⁷ represents a hydrogen or 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、Ｒ⁹は無置換の炭素数１〜４の１価の鎖状炭化水素基を表す。］ (C3) Methacrylate monomer represented by the following general formula (C-3)

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

［式（Ｃ−４）中、Ｒ¹⁰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) (Meta) acrylic acid ester monomer represented by the following general formula (C-4)

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

The monomer of (C1) 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. It is a (meth) acrylic acid ester monomer having a monovalent chain hydrocarbon group of 1 to 11. From the viewpoint of being able to react with a cross-linking agent, the monovalent chain hydrocarbon group having 1 to 11 carbon atoms is at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group. It preferably has a functional group. When a non-fluorinated polymer (α) containing a monomer of (C1) having a group capable of reacting with these cross-linking agents is treated into a textile product together with a cross-linking agent, the texture of the obtained textile product is maintained. It is possible to improve the durable water repellency while keeping it. The isocyanate group may be a blocked isocyanate group protected by a blocking agent.

The chain hydrocarbon group may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, the chain hydrocarbon group may further have a substituent in addition to the above functional group. Above all, it is preferable that it is linear and / or is a saturated hydrocarbon group in that the durable water repellency of the obtained textile product can be improved.

Specific examples of the (C1) monomer include 2-hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, and 1,1-bis (acryloyloxymethyl) ethyl. Examples thereof include isocyanate. 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 preferable because the durable water repellency of the obtained textile product can be improved. Further, dimethylaminoethyl (meth) acrylate is preferable in terms of improving the texture of the obtained textile product.

The mass of the component (C1) to be blended is 3 parts by mass or more from the viewpoint of durable water repellency with respect to a total of 100 parts by mass of the mass of the component (A1) to be blended and the mass of the component (A2). It is preferably 5 parts by mass or more, and more preferably 5 parts by mass or more. The mass of the component (C1) to be blended is the mass of the component (A1) to be blended and the mass of the component (A2) from the viewpoint of obtaining good water repellency and durable water repellency by adhering the water repellent composition to the textile product. It is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less with respect to 100 parts by mass in total.

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

The mass of the component (C2) to be blended is 3 parts by mass or more from the viewpoint of durable water repellency with respect to a total of 100 parts by mass of the mass of the component (A1) to be blended and the mass of the component (A2). It is preferably 5 parts by mass or more, and more preferably 5 parts by mass or more. The mass of the component (C2) to be blended is the mass of the component (A1) to be blended and the mass of the component (A2) from the viewpoint of obtaining good water repellency and durable water repellency by adhering the water repellent composition to the textile product. It is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less with respect to 100 parts by mass in total.

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

The mass of the component (C3) to be blended is 3 parts by mass or more from the viewpoint of durable water repellency with respect to a total of 100 parts by mass of the mass of the component (A1) and the mass of the component (A2) to be blended. It is preferably 5 parts by mass or more, and more preferably 5 parts by mass or more. The mass of the component (C3) to be blended is the mass of the component (A1) to be blended and the mass of the component (A2) from the viewpoint of obtaining good water repellency and durable water repellency by adhering the water repellent composition to the textile product. It is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less with respect to 100 parts by mass in total.

The monomer (C4) is a (meth) acrylic acid ester monomer having 3 or more polymerizable unsaturated groups in one molecule. In the present embodiment, T in the general formula (C-4) is a (meth) acryloyloxy group, and a polyfunctional (meth) acrylic acid ester simple having 3 or more (meth) acryloyloxy groups in one molecule. A metric is preferred. In formula (C-4), the p Ts 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, and the like. Examples thereof include dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate. These monomers may be used alone or in combination of two or more. Among them, tetramethylolmethanetetraacrylate and triacrylate ethoxylated isocyanuric acid are more preferable in that the durable water repellency of the obtained textile product can be improved.

The mass of the component (C4) to be blended is 3 parts by mass or more from the viewpoint of durable water repellency with respect to a total of 100 parts by mass of the mass of the component (A1) and the mass of the component (A2) to be blended. It is preferably 5 parts by mass or more, and more preferably 5 parts by mass or more. The mass of the component (C4) to be blended is the mass of the component (A1) to be blended and the mass of the component (A2) from the viewpoint of obtaining good water repellency and durable water repellency by adhering the water repellent composition to the textile product. It is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less with respect to 100 parts by mass in total.

The total composition ratio of the monomers of the above component (C) in the non-fluorinated polymer (α) of the present embodiment is the non-fluorinated polymer from the viewpoint of water repellency, durable water repellency and texture of the obtained textile product. It is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and further preferably 5 to 20% by mass with respect to the total amount of the monomer components constituting (α). ..

The mass of the component (C) to be blended is 3 parts by mass or more from the viewpoint of durable water repellency with respect to a total of 100 parts by mass of the mass of the component (A1) and the mass of the component (A2) to be blended. It is preferably 5 parts by mass or more, and more preferably 5 parts by mass or more. The mass of the component (C) to be blended is the mass of the component (A1) and the component (A2) to be blended from the viewpoint of satisfactorily adhering the water repellent composition to the textile product to obtain good water repellency and durable water repellency. It is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less with respect to 100 parts by mass in total.

The non-fluorine-based polymer (α) contained in the water-repellent composition of the present embodiment is a monofunctional monomer (D) (D) that is copolymerizable with the components (A1) and (A2) in addition to the components (A1) and (A2). Hereinafter, “component (D)”) can be contained within a range that does not impair the effects of the present invention.

Examples of the component (D) include (meth) acryloyl morpholine, (meth) acrylic acid ester having a hydrocarbon group other than the components (A) and (C), (meth) acrylic acid, fumaric acid ester, and maleic acid. Examples thereof include vinyl-based monomers other than fluorine-free (VC) components such as esters, fumaric acid, maleic acid, (meth) acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, ethylene and styrene. The (meth) acrylic acid ester having a hydrocarbon group other than the component (A) and the component (C) has a vinyl group, a hydroxyl group, an amino group, an epoxy group and an isocyanate group, and a blocked isocyanate group in the hydrocarbon group. It may have a substituent other than a group capable of reacting with a cross-linking agent such as a quaternary ammonium group, and may have an ether bond, an ester bond, an amide bond, or a urethane bond. Etc. may be possessed. Examples of the (meth) acrylic acid ester other than the component (A) and the component (C) include methyl acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate and the like. Can be mentioned. Among them, (meth) acryloyl morpholine is more preferable because it can improve the peel strength of the obtained textile product against the coating.

The mass of the component (D) to be blended is, for example, 3 parts by mass or more, or 5 parts by mass or more, based on 100 parts by mass in total of the mass of the component (A1) to be blended and the mass of the component (A2). It may be, for example, 40 parts by mass or less, or 35 parts by mass or less.

The non-fluoropolymer (α) of the present embodiment may have at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group capable of reacting with a cross-linking agent. It is preferable because it improves the durable water repellency of the obtained textile product. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. Further, it is preferable that the non-fluorine-based polymer (α) has an amino group because it improves the texture of the obtained textile product.

The weight average molecular weight of the non-fluorinated polymer (α) of the present embodiment is preferably 30,000 or more. When the weight average molecular weight is 30,000 or more, the water repellency and water repellency of the obtained textile product tends to be further improved. Further, the weight average molecular weight of the non-fluorinated polymer (α) is more preferably 100,000 or more. In this case, the water repellent composition can be satisfactorily adhered to the textile product so that the textile product exhibits good water repellency and water repellency. The upper limit of the weight average molecular weight of the non-fluorinated polymer (α) is preferably 5 million, for example.

The weight average molecular weight of the non-fluoropolymer (α) is determined by using a GPC device (GPC "HLC-8020" manufactured by Tosoh Corporation) in an eluent under the conditions of a column temperature of 40 ° C. and a flow rate of 1.0 ml / min. It is a value measured using tetrahydrofuran and converted to standard polystyrene. The column used is a column in which three columns of trade names TSK-GEL G5000HHR, G4000HHR, and G3000HHR manufactured by Tosoh Corporation are connected.

In the present embodiment, the melt viscosity of the non-fluorine-based polymer (α) at 105 ° C. is such that good water repellency and durable water repellency can be obtained while maintaining good texture of the textile product, and the non-fluorine-based polymer. When the (α) is emulsified or dispersed to form a water repellent composition, the non-fluorine-based polymer (α) can be prevented from precipitating or settling, thus improving the storage stability of the water repellent composition. In terms of good maintenance, it is preferably 1000 Pa · s or less, and more preferably 500 Pa · s or less.

"Melting viscosity at 105 ° C." means using an elevated flow tester (for example, CFT-500 manufactured by Shimadzu Corporation) and putting 1 g of a non-fluorinated polymer in a cylinder equipped with a die (length 10 mm, diameter 1 mm). Viscosity measured by holding at 105 ° C. for 6 minutes and applying ^{a load of 100 kg ・ f / cm 2 with a plunger.}

<Organo-modified silicone (β)>
The organomodified silicone (β) is a compound represented by the following general formula (1). In the following general formula (1), each structural unit may be a block, random, or may be arranged alternately.

［式（１）中、Ｒ²⁰、Ｒ²¹及びＲ²²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、Ｒ²³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８〜２２のアルキル基を表し、Ｒ³⁰、Ｒ³¹、Ｒ³²、Ｒ³³、Ｒ³⁴及びＲ³⁵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８〜２２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Ｒ²⁰及びＲ²¹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Ｒ²²及びＲ²³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 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 of number 8 to 40 or an alkyl group of number 8 to 22, and R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independent hydrogen atoms, methyl groups and ethyls, respectively. A group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 8 to 22 carbon atoms, a represents an integer of 0 or more, and b represents 1 Representing the above integers, (a + b) is 10 to 200, and when a is 2 or more, a plurality of R ²⁰ and R ²¹ may be the same or different, and when b is 2 or more. , A plurality of R ²² and R ²³ may be the same or different from each other. ]

In the organomodified silicone represented by the general formula (1), 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 a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. ^{R 20} , R ²¹ and R ²² are preferably hydrogen atoms or methyl groups independently, and more preferably methyl groups, in that they are industrially easy to manufacture and easily available.

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

［式（２）中、Ｒ⁴⁰は、炭素数２〜６のアルキレン基を表し、Ｒ⁴¹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Ｒ⁴¹は同一であっても異なっていてもよい。］

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

The above-mentioned alkylene group may be linear or branched.

［式（３）中、Ｒ⁴²は、炭素数２〜６のアルキレン基を表し、Ｒ⁴³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Ｒ⁴³は同一であっても異なっていてもよい。］

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

The above-mentioned alkylene group may be linear or branched.

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

Among the groups represented by the general formula (2), R ⁴⁰ is preferably an alkylene group having 2 to 4 carbon atoms, and c is 0 or 1, in that it is easily industrially produced and easily available. It is preferably present, and more preferably 0.

Among the groups represented by the general formula (3), R ⁴² is preferably an alkylene group having 2 to 4 carbon atoms, and d is 0 or 1, in that it is easily industrially produced and easily available. It is preferably present, and more preferably 0.

The above-mentioned hydrocarbon group having an aromatic ring and having 8 to 40 carbon atoms includes the above-mentioned aralkyl group having 8 to 40 carbon atoms and the above-mentioned general formula in that it is easily industrially produced and easily available. The group represented by 2) is preferable, and the aromatic group having 8 to 40 carbon atoms is more preferable from the viewpoint of obtaining good water repellency and durable water repellency.

The above-mentioned alkyl group having 8 to 22 carbon atoms may be linear or branched. Examples of the alkyl group having 8 to 22 carbon atoms include an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a myristyl group, a cetyl group, a stearyl group and the like. The carbon number of the alkyl group having 8 to 22 carbon atoms is 8 or more, preferably 10 or more, more preferably 12 or more, still more preferably 14 or more in one embodiment from the viewpoint of obtaining good water repellency and durable water repellency. From the viewpoint of obtaining good storage stability, it is 22 or less in one embodiment.

In the organomodified silicone represented by the above general formula (1), R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independently hydrogen atom, methyl group, ethyl group and 1 to 1 carbon atoms. It is an alkoxy group of 4, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 8 to 22 carbon atoms. ^{R 30} , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independent hydrogen atoms, methyl groups, ethyl groups or 1 carbon atoms in that they are industrially easy to manufacture and easily available. It is preferably an alkoxy group of ~ 4, and more preferably a methyl group.

In the organomodified silicone represented by the general formula (1), a is an integer of 0 or more. A is preferably 40 or less, more preferably 30 or less, in that it is industrially easy to manufacture, easily available, and the obtained textile product has more excellent peel strength against the resin coating.

In the organomodified silicone represented by the general formula (1), (a + b) is 10 to 200. (A + b) is preferably 20 to 100, more preferably 40 to 60, in that it is industrially easy to manufacture and easily available. When (a + b) is within the above range, the silicone itself tends to be easily manufactured and handled.

The organomodified silicone represented by the general formula (1) can be synthesized by a conventionally known method. The organomodified silicone represented by the general formula (1) can be obtained, for example, by hydrosilylating a silicone having a SiH group with an aromatic compound having a vinyl group and / or an α-olefin.

Examples of the above-mentioned silicone having a SiH group include methylhydrogen silicone having a degree of polymerization of 10 to 200, a copolymer of dimethylsiloxane and methylhydrogensiloxane, and the like. Among these, methylhydrogen silicone is preferable because it is industrially easy to manufacture and easily available.

The above-mentioned aromatic compound having a vinyl group is a compound from which a hydrocarbon group having an aromatic ring and having 8 to 40 carbon atoms is derived ^{in R 23 in the above general formula (1).} Examples of the aromatic compound having a vinyl group include styrene, α-methylstyrene, vinylnaphthalene, allylphenyl ether, allylnaphthyl ether, allyl-p-cumylphenyl ether, allyl-o-phenylphenyl ether, and allyl-tri. Examples thereof include (phenylethyl) -phenyl ether and allyl-tri (2-phenylpropyl) phenyl ether.

The α-olefin is a compound from which an alkyl group having 8 to 22 carbon atoms is derived in ^{R 23 in the general formula (1).} Examples of the α-olefin include α-olefins having 8 to 22 carbon atoms such as 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene. Can be mentioned.

The hydrosilylation reaction is carried out by reacting the silicone having a SiH group with the aromatic compound having a vinyl group and the α-olefin stepwise or at once in the presence of a catalyst, if necessary. May be good.

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

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

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

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

The organomodified silicone (β) may be used alone or in combination of two or more.

The amount of the organomodified silicone (β) with respect to 100 parts by mass of the non-fluorinated polymer (α) is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and further preferably 10 to 10 parts by mass from the viewpoint of storage stability. 25 parts by mass.

<Wax (γ)>
Examples of the wax (γ) include paraffin wax, microcrystalline wax, Fishertropus wax, polyethylene wax, animal and vegetable wax, mineral wax and the like. The wax (γ) is preferably paraffin wax from the viewpoint of water repellency, durable water repellency and texture.

The compound constituting the wax (γ) according to the present embodiment is not particularly limited, and examples thereof include normal alkanes and normal alkenes. The wax (γ) is preferably a normal alkane from the viewpoint of water repellency, durable water repellency and texture.

Examples of the normal alkane include tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, gentriacontane, dotriacontane, tritriacontane, tetrathoriacontane, pentatoriacontane and hexatriacontane. Be done. The normal alkane is preferably triacontane, hentaicontane and dotriacontane from the viewpoint of water repellency, durable water repellency and texture.

Normal alkenes include, for example, 1-eicosene, 1-dococene, 1-trichothecene, 1-tetracocene, 1-pentacene, 1-hexacene, 1-heptacosene, 1-octacene, nonacocene, triacontene, gentriaconten, dotria. Examples thereof include content, tritriria content, tetratria content, pentatria content and hexatria content. From the viewpoint of water repellency, durable water repellency and texture, the normal alkene is preferably Triaconten, Hentriaconten and Dotriaconten.

The carbon number of the wax (γ) according to the present embodiment is not particularly limited, but may be 20 to 60, and is preferably 25 to 45 from the viewpoint of water repellency, durable water repellency and texture.

The weight average molecular weight of the wax (γ) according to the present embodiment is not particularly limited, but may be 300 to 850, and is preferably 300 to 700 from the viewpoint of water repellency, durable water repellency, and texture.

The melting point of the wax (γ) according to the present embodiment is preferably 35 to 90 ° C., preferably 40 to 85 ° C., from the viewpoint of good water repellency and durable water repellency, particularly good water repellency and durable water repellency for cotton. The temperature is more preferably 45 to 80 ° C, and even more preferably 50 to 70 ° C. The melting point of wax (γ) refers to a value measured by the same method as JIS K 2235-1991.

The degree of needle insertion of the wax (γ) according to the present embodiment is not particularly limited, but may be, for example, 30 or less, preferably 20 or less, and 15 or less from the viewpoint of water repellency and durable water repellency. More preferably, it is more preferably 10 or less. The degree of needle insertion of the wax (γ) according to the present embodiment is not particularly limited, but may be, for example, 0.1 or more, or 1 or more. The degree of needle insertion of wax (γ) refers to a value measured by the same method as JIS K 2235-1991.

The amount of wax (γ) with respect to a total of 100 parts by mass of the non-fluoropolymer (α), organomodified silicone (β) and wax (γ) has good water repellency and durable water repellency, especially good water repellency for cotton. From the viewpoint of durable water repellency, it is preferably 20 to 70 parts by mass, more preferably 25 to 65 parts by mass, still more preferably 30 to 60 parts by mass, and particularly preferably 35 to 55 parts by mass.

From the viewpoint of water repellency and environment, the wax (γ) of the present embodiment is preferably emulsified or dispersed with an emulsification aid or a dispersion aid. The aqueous dispersion of wax (γ) according to the present embodiment can be produced by dispersing wax (γ) in water in the presence of an emulsifier for wax. The production of an aqueous dispersion of wax (γ) is preferably carried out by mixing wax (γ), water, and an emulsifier for wax. The temperature at the time of mixing is not particularly limited, but may be, for example, 60 to 90 ° C. The time for mixing is not particularly limited, but may be, for example, 10 seconds to 10 hours. Mixing is preferably carried out by using a homomixer.

<Other ingredients>
In the water repellent composition of the present embodiment, silica modified by a hydrophilic agent and a hydrophobic agent (silica having a hydrophilic group and a hydrophobic group on the silica surface) can also be used in combination. Examples of silica having a hydrophilic group and a hydrophobic group on the silica surface include Leolosil HG-09 (manufactured by Tokuyama Co., Ltd., trade name), AEROSIL NA50H, RA200H, RA200HS (above, Nippon Aerosil Co., Ltd.). ), Product name), etc.

Additives and the like can be added to the water repellent composition of the present embodiment, if necessary. Additives include other water repellents, surfactants, defoamers, pH regulators, antibacterial agents, fungicides, colorants, antioxidants, deodorants, various organic solvents, chelating agents, antistatic agents. Examples thereof include agents, catalysts, cross-linking agents, antibacterial deodorants, flame retardants, fabric softeners, and anti-wrinkle agents.

As the surfactant, known nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used. As the surfactant, one type may be used alone or two or more types may be used in combination.

Examples of the defoaming agent include fat-based defoaming agents such as castor oil, sesame oil, flaxseed oil, and animal and vegetable oils; fatty acid-based defoaming agents such as stearic acid, oleic acid, and palmitic acid; isoamyl stearate and distearyl succinate. , Ethylene glycol distearate, butyl stearate and other fatty acid ester defoamers; polyoxyalkylene monohydric alcohol, di-t-amylphenoxyethanol, 3-heptanol, 2-ethylhexanol and other alcohol-based defoamers; Ether-based defoamers such as di-t-amylphenoxyethanol, 3-heptyl cellosolve, nonyl cellosolve, 3-heptyl carbitol; phosphate defoamers such as tributyl phosphate and tris (butoxyethyl) phosphate; Amine-based defoaming agents; amide-based defoaming agents such as polyalkyleneamide and acylate polyamine; sulfuric acid ester-based defoaming agents such as sodium lauryl sulfate; mineral oil and the like can be mentioned. The defoaming agent may be used alone or in combination of two or more.

pH adjusters include organic acids such as lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, citric acid, malic acid, sulfonic acid, methanesulfonic acid and toluenesulfonic acid; hydrochloric acid, sulfuric acid, nitrate, phosphoric acid, etc. Inorganic acids such as boric acid; bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonia, alkanolamine, pyridine, morpholin and the like can be mentioned. The pH adjuster may be used alone or in combination of two or more.

Examples of the organic solvent include aliphatic alcohols having 1 to 8 carbon atoms such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, hexyl alcohol, and 2-ethylhexyl alcohol; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and the like. Ketones such as diacetone alcohol; esters such as ethyl acetate, methyl acetate, butyl acetate, methyl lactate, ethyl lactate; diethyl ether, diisopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, dioxane, methyl tertiary butyl ether, butyl carbi Ethers such as tall; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol; ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, Glycol ethers such as 3-methoxy-3-methyl-1-butanol; glycol esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate; formamide, acetamide, benzamide, N, N- Examples thereof include amides such as dimethylformamide and acetanilide. As the organic solvent, one type can be used alone or two or more types can be used in combination.

As the antistatic agent, it is preferable to use an antistatic agent that does not easily impair the water-repellent performance. Antistatic agents include, for example, cationic surfactants such as higher alcohol sulfates, sulfated oils, sulfonates, quaternary ammonium salts, imidazoline type quaternary salts, polyethylene glycol type, polyhydric alcohol ester type. Nonionic surfactants such as, imidazoline type quaternary salts, amphoteric surfactants such as alanine type and betaine type, polymer compound type antistatic polymers, polyalkylamines and the like can be mentioned. The antistatic agent may be used alone or in combination of two or more.

[Manufacturing method of water repellent composition]
Next, a method for producing the water repellent composition of the present embodiment will be described.
The composition containing the non-fluorinated polymer (α) can be produced by a radical polymerization method. Further, among these radical polymerization methods, it is preferable to polymerize by an emulsion polymerization method or a dispersion polymerization method from the viewpoint of the performance of the obtained water repellent and the environment.

For example, a non-fluorinated polymer (α) can be obtained by emulsion polymerization or dispersion polymerization of the component (A1) and the component (A2) in a medium. More specifically, for example, the component (A1), the component (A2) and, if necessary, the component (B), the component (C) and the component (D), and an emulsification aid or a dispersion aid are added to the medium. , This mixture is emulsified or dispersed to give an emulsion or dispersion. By adding a polymerization initiator to the obtained emulsion or dispersion, the polymerization reaction is started, and the monomer and the reactive emulsifier can be polymerized. Examples of the means for emulsifying or dispersing the above-mentioned mixture include a homomixer, a high-pressure emulsifier, ultrasonic waves, and the like.

Examples of the emulsification aid or dispersion aid (hereinafter, also referred to as “emulsification aid, etc.”) include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants other than the reactive emulsifier (B). One or more selected from surfactants can be used. The content of the emulsifying aid and the like is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and 1 to 10 parts by mass with respect to 100 parts by mass of the total monomer. Is more preferable. When the content of the emulsification aid or the like is 0.5 parts by mass or more, the dispersion stability of the mixed solution is further improved as compared with the case where the content of the emulsification aid or the like is less than 0.5 parts by mass. Tend to do. When the content of the emulsifying aid or the like is 30 parts by mass or less, the water repellency and the durable water repellency of the obtained non-fluorine-based polymer are further improved as compared with the case where the content of the emulsifying auxiliary agent or the like exceeds 30 parts by mass. It tends to improve.

Examples of the cationic surfactant include a monoalkyltrimethylammonium salt having 8 to 24 carbon atoms, a dialkyldimethylammonium salt having 8 to 24 carbon atoms, a monoalkylamine acetate salt having 8 to 24 carbon atoms, and a dialkylamine having 8 to 24 carbon atoms. Acetate, alkylimidazolin quaternary salt having 8 to 24 carbon atoms, and the like can be mentioned. Among these, a monoalkyltrimethylammonium salt having 12 to 18 carbon atoms and a dialkyldimethylammonium salt having 12 to 18 carbon atoms are preferable from the viewpoint of emulsifying property and processing stability.

These cationic surfactants may be used alone or in combination of two or more.

Examples of nonionic surfactants include alkylene oxide adducts of alcohols, polycyclic phenols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, fats and oils and polypropylene glycol.

Examples of alcohols include straight-chain or branched-chain alcohols or alkenols having 8 to 24 carbon atoms, acetylene alcohols represented by the following general formula (AL-1) or the following general formula (AL-2), and the like.

［式中、Ｒ⁵¹及びＲ⁵²はそれぞれ独立に、炭素数１〜８の直鎖若しくは分岐鎖を有するアルキル基又は炭素数２〜８の直鎖若しくは分岐鎖を有するアルケニル基を表す。］

[In the formula, R ⁵¹ and R ⁵² each independently represent an alkyl group having a linear or branched chain having 1 to 8 carbon atoms or an alkenyl group having a linear or branched chain having 2 to 8 carbon atoms. ]

［式中、Ｒ⁵³は、炭素数１〜８の直鎖若しくは分岐鎖を有するアルキル基又は炭素数２〜８の直鎖若しくは分岐鎖を有するアルケニル基を表す。］

[In the formula, R ⁵³ represents an alkyl group having a linear or branched chain having 1 to 8 carbon atoms or an alkenyl group having a linear or branched chain having 2 to 8 carbon atoms. ]

As polycyclic phenols, monovalent phenols such as phenol and naphthol which may have a hydrocarbon group having 1 to 12 carbon atoms or their styrenes (styrene, α-methylstyrene, vinyltoluene) are added. Products or their benzyl chloride reactants and the like can be mentioned. Examples of amines include aliphatic amines having 8 to 44 carbon atoms in a straight chain or a branched chain.

Examples of the amides include fatty acid amides having 8 to 44 carbon atoms in a straight chain or a branched chain.

Examples of fatty acids include straight-chain or branched-chain fatty acids having 8 to 24 carbon atoms.

Examples of the polyhydric alcohol fatty acid ester include a condensation reaction product of the polyhydric alcohol and a carboxylic acid having 2 to 30 carbon atoms (including carbon of a carboxyl group). Examples of such polyhydric alcohol fatty acid esters include sorbitan (alcohol) and sorbitan esters composed of carboxylic acids having 2 to 30 carbon atoms (including carbons of carboxyl groups).

The carboxylic acid constituting the sorbitan ester has 2 to 30 carbon atoms, preferably 5 to 21 carbon atoms. The sorbitan ester may be a monocarboxylic acid ester of sorbitan and one carboxylic acid, a dicarboxylic acid ester of sorbitol and two carboxylic acids, a tricarboxylic acid ester of sorbitol and three carboxylic acids, and the like, and is a monocarboxylic acid ester. Is preferable.

The sorbitan ester may be a compound represented by the following general formula (4) or the following general formula (5).

［式（４）中、Ｒ⁶¹は炭素数１〜２２のアルキル基又は炭素数２〜２２のアルケニル基を表し、Ｒ⁶⁴、Ｒ⁶⁵及びＲ⁶⁶は水素、−ＣＯ−Ｒ⁶¹で表される基、又は−（ＣＨ₂ＣＨ₂Ｏ）_e−（Ｒ⁶²Ｏ）_f−Ｒ⁶³（Ｒ⁶²は炭素数３以上のアルキレン基を表し、Ｒ⁶³は水素、炭素数１〜２２のアルキル基又は炭素数２〜２２のアルケニル基を表し、ｅは２以上の整数を表し、ｆは０以上の整数を表す。）を表す。］

[In formula (4), R ⁶¹ represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, and R ⁶⁴ , R ⁶⁵ and R ⁶⁶ are represented by hydrogen and −CO-R ^61. Group or-(CH _{2 CH 2} O) _e- (R ⁶² O) _f- R ⁶³ (R ⁶² represents an alkylene group having 3 or more carbon atoms, and R ⁶³ is a hydrogen, an alkyl group having 1 to 22 carbon atoms or It represents an alkenyl group having 2 to 22 carbon atoms, e represents an integer of 2 or more, and f represents an integer of 0 or more). ]

［式（５）中、Ｒ⁶¹は炭素数１〜２２のアルキル基又は炭素数２〜２２のアルケニル基を表し、Ｒ⁶⁴、Ｒ⁶⁵及びＲ⁶⁶は水素、−ＣＯ−Ｒ⁶¹で表される基、又は−（ＣＨ₂ＣＨ₂Ｏ）_e−（Ｒ⁶²Ｏ）_f−Ｒ⁶³（Ｒ⁶²は炭素数３以上のアルキレン基を表し、Ｒ⁶³は水素、炭素数１〜２２のアルキル基又は炭素数２〜２２のアルケニル基を表し、ｅは２以上の整数を表し、ｆは０以上の整数を表す。）を表す。］

[In formula (5), R ⁶¹ represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, and R ⁶⁴ , R ⁶⁵ and R ⁶⁶ are represented by hydrogen, −CO-R ^61. Group or-(CH _{2 CH 2} O) _e- (R ⁶² O) _f- R ⁶³ (R ⁶² represents an alkylene group having 3 or more carbon atoms, and R ⁶³ is a hydrogen, an alkyl group having 1 to 22 carbon atoms or It represents an alkenyl group having 2 to 22 carbon atoms, e represents an integer of 2 or more, and f represents an integer of 0 or more). ]

Examples of the compound represented by the general formula (4) or (5) include sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan sesquistearate, sorbitan tristearate, and monolaurine. Examples thereof include polyoxyethylene sorbitan acid, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan tristearate.

Examples of fats and oils include vegetable fats and oils, animal fats and oils, vegetable waxes, animal waxes, mineral waxes, hydrogenated oils and the like.

Among these, from the viewpoints of having little influence on water repellency and durable water repellency, little influence on light resistance, and good emulsifying property of the copolymer, the linear or branched chain has 8 to 24 carbon atoms. Alcohols or alkenols, and acetylene alcohols represented by the above general formula (AL-1) or the above general formula (AL-2) are preferable, and linear or branched alcohols having 8 to 24 carbon atoms and the above general The acetylene alcohol represented by the formula (AL-1) or the above general formula (AL-2) is more preferable.

Examples of the alkylene oxide include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,4-butylene oxide, styrene oxide, epichlorohydrin and the like. Ethylene oxide and 1,2-propylene oxide are preferable as alkylene oxides, and ethylene oxide is preferable, from the viewpoints that the effect on water repellency and durability water repellency is small and the emulsifying property of the non-fluorinated polymer (α) is improved. More preferred.

The number of moles of alkylene oxide added is preferably 1 to 200, more preferably 3 to 100, and even more preferably 5 to 50. When the number of moles of alkylene oxide added is within the above range, water repellency, durable water repellency and product stability can be easily obtained at a high level.

In the non-fluorine-based polymer (α) according to the present embodiment, when a nonionic surfactant having an HLB of 7 to 18 is used as the nonionic surfactant, a better aqueous dispersion can be obtained. Here, the HLB is based on the HLB of Griffin, and the formula of Griffin is changed to the following formula. Here, the hydrophilic group refers to an ethylene oxide group. HLB = (hydrophilic group x 20) / molecular weight

From the viewpoint of emulsion stability (hereinafter, simply referred to as emulsion stability) in the composition during and after emulsion polymerization or dispersion polymerization of the non-fluoropolymer (α) of the present embodiment, 9 to 15 are preferable. Furthermore, it is more preferable to use two or more nonionic surfactants having different HLBs within the above range in combination in terms of storage stability of the water repellent composition. Further, from the viewpoint of emulsion stability, water repellency and durable water repellency, it is preferable to use a cationic surfactant and a nonionic surfactant in combination.

Water is preferable as the medium for emulsion polymerization or dispersion polymerization, and water and an organic solvent may be mixed if necessary. The organic solvent at this time is not particularly limited as long as it is an organic solvent that can be mixed with water, but for example, alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, and diethyl. Examples thereof include ethers such as ether, and glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol. The ratio of water to the organic solvent is not particularly limited.

As the polymerization initiator, a known polymerization initiator such as an azo-based, peroxide-based, or redox-based polymerization initiator can be appropriately used. The content of the polymerization initiator is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total monomer. When the content of the polymerization initiator is in the above range, the non-fluorinated polymer (α) having a weight average molecular weight of 30,000 or more can be efficiently produced.

Further, in the polymerization reaction, a chain transfer agent such as dodecyl mercaptan or t-butyl alcohol may be used for the purpose of adjusting the molecular weight. The content of the chain transfer agent is preferably 0.3 parts by mass or less, and more preferably 0.1 parts by mass or less, based on 100 parts by mass of all the monomers. When the content of the chain transfer agent is 0.3 parts by mass or less, it is possible to suppress an excessive decrease in the molecular weight, and it is possible to efficiently produce a non-fluorinated polymer (α) having a weight average molecular weight of 30,000 or more. It tends to be easier.

A polymerization inhibitor may be used for adjusting the molecular weight. By adding a polymerization inhibitor, a non-fluorinated polymer (α) having a desired weight average molecular weight can be easily obtained.

The temperature of the polymerization reaction is preferably 20 ° C. to 150 ° C. When the temperature is 20 ° C. or higher, the polymerization tends to be sufficiently promoted as compared with the case where the temperature is lower than 20 ° C. When the temperature is 150 ° C. or lower, the heat of reaction can be easily controlled as compared with the case where the temperature exceeds 150 ° C.

In the polymerization reaction, the weight average molecular weight of the obtained non-fluoropolymer (α) 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. , The content of the polyfunctional monomer and the content of the polymerization initiator can be adjusted. If it is desired to reduce the melt viscosity at 105 ° C., the content of the monomer having two or more polymerizable functional groups may be reduced, or the content of the polymerization initiator may be increased.

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

The water repellent composition of the present embodiment is prepared by mixing the composition containing the non-fluorinated polymer (α) obtained by the above method with organomodified silicone (β) and wax (γ). be able to. The organomodified silicone (β) and wax (γ) may be commercially available products or the like, respectively.

[Water-repellent textile products]
One aspect of the present invention also provides a water repellent textile product in which the water repellent composition of the present disclosure is attached to the textile product. The water-repellent fiber product of the present embodiment is at least a fiber product to which the non-fluorinated polymer (α) of the present embodiment described above, the organomodified silicone (β), and the wax (γ) are adhered. The water-repellent textile product can be obtained by treating the textile product with a treatment liquid containing the above-mentioned water-repellent composition to form a non-fluorinated polymer (α), an organomodified silicone (β) and a wax (γ), and any of them. It is obtained by adhering other components to textile products. The material of such textile products is not particularly limited, and natural fibers such as cotton, linen, 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, non-woven fabric, and paper.

The water repellent composition according to the present embodiment may be applied to textile products in the form of a combination of a plurality of treatment liquids. For example, by preparing a treatment liquid containing a non-fluoropolymer (α) and an organomodified silicone (β) and a treatment liquid containing a wax (γ), and applying these treatment liquids to textile products separately, the present invention A textile product treated with the water repellent composition of the embodiment may be obtained.

Examples of the method for treating the textile product with the above-mentioned treatment liquid include processing methods such as dipping, spraying, and coating. When the water repellent composition contains water, it is preferably dried after being attached to the textile product to remove the water.

The amount of the water repellent composition adhered to the textile product can be appropriately adjusted according to the required degree of water repellency and durable water repellency, but from the viewpoint of water repellency, durable water repellency and texture, 100 g of the textile product On the other hand, the total amount of the non-fluoropolymer (α), the organomodified silicone (β) and the wax (γ) contained in the water repellent composition can be adjusted to be 0.01 to 10 g. It is preferable to adjust the amount to 0.05 to 5 g.

Further, after the water repellent composition of the present embodiment is attached to the textile product, it is preferable to appropriately heat-treat it. The temperature condition is not particularly limited, but when the water repellent composition of the present embodiment is used, sufficiently good water repellency and durable water repellency can be exhibited in the textile product under mild conditions of 100 to 130 ° C. The temperature condition may be a high temperature treatment of 130 ° C. or higher (preferably up to 200 ° C.), but in such a case, the treatment time can be shortened as compared with the conventional case using a fluorine-based water repellent. .. Therefore, according to the water-repellent fiber product of the present embodiment, deterioration of the fiber product due to heat is suppressed, the texture of the fiber product during the water-repellent treatment becomes flexible, and under mild heat treatment conditions, that is, low temperature cure conditions. Sufficient water repellency and durable water repellency can be imparted to textile products.

In particular, when it is desired to improve durable water repellency, the above-mentioned step of treating a textile product with a treatment liquid containing a water repellent composition and one melamine resin, glioxal resin, isocyanate group or blocked isocyanate group are used. It is preferable to make the textile product water-repellent by a method including a step of adhering a cross-linking agent typified by the compound as described above to the textile product and heating the cross-linking agent. Further, when it is desired to further improve the durable water repellency, the water repellent composition contains a non-fluorinated polymer (α) copolymerized with a monomer having a functional group capable of reacting with the above-mentioned cross-linking agent. Is preferable.

As the melamine resin, a compound having a melamine skeleton can be used. For example, polymethylol melamine such as trimethyl melamine and hexamethylol melamine; a part or all of the methylol groups of the polyether melamine have 1 to 6 carbon atoms. Alkoxymethyl melamine that has become an alkoxymethyl group having an alkyl group; asyloxymethylmelamine in which part or all of the methylol group of polymethylol melamine has become an acyloxymethyl group having an acyl group having 2 to 6 carbon atoms. Can be mentioned. These melamine resins may be either monomers or dimers or more multimers, or mixtures thereof may be used. Further, a product obtained by copolymerizing a part of melamine with urea or the like can also be used. Examples of such melamine resins include Beccamin APM, Beccamin M-3, Beccamin M-3 (60), Beccamin MA-S, Beccamin J-101, and Beccamin J-101LF manufactured by DIC Corporation. Examples include Unica Resin 380K manufactured by Miki Riken Kogyo Co., Ltd. and Riken Resin MM series manufactured by Miki Riken Kogyo Co., Ltd.

As the glyoxal resin, conventionally known ones can be used. Examples of the glyoxal resin include 1,3-dimethylglyoxal urea-based resin, dimethylol dihydroxyethylene urea-based resin, and dimethylol dihydroxypropylene urea-based resin. The functional groups of these resins may be substituted with other functional groups. Examples of such glyoxal resin include Beccamin N-80, Beccamin NS-11, Beccamin LF-K, Beccamin NS-19, Beccamin LF-55P Conch, Beccamin NS-210L, and Beccamin NS-200 manufactured by DIC Corporation. , And Beccamin NF-3, Uniresin GS-20E manufactured by Union Chemical Industry Co., Ltd., Riken Resin RG series manufactured by Miki Riken Kogyo Co., Ltd., and Riken Resin MS series.

It is preferable to use a catalyst for the melamine resin and the glyoxal resin from the viewpoint of accelerating the reaction. Such a catalyst is not particularly limited as long as it is a commonly used catalyst, and for example, a borofluorinated compound such as ammonium borofluoride or subsalt borofluoride; a neutral metal salt catalyst such as magnesium chloride or magnesium sulfate. ; Examples include inorganic acids such as phosphoric acid, hydrochloric acid, and boric acid. If necessary, organic acids such as citric acid, tartaric acid, malic acid, maleic acid, and lactic acid can be used in combination with these catalysts. Examples of such a catalyst include Catalyst ACX, Catalyst 376, Catalyst O, Catalyst M, Catalyst G (GT), Catalyst X-110, Catalyst GT-3, and Catalyst GT-3 manufactured by DIC Corporation. Catalyst NFC-1, Unica Catalyst 3-P manufactured by Union Chemical Industry Co., Ltd., and Unica Catalyst MC-109, Riken Fixer RC series, Riken Fixer MX series, and Riken Fixer RZ-manufactured by Miki Riken Kogyo Co., Ltd. 5 and the like can be mentioned.

As the compound having one or more isocyanate groups or blocked isocyanate groups, monofunctional (mono) isocyanate compounds such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate and naphthalene isocyanate, and polyfunctional isocyanate compounds can be used.

The polyisocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups in the molecule, and a known polyisocyanate compound can be used. Examples of the polyfunctional isocyanate compound include diisocyanate compounds such as alkylene diisocyanate, aryl diisocyanate and cycloalkyl diisocyanate, and modified polyisocyanate compounds such as dimers or trimers of these diisocyanate compounds. The alkylenediisocyanate preferably has 1 to 12 carbon atoms.

Examples of the diisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, trizine diisocyanate and tetramethylxylylene diisocyanate; and aliphatic polyisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate. Examples thereof include alicyclic polyisocyanates such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, norbornan diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane.

Examples of the triisocyanate compound include triphenylmethane triisocyanate, dimethyltriphenylmethanetetraisocyanate, and tris (isocyanatophenyl) -thiophosphate.

A modified polyisocyanate compound derived from a polyisocyanate compound can also be used, and such a compound is not particularly limited as long as it has two or more isocyanate groups, and is, for example, a biuret structure or an isocyanurate structure. , Urethane structure, uretdione structure, allophanate structure, polyisocyanate having a trimeric structure, etc., adduct of trimethylolpropane aliphatic isocyanate, and the like. Polymeric MDI (MDI = diphenylmethane diisocyanate) can also be used as a polyfunctional isocyanate compound.

The polyfunctional isocyanate compound may be used alone or in combination of two or more.

The isocyanate group contained in the polyfunctional isocyanate compound may be a blocked isocyanate group as it is or may be a blocked isocyanate group blocked by a blocking agent. Blocking agents include pyrazoles such as 3,5-dimethylpyrazole, 3-methylpyrazole, 3,5-dimethyl-4-nitropyrazole, 3,5-dimethyl-4-bromopyrazole, pyrazole; phenol, methylphenol, Phenols such as chlorphenol, iso-butylphenol, tert-butylphenol, iso-amylphenol, octylphenol, nonylphenol; lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam; , Active methylene compounds such as acetylacetone, methyl acetoacetate, ethyl acetoacetate; oximes such as formaldehyde, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime; imidazole, 2-methylimidazole. Oxime compounds such as; sodium bisulfite and the like. Among these, pyrazoles and oximes are preferable from the viewpoint of water repellency and durable water repellency.

As the polyfunctional isocyanate compound, a water-dispersible isocyanate obtained by imparting water dispersibility to the polyisocyanate by introducing a hydrophilic group into the polyisocyanate structure to have a surface-active effect can also be used. Further, in order to promote the reaction, known catalysts such as organic tin and organic zinc can be used in combination.

The cross-linking agent or catalyst may be used alone or in combination of two or more.

The cross-linking agent is, for example, by dissolving the cross-linking agent in an organic solvent or immersing the object to be treated (textile product) in a treatment liquid emulsified and dispersed in water and drying the treatment liquid adhering to the object to be treated. It can be attached to the object to be treated. Then, by heating the cross-linking agent adhering to the object to be treated, the reaction between the cross-linking agent and the object to be treated and the non-fluorine-based polymer (α) can be allowed to proceed. In order to sufficiently proceed the reaction of the cross-linking agent and more effectively improve the washing durability, the heating at this time is preferably performed at 110 to 180 ° C. for 1 to 5 minutes. The step of adhering the cross-linking agent and heating may be performed at the same time as the step of treating with the treatment liquid containing the above-mentioned water repellent composition. When performed at the same time, for example, a treatment liquid containing a water repellent composition and a cross-linking agent is attached to the object to be treated, water is removed, and then the cross-linking agent adhering to the object to be treated is further heated. Considering simplification of the water-repellent processing process, reduction of heat quantity, and economy, it is preferable to perform the process at the same time as the treatment process of the water-repellent composition.

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

The content ratio of the non-fluorinated polymer (α) to the cross-linking agent in the treatment liquid is preferably 95: 5 to 60:40, preferably 95: 5 to 70:30, in terms of mass ratio. More preferably, it is 90: 10 to 80:20. When the content ratio of the non-fluorine-based polymer (α) to the cross-linking agent is within the above range, the texture, water repellency and durable water repellency of the textile product, water penetration prevention property, and peel strength are good.

The water-repellent fiber product of the present embodiment thus obtained is excellent not only in initial water repellency but also in durable water repellency after being subjected to a load such as washing or abrasion. Further, since the water-repellent fiber product does not use a fluorine-based compound, it can be made environmentally friendly.

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

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

For example, in the case of producing the non-fluorinated polymer (α) contained in the water repellent composition of the present invention, in the above embodiment, the polymerization reaction is carried out by radical polymerization, but ultraviolet rays, electron beams and γ rays are used. The polymerization reaction may be carried out by photopolymerization by irradiating such ionizing radiation.

Further, in the present invention, the water-repellent composition is treated into a textile product to obtain a water-repellent fiber product, but the product treated with the water-repellent composition is not limited to textile products, and is not limited to textile products. , Resin or the like.

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

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited to these Examples.

<Synthesis example of non-fluorine polymer>
A mixed solution having the composition shown in Table 1 (in the table, the numerical value indicates (g)) was polymerized by the procedure shown below to obtain a non-fluorinated polymer.

(Synthesis Example 1)
In an autoclave, 23.4 g of stearyl acrylate, 0.6 g of diacetone acrylamide, 0.2 g of Neugen XL-100 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7), Neugen XL- 60 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 12.5) 1.3 g, Neugen XL-40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 10) .5) 0.5 g, 0.4 g of stearyltrimethylammonium sulfate, 12.5 g of tripropylene glycol and 54.9 g of water were added, and the mixture was mixed and stirred at 45 ° C. to prepare a mixed solution. The mixed solution was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.2 g of azobis (isobutylamidin) dihydrochloride was added to the mixed solution, and 6 g of vinyl chloride was continuously press-fitted under a nitrogen atmosphere so that the internal pressure of the autoclave was maintained at 0.3 MPa at 60 ° C. Radical polymerization was carried out for 6 hours to obtain a non-fluorine polymer (α) dispersion containing 30.0% by mass of the non-fluorine polymer (α).

(Synthesis Examples 2-6, Comparative Synthesis Examples 1 to 3)
Non-fluorinated polymer (α) which is polymerized in the same manner as in Synthesis Example 1 except that the materials shown in Table 1 are used and contains 30.0% by mass of non-fluorinated polymer (α) or other non-fluorinated polymer. A dispersion liquid or another non-fluorine-based polymer dispersion liquid was obtained, respectively.

The polymers in the polymer dispersions obtained in Synthesis Examples 1 to 6 and Comparative Synthesis Examples 1 to 3 were all monomeric according to a gas chromatograph (GC-15APTF, manufactured by Shimadzu Corporation). It was confirmed that 98% or more was polymerized.

<Preparation of organomodified silicone>
(Preparation Example 1)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, a nitrogen gas introduction tube and a dropping funnel, 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. The mixture was added, nitrogen was allowed to flow, and the mixture was heated until the temperature reached 65 ° C. and mixed until uniform. As a hydrosilylation catalyst, an ethylene glycol monobutyl ether / toluene mixed solution of platinum (IV) chloride was added so that the platinum concentration was 5 ppm with respect to the reaction product in the system. When the temperature of the reaction product reached 120 ° C., 252.5 g of 1 mol of 1-octadecene was added dropwise, and the mixture was reacted at 120 ° C. for 6 hours. The completion of the addition reaction was confirmed by performing an FT-IR analysis of the obtained organomodified silicone and confirming that the absorption spectrum derived from the SiH group of the methylhydrogen silicone had disappeared. Thus, in the general formula (1), 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 are methyl groups. A certain organomodified silicone was obtained.

Further, in a high-pressure reaction vessel, 4.5 parts by mass of ethylene oxide 9 mol adduct of a branched higher alcohol having 12 to 14 carbon atoms and 65.5 parts by mass of pure water were placed in 30 parts by mass of the obtained organomodified silicone and sealed. .. Then, the temperature was raised to 110 to 120 ° C. while stirring the inside of the container. Then, the inside of the container was emulsified under high pressure for 30 minutes while maintaining the high pressure to obtain an organomodified silicone (β) dispersion containing 30% by mass of the organomodified silicone (β).

(Preparation Example 2)
Didimethylsiloxane having a SiH group equivalent of 140.5 g / mol and a degree of polymerization of 50 instead of 63.2 g of methylhydrogen silicone having a SiH group equivalent of 63.2 g / mol and a degree of polymerization of 50. An organomodified silicone (β) dispersion was obtained in the same manner as in Preparation Example 1 except that 140.5 g of a copolymer of methylhydrogensiloxane and methylhydrogensiloxane was used. In the organomodified silicone, a in the general formula (1) is 25, b is 25, R ²⁰ and R ²¹ are methyl groups, R ²² is a methyl group, R ²³ is an octadecyl group, R ³⁰ , R ³¹ , R ^32. , R ³³ , R ³⁴ and R ³⁵ are methyl groups to give organomodified silicones.

(Preparation Example 3)
An organomodified silicone (β) dispersion was obtained in the same manner as in Preparation Example 1 except that 1 mol of 1-docosene was used instead of 252.5 g of 1 mol of 1-octadecene. In the organomodified silicone, a in the general formula (1) is 0, b is 50, R ²² is a methyl group, R ²³ is a docosyl group, R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R. ^An organomodified silicone having 35 as a methyl group was obtained.

(Preparation Example 4)
An organomodified silicone (β) dispersion was obtained in the same manner as in Preparation Example 3 except that 112.21 g of 1-octene was used instead of 308.59 g of 1-docosen. The organomodified silicone had the same structure as the organomodified silicone of Preparation Example 3 except that ^{R 23} of the general formula (1) was an octyl group.

(Comparative Preparation Example 1)
An organomodified silicone (β) dispersion was obtained in the same manner as in Preparation Example 3 except that 56.11 g of 1-butene was used instead of 308.59 g of 1-docosen. The organomodified silicone had the same structure as the organomodified silicone of Preparation Example 3 except that ^{R 23} of the general formula (1) was a butyl group.

(Comparative Preparation Example 2)
An organomodified silicone (β) dispersion was obtained in the same manner as in Preparation Example 3 except that 420.8 g of 1-triacontene was used instead of 308.59 g of 1-docosen. The organomodified silicone had the same structure as the organomodified silicone of Preparation Example 3 except that ^{R 23} of the general formula (1) was a triacontyl group.

<Preparation example of wax emulsion>
(Preparation Example 5)
30 g of paraffin wax (melting point 40 ° C.), 67 g of pure water, 1.5 g of polyoxyethylene stearyl ether (HLB = 10.7), and 1.5 g of polyoxyalkylene branched decyl ether (HLB = 14.7) are placed in a high-pressure reaction vessel. It was put in and sealed. Then, the temperature was raised to 110 to 120 ° C. while stirring the inside of the container. Then, the inside of the container was emulsified under high pressure for 30 minutes while maintaining the high pressure to obtain a wax emulsion containing 30% by mass of paraffin wax.

(Preparation Example 6)
A wax emulsion containing 30% by mass of paraffin wax was obtained in the same manner as in Preparation Example 5 except that paraffin wax (melting point 69 ° C.) was used instead of paraffin wax (melting point 40 ° C.).

(Preparation Example 7)
A wax emulsion containing 30% by mass of paraffin wax was obtained in the same manner as in Preparation Example 5 except that liquid paraffin was used instead of paraffin wax (melting point 40 ° C.).

<Preparation of water repellent composition>
(Examples 1 to 17, Comparative Examples 1 to 7)
Non-fluoropolymer (α) dispersion, other non-fluorine polymer dispersion, organomodified silicone (β) so as to have the composition shown in Tables 2 and 3 (in the table, the numerical value indicates (part by mass)). The dispersion liquid, other organomodified silicone dispersion liquid, and the wax emulsion were mixed to obtain a water repellent composition.

(Evaluation of water repellency of textile products)
The test was conducted with the shower water temperature set to 20 ° C. according to the spray method of JIS L 1092 (2009). In this test, the water repellency of the cloth obtained by immersing the following treated cloths in the following treatment liquids (pickup rate 80%) and then drying and heating under the following treatment conditions was evaluated.
-Treatment cloth (1) 100% cotton woven cloth (fixed with Neofix R-800 (manufactured by NICCA CHEMICAL CO., LTD.))
(2) 100% cotton woven fabric (without fixing treatment)
(3) Polyester (PET) / Polyurethane (PU) blended fabric (Polyester / Polyurethane = 80/20) (without fixing treatment)
-Treatment liquid (1) 100% cotton woven fabric (with fixing treatment) and (2) 100% cotton woven fabric (without fixing treatment):
Adjusted with pure water so that the water-repellent composition of Examples and Comparative Examples is 10% by mass and the blocked isocyanate-based cross-linking agent (NK Assist NY-50 (manufactured by NICCA CHEMICAL CO., LTD.)) Is 1% by mass. Processing liquid.
(Therefore, for example, in the case of Example 1, the amount of the non-fluorinated polymer contained in the treatment liquid is 13.5% by mass (45 parts by mass × 30% by mass) × 10% by mass = 1.35% by mass. It becomes.)
(3) About PET / PU blended fabrics:
Adjusted with pure water so that the water-repellent composition of Examples and Comparative Examples is 1% by mass and the blocked isocyanate-based cross-linking agent (NK Assist NY-50 (manufactured by NICCA CHEMICAL CO., LTD.)) Is 1% by mass. Processing liquid.
-Treatment conditions (1) 100% cotton woven fabric (with fixing treatment) and (2) 100% cotton woven fabric (without fixing treatment):
Dry in a drying oven at 120 ° C. and normal pressure for 1 minute, and then heat-treat under the conditions of 160 ° C. and normal pressure for 1 minute. (3) PET / PU blended fabric:
Dry in a drying oven at 130 ° C. and normal pressure for 2 minutes, and then heat-treat at 160 ° C. and normal pressure for 1 minute.

The results were visually evaluated according to the following grades. 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 2 and 3.
Water repellency: Condition 5: No wetness adhered to the surface 4: Slightly adhered to the surface Wetness 3: Partial wetness on the surface 2: Wetness on the surface 1: Wetness on the entire surface Item 0: Both front and back sides are completely moist.

(Evaluation of washing durability and water repellency of textile products)
The test was conducted with the shower water temperature set to 20 ° C. according to the spray method of JIS L 1092 (2009). A blocked isocyanate-based cross-linking agent (NK Assist NY-50) was added to the water-repellent compositions of Examples and Comparative Examples at a concentration of 0.03% by mass to prepare a treatment liquid. Next, the same polyester (PET) / polyurethane (PU) blended fabric (polyester / polyurethane = 80/20) as in (3) above was immersed in the prepared treatment liquid. After the dipping treatment, the cloth (L-0) and the cloth (L-0) obtained by drying in a drying oven at 130 ° C. and normal pressure for 2 minutes and further heat-treating at 160 ° C. and normal pressure for 60 seconds. The water repellency of each cloth after washing by the 103 method of JIS L 0217 (1995) 30 times (L-30) was evaluated in the same manner as in the above water repellency evaluation method.

(Evaluation of abrasion durability and water repellency of textile products)
Adjusted with pure water by the method of ISO5470-1 so that the water repellent composition of Examples and Comparative Examples is 6% by mass and the blocked isocyanate-based cross-linking agent (NK Assist NY-50) is 0.6% by mass. A 100% polyester cloth (without fixing treatment) is dipped in the treated solution, dried in a drying oven at 130 ° C. and normal pressure for 2 minutes, further heat-treated at 160 ° C. and normal pressure for 1 minute, and then worn. bottom.
A 5135 ABRASER (Rotary Platform Abraser) (manufactured by TABER INDUSTRIES) was used as the wearer, and a CS-10 (manufactured by TABER INDUSTRIES) was used as the wear wheel.
Then, 0.2 mL of ion-exchanged water was placed on the surface of the worn treated cloth at 10 locations on the cloth. The number of water droplets remaining on the surface of the treated cloth after one hour was counted and evaluated according to the following criteria.
5: 9 to 10 water droplets remain
4: 7 to 8 water droplets remain
3: 5 to 6 water droplets remain
2: 3-4 water droplets remain
1: 0 to 2 water droplets remain

(Evaluation of storage stability)
100 g of the water repellent composition of Examples and Comparative Examples was placed in a glass bottle, sealed, and stored in a dryer at 60 ° C. After 2 weeks, the glass bottle was taken out, cooled to room temperature while being sealed, and the water repellent composition was filtered under reduced pressure with a black cotton cloth, and the surface condition of the black cotton cloth was visually evaluated according to the following criteria.
5: The liquid passes smoothly and there are no particles on the surface of the cotton cloth.
4: The liquid passes smoothly and there are few particles on the surface of the cotton cloth.
3: The liquid passes smoothly and there are many particles on the surface of the cotton cloth.
2: Liquid passes through, but causes slight clogging
1: Liquid does not pass and causes clogging

Claims (6)

A structural unit derived from the (meth) acrylic acid ester monomer (A1) represented by the following general formula (A-1) and a configuration derived from the compound (A2) represented by the following general formula (A-2). A non-fluorinated polymer (α) containing a unit and
Organo-modified silicone (β) represented by the following general formula (1) and
A water repellent composition comprising wax (γ).

[In the formula (A-1), R ¹ represents a hydrogen or a methyl group, and R ² represents a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent. ]

[In formula (A-2), R ¹¹ represents a hydrogen or methyl group, R ¹² represents a divalent hydrocarbon group having 1 to 6 carbon atoms, Z represents an ester group or an amide group, and W represents a − A group represented by CO-R ¹³ (in the formula, R ¹³ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms), a group represented by -NH-CO-NH ₂ , or the following formula (A). Represents the group represented by -3). ]

[In formula (1), R ²⁰ , R ²¹ and R ²² 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 of number 8 to 40 or an alkyl group of number 8 to 22, and R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independent hydrogen atoms, methyl groups and ethyls, respectively. A group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 8 to 22 carbon atoms, a represents an integer of 0 or more, and b represents 1 Representing the above integers, (a + b) is 10 to 200, and when a is 2 or more, a plurality of R ²⁰ and R ²¹ may be the same or different, and when b is 2 or more. , A plurality of R ²² and R ²³ may be the same or different from each other. ] The water repellent composition according to claim 1, wherein the non-fluorinated polymer (α) further contains a structural unit derived from at least one monomer (VC) of vinyl chloride and vinylidene chloride. The water repellent composition according to claim 1 or 2, wherein the content of the organomodified silicone (β) is 1 to 50 parts by mass with respect to 100 parts by mass of the non-fluorinated polymer (α). The water repellent composition according to any one of claims 1 to 3, wherein the wax (γ) has a melting point of 35 ° C. to 90 ° C. A water-repellent textile product to which the water-repellent composition according to any one of claims 1 to 4 is attached. A method for producing a water-repellent textile product, comprising a step of treating the textile product with a treatment liquid containing the water-repellent composition according to any one of claims 1 to 4.