JP2016102272A - Oil repellent solution for fiber treatment, method for the production thereof and fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil repellent solution for fiber treatment that can impart oil repellency to fiber without using a compound having a perfluoroalkyl group and fluorine.SOLUTION: A fiber treatment agent comprises a silicone acryl copolymer (D) obtained by polymerization of a monomer comprising acrylate (a1') having a quaternary ammonium group, both-terminals (meth) acryl modified silicone oil (b'), and nonionic hydrophobic ethylenic unsaturated monomer (c'), with its mass ratio satisfying (a1'):(b'):(c')=5-30:0.5-25:45-94.5.SELECTED DRAWING: None

Description

The present invention relates to an oil repellent for fiber treatment containing a non-fluorine-based copolymer that imparts oil repellency to fibers and the like, a method for producing the same, and a fiber treated with the oil repellent for fiber treatment.

It is known that a polymer of a polymerizable compound having a perfluoroalkyl group is useful as a water / oil repellent for fiber treatment. In particular, an aqueous dispersion in which the polymer is dispersed in an aqueous solvent with an emulsifier is widely used industrially. In particular, aqueous dispersions using cationic surfactants are widely used from the viewpoints of environmental effects of nonionic surfactants, effects of combined use with other fiber treatment agents, adsorptive power to fibers, and flexibility. ing. (Patent Documents 1, 2, and 3)

On the other hand, the US Environmental Protection Agency has announced that a compound containing perfluorooctane as a structure may generate perfluoro-octanoic acid (hereinafter abbreviated as PFOA) by decomposition or metabolism. PFOA is a substance subject to restriction of use in each country because it exhibits bioaccumulation and is not decomposed in the environment.

In order to solve the PFOA problem, a water / oil repellent for fiber treatment having a perfluoroalkyl group having a short carbon chain has been reported (Patent Document 4). Although bioaccumulation and toxicity are said to be reduced by using a perfluoroalkyl group having a short carbon chain, there is no report that the perfluoroalkyl group's persistent property in the environment has been improved.

Also, other perfluoroalkyl groups and fluorine compounds having a similar structure cannot deny the possibility of being subject to regulations related to environmental problems in the near future.

On the other hand, as a non-fluorine fiber treatment agent, there has been reported a water repellent for fiber treatment containing a polymer obtained by graft polymerization of a silicone oil to a cationic acrylic resin (Patent Document 5). However, an oil repellent for fiber treatment using a non-fluorine compound exhibiting oil repellency has not been reported.

Japanese Examined Patent Publication No. 63-14027 JP 2002-275453 A JP 2012-031285 A International Publication No. 2012/020806 Japanese Patent Laid-Open No. 2004-210962

This invention is made | formed in view of such a situation, and provides the oil repellent for fiber treatment which can provide oil repellency to a fiber, without using the compound which has the fluorine represented by the perfluoroalkyl group. This is a technical issue.

As a result of intensive studies, the present inventor has found that the silicone-acrylic copolymer (D) having a specific structure can impart oil repellency to the fiber, and has led to the present invention.

That is, the present invention
(1) containing a silicone-acrylic copolymer (D) having at least a structure represented by the general formulas (a), (b), and (c),
An oil repellent for fiber treatment, which satisfies the following (i) and (ii):
(I) Mass ratio is (a) :( b) :( c) = 5-30: 0.5-25: 45-94.5
(Ii) The silicon content of the copolymer (D) is 0.1 to 10% by mass.

（式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２はメチル基又はエチル基を表し、Ｔは炭素数１〜６のアルキレン基又はＣＨ_２ＣＨ（ＯＨ）ＣＨ_２を表し、Ｕは炭素数１〜６のアルキル基又は炭素数２〜４のアルキレンオキサイド付加残基又はＣＨ_２ＣＨ（ＯＨ）ＣＨ_２Ｘ（但し、Ｘはハロゲン原子）又はＣＨ_２ＣＨ（Ｏ）ＣＨ_３又はＣＨ_２Ｃ_６Ｈ_５を表し、Ｙは有機又は無機の１価のアニオンを表す。）

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a methyl group or an ethyl group, T represents an alkylene group having 1 to 6 carbon atoms or CH ₂ CH (OH) CH ₂ , U represents An alkyl group having 1 to 6 carbon atoms, an alkylene oxide addition residue having 2 to 4 carbon atoms, or CH ₂ CH (OH) CH ₂ X (where X is a halogen atom) or CH ₂ CH (O) CH ₃ or CH ₂ C ₆ H ₅ is represented, Y represents an organic or inorganic monovalent anion.)

（式中、Ｒ^３、Ｒ^４はそれぞれ同一又は異なる水素原子又はメチル基を表し、ｍ、ｎはそれぞれ１〜６の整数を表し、ｐは１以上の整数を表す。）

(Wherein R ³ and R ⁴ each represent the same or different hydrogen atom or methyl group, m and n each represent an integer of 1 to 6, and p represents an integer of 1 or more.)

（式中、Ｒ^５は水素原子又はメチル基を表し、Ｒ^６は炭素数１〜１８のアルキル基を表す。）

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group having 1 to 18 carbon atoms.)

(2) Contains a (meth) acrylate (a1 ′) having a quaternary ammonium group, a (meth) acryl-modified silicone oil (b ′) at both ends, and a nonionic hydrophobic ethylenically unsaturated monomer (c ′) A silicone-acrylic copolymer (D1) obtained by polymerizing the monomer
A method for producing an oil repellent for fiber treatment, characterized by satisfying (a1 ′) :( b ′) :( c ′) = 5-30: 0.5-25: 45-94.5 in terms of mass ratio.

(3) Monomer containing (meth) acrylate (a2 ′) having an amino group, (meth) acryl-modified silicone oil (b ′) at both ends, and nonionic hydrophobic ethylenically unsaturated monomer (c ′) And a silicone-acrylic copolymer (D2) obtained by quaternizing the amino group of (a2 ′),
The above-mentioned (a2 ′) :( b ′) :( c ′) = 5-30: 0.5-25: 45-94.5 in which the amino group is quaternized by mass ratio is satisfied. A method for producing an oil repellent for fiber treatment.

(4) An acrylic polymer (E) obtained by copolymerizing a monomer containing a nonionic hydrophobic ethylenically unsaturated monomer (c ′) in the presence of the copolymer (D1) or (D2). ), And a method for producing an oil repellent for fiber treatment.

(5) The oil repellent for fiber treatment according to any one of (2) to (4), wherein the nonionic hydrophobic ethylenically unsaturated monomer (c ′) is a (meth) acrylic ester. Production method.

(6) An oil repellent for fiber treatment obtained by the production method according to any one of (2) to (5) above, wherein the silicon content of the copolymer (D1) or (D2) is 0.1. An oil repellent for fiber processing, characterized in that the content is 10 to 10% by mass.

(7) A fiber treated with the fiber treatment oil repellent according to (1) or (6).
I will provide a.

According to the present invention, it is possible to provide an oil repellent for fiber treatment that can impart oil repellency to a fiber without using a compound having a perfluoroalkyl group and fluorine that may affect the environment and the human body. it can.

The configuration of the present invention will be described in more detail as follows.

The oil repellent for fiber treatment of the present invention contains a silicone-acrylic copolymer (D) having at least a structure represented by the following general formulas (a), (b), and (c).

（式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２はメチル基又はエチル基を表し、Ｔは炭素数１〜６のアルキレン基又はＣＨ_２ＣＨ（ＯＨ）ＣＨ_２を表し、Ｕは炭素数１〜６のアルキル基又は炭素数２〜４のアルキレンオキサイド付加残基又はＣＨ_２ＣＨ（ＯＨ）ＣＨ_２Ｘ（但し、Ｘはハロゲン原子）又はＣＨ_２ＣＨ（Ｏ）ＣＨ_３又はＣＨ_２Ｃ_６Ｈ_５を表し、Ｙは有機又は無機の１価のアニオンを表す。）

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a methyl group or an ethyl group, T represents an alkylene group having 1 to 6 carbon atoms or CH ₂ CH (OH) CH ₂ , U represents An alkyl group having 1 to 6 carbon atoms, an alkylene oxide addition residue having 2 to 4 carbon atoms, or CH ₂ CH (OH) CH ₂ X (where X is a halogen atom) or CH ₂ CH (O) CH ₃ or CH ₂ C ₆ H ₅ is represented, Y represents an organic or inorganic monovalent anion.)

（式中、Ｒ^３、Ｒ^４はそれぞれ同一又は異なる水素原子又はメチル基を表し、ｍ、ｎはそれぞれ１〜６の整数を表し、ｐは１以上の整数を表す。）

(Wherein R ³ and R ⁴ each represent the same or different hydrogen atom or methyl group, m and n each represent an integer of 1 to 6, and p represents an integer of 1 or more.)

（式中、Ｒ^５は水素原子又はメチル基を表し、Ｒ^６は炭素数１〜１８のアルキル基を表す。）

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group having 1 to 18 carbon atoms.)

The structures represented by the general formulas (a), (b), and (c) are respectively a (meth) acrylate (a1 ′) having a quaternary ammonium group and a (meth) acryl-modified silicone oil (b ′) having both ends. This is a structure formed by polymerizing a nonionic hydrophobic ethylenically unsaturated monomer (c ′).

Although the manufacturing method of the oil repellent for fiber treatment will be described later, the structure represented by the general formula (a) may be introduced by copolymerizing (meth) acrylate (a1 ′) having a quaternary ammonium group. Alternatively, after the (meth) acrylate (a2 ′) having an amino group is copolymerized, the amino group may be introduced by quaternization with a quaternizing agent.

Examples of the (meth) acrylate (a2 ′) having an amino group include diethylaminomethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, dimethylaminohydroxypropyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.

Examples of the quaternizing agent for quaternizing the amino group include epihalohydrin, alkylene oxide, halogenated alkyl, aryl halide and the like, and these can be used alone or in combination of two or more.

As the (meth) acrylate (a1 ′) having a quaternary ammonium group, the epihalohydrin quaternized, alkylene oxide quaternized, alkyl halide or alkyl halide of the (meth) acrylate (a2 ′) having an amino group described above A quaternized compound etc. are mentioned, These can be used 1 type or in combination of 2 or more types.

Among these, the structure represented by the general formula (a) is preferably a structure in which the amino group is quaternized with epichlorohydrin, alkyl chloride having 1 to 4 carbon atoms, benzyl chloride, or alkylene oxide. Specifically, methyl chloride quaternized product, epichlorohydrin quaternized product, and benzyl chloride quaternized product of dimethylaminoethyl (meth) acrylate are more preferable.

The quaternary ammonium group counter ion (Y ⁻ ) may be an organic or inorganic monovalent anion. For example, acetate ion, sulfonate ion, halide ion and the like can be mentioned, and these can be used alone or in combination of two or more.

The fiber treatment oil repellent of the present invention is provided as an aqueous dispersion of the silicone-acrylic copolymer (D). As the aqueous solvent, water or an organic solvent that can be mixed with water can be used. Preferred aqueous solvents include water, alcohols, ethers and ketones, more preferably water, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tertiary butanol, ethylene glycol, propylene glycol, glycerin. , Alcohols such as methyl carbitol, ethyl carbitol, and butyl carbitol. These solvents can be used alone or in combination of two or more. Of these, water or a mixed solvent of water and isopropanol is preferable.

The structure represented by the general formula (a) needs to be contained in a proportion of 5% by mass or more and 30% by mass or less with respect to the silicone-acrylic copolymer (D). When the content of the structure represented by the general formula (a) is less than 5% by mass, the silicone-acrylic copolymer (D) has poor dispersibility, and when it exceeds 30% by mass, (a1 ′) and (a2 The copolymerizability of ') with (b') and (c ') deteriorates and a stable aqueous dispersion cannot be obtained.

The structure represented by the general formula (b) can be obtained by copolymerizing both terminal (meth) acryl-modified silicone oils (b ′). The both-end (meth) acryl-modified silicone oil (b ′) is a compound containing two unsaturated groups obtained by modifying both ends of polydimethylsiloxane with (meth) acrylic acid ester. (B ').

（式中、Ｒ^３、Ｒ^４はそれぞれ同一又は異なる水素原子又はメチル基を表し、ｍ、ｎはそれぞれ１〜６の整数を表し、ｐは１以上の整数であり、好ましくは１以上１００以下の整数を表す。）

(In the formula, R ³ and R ⁴ each represent the same or different hydrogen atom or methyl group, m and n each represent an integer of 1 to 6, and p is an integer of 1 or more, preferably 1 or more and 100 or less. Represents an integer.)

As both-end (meth) acryl-modified silicone oil (b ′), for example, a commercially available product can be used. For example, X-22-164A, X-22-164B, X-22-164C, X-22-164E (manufactured by Shin-Etsu Chemical Co., Ltd.), FM-7711, FM-7721, FM-7725, (JNC Corporation) Manufactured). Both terminal (meth) acryl-modified silicone oils (b ') can be used alone or in combination of two or more.

It is preferable to use those having a molecular weight of 800 to 30,000 as the both end (meth) acryl-modified silicone oil (b ′). If the molecular weight is 800 or more, the resulting oil-repellent agent for fiber treatment containing the silicone-acrylic copolymer (D) is expressed. If the molecular weight is 30000 or less, the copolymerization with other monomers is good. It is.

The structure represented by the general formula (b) needs to be contained in a proportion of 0.5% by mass or more and 25% by mass or less with respect to the silicone-acrylic copolymer (D). When the structure content represented by the general formula (a) is less than 0.5% by mass, the oil repellency expressed by the fiber treatment oil repellant containing the silicone-acrylic copolymer (D) is lowered, and 25 When it exceeds mass%, the copolymerizability with other monomers of (b ′) deteriorates, and a stable aqueous dispersion cannot be obtained.

The structure represented by the general formula (c) is obtained by polymerizing a (meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms in the nonionic hydrophobic ethylenically unsaturated monomer (c ′). Can be obtained. The nonionic hydrophobic ethylenically unsaturated monomer (c ′) may be any one that can be copolymerized with the above (a1 ′), (a2 ′) and (b ′), for example, methyl (meth) acrylate. , Ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, lauryl (meth) ) Acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, phenyl (meth) acrylate, tetrahydrofurfural (meth) acrylate, etc. Acrylic ester or methacrylic Esters, styrene monomers such as styrene, α-methylstyrene and divinylbenzene, olefins such as ethylene, propylene and butene, alkadienes such as butadiene and isoprene, vinyl esters such as vinyl acetate and vinyl propionate, isobutyl vinyl ether, dodecyl vinyl ether And cyclohexyl vinyl ether. Among them, from the viewpoint of industrial use, (meth) such as methyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, etc. Alkyl acrylate is preferred. The nonionic hydrophobic ethylenically unsaturated monomer (c ′) can be used alone or in combination of two or more.

The structure represented by the general formula (c) needs to be contained in a proportion of 45% by mass or more and less than 94.5% by mass with respect to the silicone-acrylic copolymer (D). When the structure content represented by the general formula (c) is within this range, a stable aqueous dispersion of the silicone-acrylic copolymer (D) can be obtained.

As long as the effects of the present invention are not impaired, the silicone-acrylic copolymer (D) may have a structure other than the structure represented by the general formulas (a), (b), and (c). When the acrylic copolymer (D) is produced, other ethylenically unsaturated monomers (f ′) other than the above (a1 ′), (a2 ′), (b ′), and (c ′) are used together. Can be polymerized. Other examples of the ethylenically unsaturated monomer (f ′) include acrylic acid, methacrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, etc. are mentioned. These (f ′) are preferably used within 5 mass% with respect to the silicone-acrylic copolymer (D).

  The silicone-acrylic copolymer (D) of the present invention can be produced, for example, by the following two production methods.

(Manufacturing method 1)
Monomer containing at least a (meth) acrylate (a1 ′) having a quaternary ammonium group, a (meth) acryl-modified silicone oil (b ′) at both ends, and a nonionic hydrophobic ethylenically unsaturated monomer (c ′) A production method of obtaining a target silicone-acrylic copolymer (D1) by adding a polymerization initiator to the polymer and polymerizing it.
(Manufacturing method 2)
Polymerized to a monomer containing at least an amino group-containing (meth) acrylate (a2 ′), both terminal (meth) acryl-modified silicone oil (b ′), and a nonionic hydrophobic ethylenically unsaturated monomer (c ′) A production method for obtaining a target silicone-acrylic copolymer (D2) by adding an initiator and polymerizing, followed by reaction with a quaternizing agent.

The polymerization in the production of the silicone-acrylic copolymer (D1) and the silicone-acrylic copolymer (D2) can be performed by a known polymerization method. For example, the method of superposing | polymerizing by heating using a polymerization initiator in a solvent is mentioned.

The solvent used for production is not particularly limited, and known solvents can be used. For example, water, a mixture of water and an organic solvent, or an organic solvent may be used. The aqueous solvent that can be used for the aqueous dispersion of the silicone-acrylic copolymer (D) is preferable because the production becomes simple. Organic solvents include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, dioxane, ethylene glycol, propylene glycol, glycerin, methyl carbitol, ethyl carbitol, butyl carbitol, ethers such as dioxane, tetrahydrofuran, etc. , Esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, acetic acid, acetic anhydride and the like, among which isopropanol is preferred. These solvents can be used alone or in combination of two or more.

In the case of a production method using an organic solvent, the organic solvent may be distilled off during or at the end of production from the viewpoint of the load on the environment where the oil repellent for fiber treatment is used.

In the production of the silicone-acrylic copolymer (D2), the quaternization of the amino group in the obtained polymer may be carried out at any stage of production, and is preferably in the presence of an acid.

  Examples of the acid include organic acids such as formic acid, acetic acid, and oxalic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid.

Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, 2,2′-azobisaminodipropane hydrochloride, ammonium persulfate, and potassium persulfate.

The weight average molecular weight of the silicone-acrylic copolymer (D) is preferably 3,000 to 100,000. When the weight average molecular weight is less than 3,000, the solubility of the resulting silicone-acrylic copolymer (D) in oil increases, and the oil repellency after fiber treatment may decrease. If it exceeds 100,000, the solution viscosity of the silicone-acrylic copolymer (D) becomes high, so that the handling property may be lowered or the dispersion stability of the solution may be lowered.

Another embodiment of the present invention is an acrylic polymer obtained by copolymerizing the above-described nonionic hydrophobic ethylenically unsaturated monomer (c ′) in the presence of the silicone-acrylic copolymer (D). There is an oil repellent for fiber treatment containing (E).

(C ′) used for the polymerization of the acrylic polymer (E) may be the same as or different from that used for the polymerization of the silicone-acrylic copolymer (D). From the viewpoint of dispersion stability of the acrylic polymer (E), the amount of the hydrophobic ethylenically unsaturated monomer (c ′) used for the polymerization of the acrylic polymer (E) is determined according to the silicone-acrylic copolymer (D). It is preferable that it is 100 mass% or less with respect to the quantity of.

In addition to the nonionic hydrophobic ethylenically unsaturated monomer (c ′) as a monomer used for the polymerization of the acrylic polymer (E) in the presence of the silicone-acrylic copolymer (D), You may copolymerize the said other ethylenically unsaturated monomer (f ') and / or (meth) acryl modified silicone oil in the range which does not impair an effect. The modification site of the (meth) acryl-modified silicone oil may be one end or both ends of polydimethylsiloxane. In the presence of the silicone-acrylic copolymer (D), the monomers used for the polymerization of the acrylic polymer (E) can be used alone or in combination of two or more.

As a method for producing an acrylic polymer (E) obtained by polymerizing a nonionic hydrophobic ethylenically unsaturated monomer (c ′) in the presence of a silicone-acrylic copolymer (D), a known polymerization method is used. Can be done. After the polymerization of the silicone-acrylic copolymer (D) in a solvent, the acrylic polymer (E) may be continuously polymerized, and after forming an aqueous dispersion of the silicone-acrylic copolymer (D), it is known. The acrylic polymer (E) may be polymerized by the emulsion polymerization method.

The glass transition temperature of the silicone-acrylic copolymer (D) and acrylic polymer (E) is not particularly limited as long as it satisfies the performance desired for the fiber, but preferably the silicone-acrylic copolymer (D) and acrylic The glass transition temperature of the polymer (E) is preferably in the range of −50 ° C. to 50 ° C. If the glass transition temperature is lower than −50 ° C., it may cause gum-up during fiber processing. If the glass transition temperature is higher than 50 ° C., the texture of the fiber may be impaired.

The silicone-acrylic copolymer (D) or a mixture of the silicone-acrylic copolymer (D) and the acrylic polymer (E) is dissolved or dispersed in a solvent to form the oil repellent for fiber treatment of the present invention. be able to. In particular, the oil repellent for fiber treatment of the present invention is preferably used in the form of an aqueous dispersion or emulsion. The solid content of the aqueous dispersion or emulsion is preferably 10 to 40% by mass from the viewpoint of handling during production and use. Further, the viscosity in the case of an aqueous dispersion or emulsion is preferably 5000 mPa · s or less.

The oil-repellent agent for fiber treatment of the present invention can be used in the form of the aqueous dispersion or emulsion as a stock solution, but is diluted with water or an organic solvent as necessary. Further, other additives may be mixed in advance with the fiber treatment agent of the present invention. Examples of other additives include antifoaming agents, pigments, thickening inhibitors, pH adjusters, surfactants, and crosslinking agents.

The antifoaming agent is not particularly limited, and known ones can be used. For example, an ester type antifoaming agent, a polyether type antifoaming agent, a mineral oil type antifoaming agent, a silicone type antifoaming agent, etc. are mentioned. In particular, silicone-based antifoaming agents such as siloxane and silicone resin are preferable. The said antifoamer can be used 1 type or in combination of 2 or more types.

The surfactant is not particularly limited, and a known one can be used. Examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. In particular, cationic surfactants such as alkylamine salts and alkyl quaternary ammonium salts are preferred. The said surfactant can be used 1 type or in combination of 2 or more types.

As a crosslinking agent, it does not specifically limit but a well-known thing can be used. For example, an epoxy crosslinking agent, an isocyanate crosslinking agent, a carbodiimide crosslinking agent, or the like may be used. The said crosslinking agent can be used 1 type or in combination of 2 or more types.

Furthermore, the oil repellent for fiber treatment of the present invention may be used as needed with other oil repellents, water repellents, insect repellents, softeners, antibacterial agents, flame retardants, antistatic agents, paint fixing agents, anti-wrinkle agents, Other fiber treatment chemicals such as a soiling agent may be mixed in one kind or a combination of two or more kinds and used for fiber treatment.

The fiber treatment oil repellent of the present invention can be used by a known fiber processing method. At the time of fiber processing, the oil repellent for fiber processing of the present invention can be used after diluted to an appropriate concentration according to the processing method. Usually 0.5 mass%-30 mass% is preferable. When the fiber is a cloth, the cloth may be dipped in the solution, or the cloth may be surface-coated or sprayed on the cloth. The treated fiber may be dried to develop oil repellency. Furthermore, you may cure at 100 to 200 degreeC as needed.

The fiber treated with the oil repellent for fiber treatment of the present invention may be any known type of fiber such as natural fiber, chemical fiber, synthetic fiber, or a mixture of these fibers, and the fiber is processed. The present invention can be applied to woven fabrics, paper products, knitted fabrics and nonwoven fabrics, clothing-form fabrics and carpets, curtains, and the like, and can also be applied in the course of these processing.

In addition, the oil repellent for fiber treatment of the present invention may be used not only for the oil repellent processing of fibers, but also for fiber processing for the purpose of oil resistance treatment, antifouling treatment, softening treatment, etc., and the fiber treatment application is not limited. .

The oil repellency of the fiber treated with the oil repellent for fiber treatment of the present invention can be evaluated by, for example, a method defined in AATCC Test Method 118-1997 Oil Repellency: Hydrocarbon Resistance Test.

Hereinafter, although the synthesis example of this invention, a comparative synthesis example, an Example, and a comparative example are given and demonstrated concretely, this invention is not limited to these examples. In each table, “parts” and “%” indicate “parts by mass” and “mass%” unless otherwise specified.

<Synthesis of 30% solid dispersion of silicone-acrylic copolymer (D1)>
(Synthesis Example 1)
A four-necked flask equipped with a stirring blade, a thermometer, a dropping funnel and a reflux condenser was charged with 64 parts of isopropyl alcohol as a solvent and heated to 80 ° C. Next, 18.75 parts of dimethylaminoethyl methacrylate methyl chloride quaternary product (DMC) (80% aqueous solution) as a (meth) acrylate (a1 ′) having a quaternary ammonium group in the dropping funnel, both end (meth) acrylic 2 parts of X-22-164E (manufactured by Shin-Etsu Chemical Co., Ltd.) as the modified silicone oil (b ′), 73 parts of normal butyl acrylate (nBA) as the nonionic hydrophobic ethylenically unsaturated monomer (c ′), Mix 10 parts of normal butyl methacrylate (nBMA), 120 parts of isopropyl alcohol as a solvent, and 1 part of azobisisobutyronitrile as a polymerization initiator. Add the dissolved mixture and stir for 3 hours while maintaining the internal temperature. And dripped. Furthermore, it was made to react at the same temperature for 6 hours. Thereafter, isopropyl alcohol was distilled off under reduced pressure, and 220 parts of warm water was added to uniformly disperse the resin. Subsequently, it cooled to room temperature and added the water suitably, The solid content 30% aqueous dispersion (D-1) of the silicone-acrylic copolymer (D1) was obtained.

(Synthesis Example 2, Synthesis Example 3)
A silicone-acrylic copolymer (D1) with a solid content of 30% aqueous dispersions (D-2) and (D-3) was obtained in the same manner as in Synthesis Example 1 except that the changes were made as shown in Table 1. .

(Synthesis Example 4)
The same as Synthesis Example 1 except that (meth) acrylate (a1 ′) having a quaternary ammonium group was replaced with 18.75 parts of dimethylaminoethyl methacrylate epichlorohydrin quaternized product (DM-Epi) (80% aqueous solution). Thus, a 30% solids aqueous dispersion (D-4) of silicone-acrylic copolymer (D1) was obtained.

(Synthesis Example 5)
The same procedure as in Synthesis Example 1 except that (meth) acrylate (a1 ′) having a quaternary ammonium group was replaced with 18.75 parts of dimethylaminoethyl methacrylate benzyl chloride quaternized product (DM-Bz) (80% aqueous solution). A 30% solids dispersion (D-5) of a silicone-acrylic copolymer (D1) was obtained.

(Synthesis Example 6, Synthesis Example 7)
The same procedure as in Synthesis Example 1 except that the ratio of the both terminal (meth) acryl-modified silicone oil (b ′) and the nonionic hydrophobic ethylenically unsaturated monomer (c ′) was changed to the ratio shown in Table 1. And 30% aqueous dispersions (D-6) and (D-7) of silicone-acrylic copolymer (D1), respectively.

(Synthesis Example 8)
A silicone-acrylic copolymer (D1) was prepared in the same manner as in Synthesis Example 1 except that 2 parts of both end (meth) acryl-modified silicone oil (b ′) was replaced with 2 parts of X-22-164B (manufactured by Shin-Etsu Chemical Co., Ltd.). ) 30% solids dispersion (D-8).

(Synthesis Examples 9-14)
30% solid dispersions (D-9) to (D-14) of a silicone-acrylic copolymer (D1) were obtained in the same manner as in Synthesis Example 1 except that the changes were made as shown in Table 1. .

<Synthesis of 30% solid dispersion of silicone-acrylic copolymer (D2)>
(Synthesis Example 15)
A four-necked flask equipped with a stirring blade, a thermometer, a dropping funnel and a reflux condenser was charged with 64 parts of isopropyl alcohol as a solvent and heated to 80 ° C. Then, 9 parts of dimethylaminoethyl methacrylate (DM) as (meth) acrylate (a2 ′) having an amino group and X-22-164E (both ends) of (meth) acryl-modified silicone oil (b ′) in the dropping funnel 2 parts manufactured by Shin-Etsu Chemical Co., Ltd., 73 parts normal butyl acrylate (nBA) as nonionic hydrophobic ethylenically unsaturated monomer (c ′), 10 parts normal butyl methacrylate (nBMA), and isopropyl alcohol 120 as solvent 1 part of azobisisobutyronitrile as a polymerization initiator was mixed and dissolved, and the mixture was added dropwise over 3 hours while maintaining the internal temperature while stirring. Furthermore, it was made to react at the same temperature for 6 hours. Thereafter, isopropyl alcohol was distilled off under reduced pressure, and 2.9 parts of acetic acid and 200 parts of warm water were added to uniformly disperse the resin. Subsequently, 6 parts of benzyl chloride (BzCl) was added as a quaternizing agent, and the mixture was kept at 80 ° C. for 3 hours to carry out a quaternization reaction. Thereafter, the mixture was cooled to room temperature, and water was added appropriately to obtain a 30% solids aqueous dispersion (D-15) of silicone-acrylic copolymer (D2).

(Comparative Synthesis Examples 1 to 4)
Comparative Synthesis Example 1 to Comparative Synthesis Example 4 were synthesized in the same manner as Synthesis Example 1 except that the changes were made as shown in Table 1. In Comparative Synthesis Example 1, Comparative Synthesis Example 2 and Comparative Synthesis Example 4, an aqueous copolymer dispersion having good dispersion stability could not be obtained. In Comparative Synthesis Example 3, a 30% aqueous dispersion (RD-3) of a copolymer was obtained.

(Comparative Synthesis Examples 5 to 7)
Both end (meth) acryl-modified silicone oil (b ′) is changed to KF-2012 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is a methacryl-modified silicone oil at one end, and KF-2012 and nonionic hydrophobic ethylenic unsaturated A copolymer 30% solids dispersion (RD-5) to (RD-7), respectively, in the same manner as in Synthesis Example 1 except that the ratio of the monomer (c ′) was changed to the ratio shown in Table 1. )

The silicon content of the copolymers contained in (D-1) to (D-15) and (RD-1) to (RD-7) obtained in Synthesis Examples 1 to 15 and Comparative Synthesis Examples 1 to 7 is The measurement was performed according to the following method.
<Measurement of silicon content in copolymer>
0.5 g of a 30% solids aqueous dispersion of the copolymer was accurately weighed in a zircon crucible and dried at 105 ° C. for 3 hours, and then 2 ml of concentrated sulfuric acid was added to effect sulfuric acid ashing. Add 2.5 g of sodium peroxide and 2.5 g of sodium carbonate to the sulfated ash residue, melt in an electric furnace, allow to cool, and then wash with 100 ml of pure water and 30 ml of concentrated hydrochloric acid in a Teflon (registered trademark) beaker. After dissolution, the total amount was adjusted to 250 ml using a pure water in a 250 ml Teflon (registered trademark) measuring flask, and then ICP measurement was performed.

Use monomers and quaternizing agent contents of (D-1) to (D-15) and (RD-1) to (RD-7) obtained in Synthesis Examples 1 to 15 and Comparative Synthesis Examples 1 to 7, Table 1 shows the dispersion stability of the copolymer and the silicon content of the copolymer.

<Synthesis of Emulsion Containing Acrylic Polymer (E)>
(Synthesis Example 16)
A silicone-acrylic copolymer aqueous dispersion (D-1) 316 having a solid content of 30% obtained in Synthesis Example 1 was added to a four-necked flask equipped with a stirring blade, a nitrogen introducing tube, a thermometer, and a reflux condenser. .6 parts, 0.5 parts of methyl methacrylate (MMA), 2.5 parts of 2-ethylhexyl acrylate (2EHA), normal butyl methacrylate (nBMA) 2 as a nonionic hydrophobic ethylenically unsaturated monomer (c ′) Part and 2 parts of water were added, and nitrogen substitution was performed for 1 hour with stirring. Subsequently, after raising the temperature to 80 ° C., 0.01 part of ammonium peroxodisulfate, which is a polymerization initiator dissolved in 10 parts of water, was added. After making it react at 80 degreeC for 4 hours under stirring, it cooled and added water suitably, and the emulsion (E-1) of 30% of solid content was obtained.

(Synthesis Example 17)
A silicone-acrylic copolymer aqueous dispersion (D-1) 266 having a solid content of 30% obtained in Synthesis Example 1 was added to a four-necked flask equipped with a stirring blade, a nitrogen introducing tube, a thermometer, and a reflux condenser. .6 parts, nonionic hydrophobic ethylenically unsaturated monomer (c ′) as methyl methacrylate (MMA) 2 parts, 2-ethylhexyl acrylate (2EHA) 10 parts, normal butyl methacrylate (nBMA) 8 parts, water 36 7 parts were added, and nitrogen substitution was performed for 1 hour with stirring. Subsequently, after raising the temperature to 80 ° C., 0.04 part of ammonium peroxodisulfate, which is a polymerization initiator dissolved in 10 parts of water, was added. After reacting at 80 ° C. for 4 hours under stirring, the mixture was cooled and water was added appropriately to obtain an emulsion (E-2) having a solid content of 30%.

(Synthesis Example 18)
A silicone-acrylic copolymer aqueous dispersion (D-1) 200 having a solid content of 30% obtained in Synthesis Example 1 was added to a four-necked flask equipped with a stirring blade, a nitrogen inlet tube, a thermometer, and a reflux condenser. Part, 4 parts of methyl methacrylate (MMA), 20 parts of 2-ethylhexyl acrylate (2EHA), 16 parts of normal butyl methacrylate (nBMA), 83.3 water as a nonionic hydrophobic ethylenically unsaturated monomer (c ′) Then, nitrogen was substituted for 1 hour with stirring. Subsequently, after raising the temperature to 80 ° C., 0.08 part of ammonium peroxodisulfate, which is a polymerization initiator dissolved in 10 parts of water, was added. After reacting at 80 ° C. for 4 hours under stirring, the mixture was cooled and water was appropriately added to obtain an emulsion (E-3) having a solid content of 30%.

(Synthesis Examples 19-21)
Nonionic hydrophobic ethylenically unsaturated monomer (c ′) as ethyl acrylate (EA), styrene (ST) and other ethylenically unsaturated monomer (f ′) as 4-hydroxybutyl acrylate (4HBA) 30% solid content emulsions (E-4) to (E-6) were obtained in the same manner as in Synthesis Example 17 except that the ratio was changed to the ratio shown in Table 2.

Table 2 shows the contents of (D-1), (c ') and (f') of the emulsions (E-1) to (E-6) obtained in Synthesis Examples 16 to 21, and the dispersion stability of the emulsion. Shown in

In the table, each abbreviation is
DMC: dimethylaminoethyl methacrylate-methyl chloride quaternized product DM-Epi: dimethylaminoethyl methacrylate-epichlorohydrin quaternized product DM-Bz: dimethylaminoethyl methacrylate-benzyl chloride quaternized product DM: dimethylaminoethyl methacrylate BzCl: Benzyl chloride X-22-146E: methacryl-modified silicone oil at both ends (manufactured by Shin-Etsu Chemical Co., Ltd.)
X-22-146B: Methacrylate-modified silicone oil at both ends (manufactured by Shin-Etsu Chemical Co., Ltd.)
KF-2012: One-end methacryl-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.)
nBA: normal butyl acrylate nBMA: normal butyl methacrylate MMA: methyl methacrylate 2EHA: 2 ethylhexyl acrylate ST: styrene 4HBA: 4-hydroxybutyl acrylate AA: acrylic acid.

(Examples 1-21, Comparative Examples 1-4)
Aqueous dispersions (D-1) to (D-15), (RD-3) and (RD-5) to (RD-7), emulsion (E-1) obtained in each synthesis example and comparative synthesis example -(E-6) was each diluted with water to a solid content of 15% to prepare an oil repellent for fiber treatment. A polyester cloth (100% polyester tropical manufactured by Teijin Ltd.) was immersed in a bath containing the above-described oil repellent for fiber treatment, and then dehydrated with a mangle. Then, after drying at 110 ° C. for 2 minutes, curing was performed at 170 ° C. for 1 minute to prepare a test cloth for evaluation of oil repellency.

<Evaluation of oil repellency>
On one side of the test fabrics obtained in Examples and Comparative Examples, an oil repellent first grade test solution (Kaydol) and an oil repellent second grade test solution (AATCC Test Method 118-1997 Oil Repellency: Hydrocarbon Resistance Test) Gently place 0.03 ml of 65:35 Kaydol: n-Hexadecan by Volume), measure the vertical and horizontal diameters of the droplets in contact with the test cloth after 1 minute, and calculate the droplet area using the average value. did. The test was conducted in a constant temperature room at 25 ° C., using both test cloth and test solution stored at 25 ° C.

The oil repellency performance evaluation criteria are as follows: the droplet area% of the test liquid in an untreated polyester cloth (100% polyester tropical Teijin Ltd.) is taken as 100% and compared with the droplet area on the test cloth. Was calculated. A smaller droplet area% indicates better oil repellency. Table 3 shows the oil repellency test evaluation results of the test fabrics obtained in the examples and comparative examples.

From Synthesis Examples 1-21, Comparative Synthesis Example 1, Comparative Synthesis Example 2, and Comparative Synthesis Example 4, it can be seen that the dispersion stability of the oil repellent for fiber treatment defined in the present invention is excellent.

Moreover, from Examples 1-21 and Comparative Examples 1-4, it turns out that the oil repellency of the oil repellent for fiber treatment prescribed | regulated by this invention is excellent.

In particular, from the comparison between Example 1 and Comparative Example 2, when one-end methacryl-modified silicone oil is used instead of both-end (meth) acryl-modified silicone oil (b ′), excellent oil repellency can be obtained. I understand that I can't.

From the above results, it was shown that the oil repellency can be imparted to the fiber by treating the fiber with the fiber repellant obtained in the present invention without using the fluorine-based fiber repellant.

The oil repellent for fiber treatment of the present invention can be used for imparting oil repellency to fibers such as natural fibers, chemical fibers, and synthetic fibers.

Claims (7)

Containing a silicone-acrylic copolymer (D) having at least a structure represented by general formula (a), (b), (c),
An oil repellent for fiber treatment, which satisfies the following (i) and (ii):
(I) Mass ratio is (a) :( b) :( c) = 5-30: 0.5-25: 45-94.5
(Ii) The silicon content of the copolymer (D) is 0.1 to 10% by mass.

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a methyl group or an ethyl group, T represents an alkylene group having 1 to 6 carbon atoms or CH ₂ CH (OH) CH ₂ , U represents An alkyl group having 1 to 6 carbon atoms, an alkylene oxide addition residue having 2 to 4 carbon atoms, or CH ₂ CH (OH) CH ₂ X (where X is a halogen atom) or CH ₂ CH (O) CH ₃ or CH ₂ C ₆ H ₅ is represented, Y represents an organic or inorganic monovalent anion.)

(Wherein R ³ and R ⁴ each represent the same or different hydrogen atom or methyl group, m and n each represent an integer of 1 to 6, and p represents an integer of 1 or more.)

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group having 1 to 18 carbon atoms.) A monomer containing a (meth) acrylate (a1 ′) having a quaternary ammonium group, a both-end (meth) acryl-modified silicone oil (b ′), and a nonionic hydrophobic ethylenically unsaturated monomer (c ′) Containing a silicone-acrylic copolymer (D1) obtained by polymerization,
A method for producing an oil repellent for fiber treatment, characterized by satisfying (a1 ′) :( b ′) :( c ′) = 5-30: 0.5-25: 45-94.5 in terms of mass ratio. A monomer containing an amino group-containing (meth) acrylate (a2 ′), both terminal (meth) acryl-modified silicone oil (b ′), and a nonionic hydrophobic ethylenically unsaturated monomer (c ′) was polymerized. And a silicone-acrylic copolymer (D2) obtained by quaternizing the amino group of (a2 ′).
The above-mentioned (a2 ′) :( b ′) :( c ′) = 5-30: 0.5-25: 45-94.5 in which the amino group is quaternized by mass ratio is satisfied. A method for producing an oil repellent for fiber treatment. In the presence of the copolymer (D1) according to claim 2 or (D2) according to claim 3, a monomer containing a nonionic hydrophobic ethylenically unsaturated monomer (c ′) is polymerized. A method for producing an oil repellent for fiber treatment, comprising the obtained acrylic polymer (E). The method for producing an oil repellent for fiber treatment according to any one of claims 2 to 4, wherein the nonionic hydrophobic ethylenically unsaturated monomer (c ') is a (meth) acrylic acid ester. An oil repellent for fiber treatment obtained by the production method according to any one of claims 2 to 5, wherein the silicon content of the copolymer (D1) or (D2) is 0.1 to 10% by mass. An oil repellent for fiber treatment, characterized in that A fiber treated with the fiber treatment oil repellent according to claim 1 or 6.