CN105765025B - Water based surface treatment agent - Google Patents

Abstract

The present invention provides a surface treatment agent which does not use a fluorine-containing monomer, particularly a fluoroalkyl group-containing monomer. The surface treatment agent is an aqueous emulsion, and contains: (1) a non-fluoropolymer having a structure derived from (a) formula: CH (CH)₂＝CA¹¹－C(＝O)－O－A¹²[ in the formula, A¹¹Is a hydrogen atom or a methyl group, A¹²Is a linear or branched aliphatic hydrocarbon group having 18 to 30 carbon atoms]Repeating units of the long-chain (methyl) acrylate monomer; (2) a surfactant that includes both a nonionic surfactant and a cationic surfactant, and the amount of the cationic surfactant is 22 wt% or more relative to the total amount of the nonionic surfactant and the cationic surfactant; and (3) an aqueous liquid medium.

Description

Water based surface treatment agent

technical field

The invention relates to a water-based surface treatment agent, especially a water- and oil-repellent agent and an antifouling agent.

Background technique

Fluorine-containing water and oil repellent agents containing fluorine-containing compounds are currently known. The water and oil repellent agent exhibits good water and oil repellency when treating substrates such as fiber products.

According to recent research results [EPA report "PRELIMINARY RISK ASSESSMENT OF THEDEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID ANDITS SALTS" (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)], etc., as long-chain fluorine PFOA (perfluorooctanoic acid), a kind of substituted alkyl compound, has gradually become clear about the environmental load concerns. On April 14, 2003, the EPA (US Environmental Protection Agency) issued an intensified scientific investigation on PFOA.

On the other hand, Federal Register (FR Vol.68, No.73/April 16, 2003 [FRL-2303-8], http://www.epa.gov/opptintr/pfoa/pfoafr.pdf), EPA Environmental News FORRELEASE: MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF ACHEMICAL PROCESSING AID (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) and EPAOPPT FACT SHEET April 14, 2003 (http://www.epa. gov/opptintr/pfoa/pfoafacts.pdf) published that telomers may generate PFOA through decomposition or metabolism (the so-called telomers refer to long-chain fluoroalkyl groups). In addition, it has also been announced that telomers can be used in various products such as fire extinguishing foams, care products, cleaning products, carpets, textiles, paper, and leather imparted with water and oil repellency and antifouling properties. The accumulation of fluorinated compounds in the environment is a concern.

In addition, fluorine-containing water and oil repellent agents containing fluorine-containing polymers must be heat-treated at high temperatures (for example, 100° C. or higher) after being attached to substrates such as fiber products in order to exhibit water and oil repellency. Heat treatment at high temperature requires high energy.

Also, fluoropolymers are expensive.

Therefore, it is desirable to eliminate or reduce the amount of fluoropolymer.

Japanese Patent Laid-Open No. 2006-328624 discloses a water-repellent agent containing a non-fluorine-based polymer containing (meth)acrylate having 12 or more carbon atoms in the ester portion as a monomer unit , The constituent ratio of (meth)acrylate is 80-100 mass % with respect to the monomer unit total amount which comprises a fluorine-free polymer.

However, this water repellent was poor in water and oil repellency.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2006-328624

Contents of the invention

The problem to be solved by the invention

An object of the present invention is to provide a surface treatment agent which imparts excellent water and oil repellency and preferably does not use a fluorine-containing monomer, especially a fluorinated alkyl-containing monomer.

means to solve the problem

The present invention relates to an aqueous emulsion treatment agent, which contains:

(1) polymers having repeating units derived from long-chain (meth)acrylate monomers;

(2) Surfactants; and

(3) Liquid medium containing water.

[1] A surface treatment agent which is an aqueous emulsion comprising:

(1) A non-fluoropolymer having the formula derived from (a): CH ₂ =CA ¹¹ -C(=O)-O—A ¹² [wherein, A ¹¹ is a hydrogen atom or a methyl group, and A ¹² is a carbon A repeating unit of a long-chain (meth)acrylate monomer represented by a linear or branched aliphatic hydrocarbon group with 18 to 30 atoms;

(2) A surfactant comprising both a nonionic surfactant and a cationic surfactant, and the amount of the cationic surfactant relative to the total amount of the nonionic surfactant and the cationic surfactant is within More than 22% by weight; and

(3) Liquid medium containing water.

[2] The surface treatment agent according to [1], wherein the non-fluoropolymer (1) does not contain a (meth)acrylate monomer having a cyclic hydrocarbon group.

[3] The surface treatment agent according to [1] or [2], wherein the nonionic surfactant is at least one selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides, The cationic surfactant is at least one selected from the group consisting of amines, amine salts, quaternary ammonium salts, imidazolines, and imidazolinium salts.

[4] The surface treatment agent according to any one of [1] to [3], wherein the surface treatment agent does not contain a fluoropolymer.

[5] The surface treatment agent according to any one of [1] to [3], wherein the surface treatment agent contains a fluoropolymer.

[6] The surface treatment agent according to any one of [1] to [5], which is a water and oil repellent or an antifouling agent.

[7] A method for treating a fiber product, comprising the step of treating the fiber product with the surface treatment agent described in any one of [1] to [6].

Invention effect

The treating agent of the present invention does not use a monomer containing a fluorinated alkyl group, so there is no concern of accumulating fluorine-containing compounds in the environment. The treating agent of the present invention can impart excellent water and oil repellency to the substrate. In addition, water and oil repellency can be expressed by low temperature treatment without heat treatment at high temperature.

The treatment agent of the present invention has good stability (emulsion stability). The treatment agent of the present invention is excellent in durability (especially washing durability) of water and oil repellency (especially water repellency). Also, the texture of the base material is good.

Utilize the treatment agent that only contains non-fluorine polymer as active ingredient, can obtain the performance equal to or more than that of the treatment agent that only contains fluorine-containing alkyl-containing monomer as structural unit fluoropolymer as active ingredient (especially It is water-repellent and oil-repellent including initial water-repellent and oil-repellent).

detailed description

In the present invention, the polymer (preferably non-fluoropolymer) has repeating units derived from (a) long-chain (meth)acrylate monomers.

The polymer may be a copolymer, and may further have a repeating unit derived from (b) a short-chain (meth)acrylate monomer, a repeating unit derived from (c) a non-fluorinated crosslinkable monomer, and a repeating unit derived from ( d) Repeating units of at least one type of repeating units of halogenated olefin monomers.

The polymer may have fluorine atoms, but preferably does not have fluorine atoms. That is, the polymer is preferably a non-fluoropolymer.

(a) Long chain (meth)acrylate monomer

The long-chain (meth)acrylate monomer has the formula: CH ₂ =CA ¹¹ -C(=O)-O-A ¹² [In the formula, A ¹¹ is a hydrogen atom or a methyl group, and A ¹² is a carbon number of 18 to 30 straight-chain or branched aliphatic hydrocarbon group] shown in the compound.

The long-chain (meth)acrylate monomer does not have a fluoroalkyl group. The long-chain (meth)acrylate monomer may contain fluorine atoms, but preferably does not contain fluorine atoms.

A ¹¹ is particularly preferably methyl.

A ¹² is a linear or branched hydrocarbon group. The linear or branched hydrocarbon group may be, in particular, a linear hydrocarbon group. The linear or branched hydrocarbon group has 18-30 carbon atoms. The straight-chain or branched hydrocarbon group has 18 to 28 carbon atoms, particularly preferably 18 or 22, and is usually preferably a saturated aliphatic hydrocarbon group, particularly preferably an alkyl group.

Preferable specific examples of long-chain (meth)acrylate monomers are stearyl (meth)acrylate and behenyl (meth)acrylate. Particularly preferred is stearyl (meth)acrylate.

By the presence of long-chain (meth)acrylate monomers, the water and oil repellency imparted by the polymer increases.

(b) short chain (meth)acrylate monomer

The polymer may have repeat units derived from short chain (meth)acrylate monomers.

The short-chain (meth)acrylate monomer preferably has the formula: CH ₂ =CA ²¹ -C(=O)-O—A ²² [wherein, A ²¹ is a hydrogen atom or a methyl group, and A ²² is a carbon number less than 18 straight-chain or branched aliphatic hydrocarbon group] compound shown.

The short-chain (meth)acrylate monomer does not have a fluoroalkyl group. The short-chain (meth)acrylate monomer may contain fluorine atoms, but preferably does not contain fluorine atoms.

A ²¹ is particularly preferably methyl.

^A22 is a linear or branched hydrocarbon group. The linear or branched hydrocarbon group may be, in particular, a linear hydrocarbon group. The linear or branched hydrocarbon group has 1-17 carbon atoms. The linear or branched hydrocarbon group preferably has 1 to 14 carbon atoms, usually a saturated aliphatic hydrocarbon group is preferred, and an alkyl group is particularly preferred.

Specific examples of short-chain (meth)acrylate monomers are meth (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate ester, lauryl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate. Particularly preferable specific examples of short-chain (meth)acrylate monomers are lauryl (meth)acrylate and cetyl (meth)acrylate.

By the presence of a short-chain (meth)acrylate monomer, the water repellency and texture imparted by the polymer become better.

(c) Non-fluorinated cross-linking monomer

The polymer may or may not have a repeating unit derived from a non-fluorinated cross-linkable monomer.

A fluorine-free cross-linking monomer is a monomer not containing a fluorine atom. The non-fluorinated cross-linking monomer is a compound which has at least two reactive groups and/or ethylenic carbon-carbon double bonds (preferably (meth)acrylate groups), and does not contain fluorine. The non-fluorine cross-linking monomer can be a compound having at least 2 ethylenic carbon-carbon double bonds (preferably (meth)acrylate group), or a compound having at least 1 ethylenic carbon-carbon double bond and at least 1 compounds with reactive groups. Examples of reactive groups are hydroxyl, epoxy, chloromethyl, blocked isocyanate, amino, carboxyl and the like.

The non-fluorine cross-linking monomer may be mono(meth)acrylate, di(meth)acrylate or mono(meth)acrylamide having a reactive group. Alternatively, the non-fluorinated crosslinkable monomer may be di(meth)acrylate.

An example of a non-fluorine crosslinkable monomer is a vinyl monomer having a hydroxyl group.

Examples of non-fluorinated cross-linking monomers include: diacetone (meth)acrylamide, N-methylol (meth)acrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylamide ) acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, mono Vinyl chloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc., but It is not limited to these.

The washing durability imparted by the polymer is improved by the presence of the non-fluorinated cross-linkable monomer.

(d) Halogenated olefin monomer

The halogenated olefin preferably does not have a fluorine atom.

The halogenated olefin is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly preferably a olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferable specific examples of halogenated olefins include vinyl halides such as vinyl chloride, vinyl bromide, and vinyl iodide; and vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride is preferred.

The washing durability imparted by the polymer is enhanced by the presence of the halogenated olefin.

(e) Other monomers

Other monomers (e) other than the monomers (a) to (d), such as non-fluorine non-crosslinking monomers, can also be used.

Examples of other monomers include, for example: ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (methyl ) acrylates, methoxypolypropylene glycol (meth)acrylates and vinyl alkyl ethers. Other monomers are not limited to these examples.

The non-fluoropolymer (1) may contain a (meth)acrylate monomer having a cyclic hydrocarbon group, but preferably does not contain it.

In this specification, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylamide" means acrylamide or methacrylamide.

Since the water and oil repellency is high, each monomer is preferably an acrylate.

Monomers (a) to (e) may be used alone or in combination of two or more.

The amount of the monomer (a) is 40% by weight or more, preferably 50 parts by weight or more, based on the polymer. The amount of the monomer (a) is 95 parts by weight or less, for example, 80 parts by weight or less, or 75 parts by weight or less, or 70 parts by weight or less with respect to the polymer.

In the polymer, relative to 100 parts by weight of the monomer (a),

The amount of repeating unit (b) can be 0 to 150 parts by weight, preferably 1 to 30 parts by weight,

The amount of repeating unit (c) can be 0 to 50 parts by weight, preferably 1 to 10 parts by weight,

The amount of repeating unit (d) can be 0 to 100 parts by weight, preferably 1 to 30 parts by weight,

The amount of the repeating unit (e) may be 0 to 100 parts by weight, preferably 1 to 30 parts by weight.

The number average molecular weight (Mn) of a polymer is 1000-1000000 normally, for example, it is 5000-500000, especially 3000-200000. The number average molecular weight (Mn) of a polymer is usually determined by GPC (Gel Permeation Chromatography).

The polymer may be one type of polymer or a combination of two or more types of polymers.

In the present invention, a treatment agent composition in which a polymer is dispersed or dissolved in a medium is obtained by polymerizing a monomer.

The monomer used in the present invention can be as follows:

Monomer (a),

Monomer (a)+(b),

Monomer (a)+(c),

Monomer (a)+(b)+(c),

Monomer (a)+(d),

Monomer (a)+(b)+(d),

Monomer (a)+(c)+(d) or

Monomer (a)+(b)+(c)+(d).

Besides these, monomer (e) can also be used.

It is preferable to use a non-fluorine crosslinkable monomer (c). The monomer is preferably a combination of monomer (a) + non-fluorine cross-linking monomer (c) or a combination of monomer (a) + non-fluorine cross-linking monomer (c) + halogenated olefin monomer (d) . In this combination, the water-repellent property has high washing durability.

(2) Surfactant

In the treatment agent of the present invention, the surfactant includes a nonionic surfactant and a cationic surfactant. The surfactant may consist only of nonionic surfactants and cationic surfactants, or may contain other surfactants (other than nonionic surfactants and cationic surfactants). Examples of other surfactants are amphoteric surfactants. The surfactant is preferably free of anionic surfactants.

(2-1) Non-ionic surfactants

Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides.

Examples of ethers are compounds having an oxyalkylene group, preferably a polyoxyethylene group.

Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are 1 to 6 valent (especially 2 to 5 valent) alcohols having 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

An example of ester ether is a compound obtained by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are 1 to 6 valent (especially 2 to 5 valent) alcohols having 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamides may be monoalkanolamides or dialkanolamides. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

The polyhydric alcohol may be a 2- to 5-membered alcohol having 3 to 30 carbon atoms.

The amine oxide may be an oxide (for example, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably a tertiary amine).

The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably polyoxyethylene group). The number of carbon atoms of the alkylene group in the oxyalkylene group is preferably 2-10. It is preferable that the number of the oxyalkylene groups in the molecule of a nonionic surfactant is 2-100 normally.

The nonionic surfactant is selected from ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, preferably nonionic surfactants having an oxyalkylene group.

Nonionic surfactants can be linear and/or branched aliphatic (saturated and/or unsaturated) groups of alkylene oxide adducts, linear and/or branched fatty acids (saturated and/or unsaturated) polyalkylene glycol esters, polyoxyethylene (POE)/polyoxypropylene (POP) copolymers (random copolymers or block copolymers), acetylene glycols Alkylene oxide adducts, etc. Among them, the structure of the alkylene oxide addition part and the polyalkylene glycol part is preferably polyoxyethylene (POE), polyoxypropylene (POP) or POE/POP copolymer (which can be a random copolymer , can also be a block copolymer) substance.

In addition, from the viewpoint of environmental problems (biodegradability, environmental hormones, etc.), it is preferable that the nonionic surfactant has no aromatic group structure.

The nonionic surfactant can be a compound represented by the formula: R ¹ O—(CH ₂ CH ₂ O) _p— (R ² O) _q —R ³ .

[wherein, R ¹ is an alkyl group with 1 to 22 carbon atoms or an alkenyl or acyl group with 2 to 22 carbon atoms, and R ² are independently, the same or different, and are 3 or more carbon atoms (such as 3 to 10) ^R3 is a hydrogen atom, an alkyl group with 1 to 22 carbon atoms or an alkenyl group with 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more. ]

R ¹ preferably has 8-20 carbon atoms, especially 10-18 carbon atoms. Preferable specific examples of R ¹ include lauryl, tridecyl, and oleyl.

Examples of R ² are propylene, butylene.

In nonionic surfactants, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R ² O) _q - may form a polyoxyalkylene chain.

The nonionic surfactant can be a polyoxyethylene alkylene alkyl group containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (especially a polyoxyalkylene chain) in the center. ether. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, among which an oxypropylene chain is preferable.

A preferred nonionic surfactant is a surfactant represented by the formula: R ¹ O—(CH ₂ CH ₂ O) _p —H.

[In the formula, R ¹ and p have the same meaning as above. ]

Specific examples of nonionic surfactants are:

C ₁₀ H ₂₁ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₂ H ₂₅ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₆ H ₃₁ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₆ H ₃₃ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₈ H ₃₅ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₈ H ₃₇ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₂ H ₂₅ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -C ₁₂ H ₂₅

C ₁₆ H ₃₁ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -C ₁₆ H ₃₁

C ₁₆ H ₃₃ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -C ₁₂ H ₂₅

iso-C ₁₃ H ₂₇ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₀ H ₂₁ COO-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₆ H ₃₃ COO-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -C ₁₂ H ₂₅ and so on.

[In the formula, p and q have the same meaning as above. ]

Specific examples of nonionic surfactants include: ethylene oxide and hexylphenol, isooctylphenol, cetyl alcohol, oleic acid, alkane (C ₁₂ -C ₁₆ ) mercaptan, sorbitan monofatty acid ( Condensation products such as C ₇ -C ₁₉ ) or alkyl (C ₁₂ -C ₁₈ ) amines.

The ratio of the polyoxyethylene block to the molecular weight of the nonionic surfactant (copolymer) may be 5 to 80% by weight, for example, 30 to 75% by weight, particularly 40 to 70% by weight.

The average molecular weight of a nonionic surfactant is 300-5,000 normally, for example, 500-3,000.

A nonionic surfactant may be used individually by 1 type, and may use 2 or more types together.

The nonionic surfactant is preferably a combination of two or more. In the combination of two or more types, at least ^{one nonionic surfactant may be R 1 O— (} CH A compound represented by ₂ CH ₂ O) _p -(R ² O) _q -R ³ [particularly R ¹ O -(CH ₂ CH ₂ O) _p -H]. The amount of the nonionic surfactant whose R group is ^a branched alkyl group can be 5 to 100 parts by weight, for example, 8 to 50 parts by weight, particularly 100 parts by weight of the total nonionic surfactant (B2). 10 to 40 parts by weight. In the combination of two or more, the rest of the nonionic surfactants can be that the R ¹ group (and/or R ³ group) is a (saturated and/or unsaturated) straight-chain alkyl group (such as lauryl (n-lauric) group)) R ¹ O-(CH ₂ CH ₂ O) _p -(R ² O) _q -R ³ [particularly R ¹ O-(CH ₂ CH ₂ O) _p -H] compounds.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene fatty acid esters, Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, Polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkyl alcohol amide, alkyl alkanol amide, acetylene glycol, oxyethylene adduct of acetylene glycol, polyethylene glycol poly Propylene glycol block copolymer, etc.

Since the dynamic surface tension of the water-based emulsion is reduced (that is, the water-based emulsion is easy to penetrate the substrate), it is preferred as a non-ionic surfactant to use acetylenic alcohols (especially acetylenic diols) or ethylene oxides of acetylenic alcohols (especially acetylenic diols). Base adducts.

A preferred nonionic surfactant is an alcohol having an unsaturated triple bond or an alkylene oxide adduct of the alcohol (both the alcohol and the alkylene oxide adduct are referred to as "alkynol compounds"). Particularly preferred nonionic surfactants are alkylene oxide adducts of monoalcohols or polyalcohols having unsaturated triple bonds.

The acetylenic alcohol compound is a compound containing one or more triple bonds and one or more hydroxyl groups. The acetylenic alcohol compound may be a compound containing a polyoxyalkylene moiety. Examples of polyoxyalkylene moieties include polyoxyethylene, polyoxypropylene, random addition structures of polyoxyethylene and polyoxypropylene, polyoxyethylene and polyoxypropylene Block addition structure of propylene.

Alkynol compounds can be of the formula:

HO－CR ¹¹ R ¹² －C≡C－CR ¹³ R ¹⁴ －OH, or

A compound represented by HO-CR ¹⁵ R ¹⁶ -C≡C-H.

[In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently, the same or different, and are a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ]

The acetylenic alcohol compound may be an alkylene oxide adduct of the compound represented by the chemical formula. The alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and particularly preferably a linear or branched alkyl group having 6 to 12 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group etc. are mentioned. In addition, examples of the alkylene oxide include alkylene oxides having 1 to 20 (especially 2 to 5) carbon atoms such as ethylene oxide and propylene oxide, and the addition number of the alkylene oxide is preferably 1 to 50.

Specific examples of acetylene alcohol compounds include acetylene diol, propynyl alcohol, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne -3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyne-3-ol, 3 -Methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 3-hexyne-2,5-diol, 2-butyne-1,4-diol Wait. Also listed are polyethoxylates and ethylene oxide adducts of the compounds of these specific examples.

A nonionic surfactant may not have a triple bond, or may have a triple bond. Nonionic surfactant can be only one of nonionic surfactant without triple bond or nonionic surfactant with triple bond, also can be nonionic surfactant without triple bond and with A combination of nonionic surfactants with a triple bond. In the combination of a nonionic surfactant not having a triple bond and a nonionic surfactant having a triple bond, the nonionic surfactant not having a triple bond (such as a nonionic surfactant having an oxyalkylene group) The weight ratio of active agent) to the non-ionic surfactant having a triple bond (such as acetylenic alcohol compound) may be 10:90-90:10, for example, 20:80-80:20.

(2－2) Cationic surfactant

The cationic surfactant is preferably a compound not having an amide group.

Examples of cationic surfactants include amines, amine salts, quaternary ammonium salts, imidazoline and imidazolinium salts.

Cationic surfactants are preferably amine salts, quaternary ammonium salts, and oxyethylene addition type ammonium salts. Specific examples of cationic surfactants are not particularly limited, and include: amine salt-type surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; alkyltrimethylammonium salts , Dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, quaternary ammonium salt type surfactant such as benzethonium chloride, etc.

Examples of cationic surfactants are compounds of R ²¹ -N ⁺ (-R ²² )(-R ²³ )(-R ²⁴ )X ^- .

[In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ are independently identical or different, and are hydrogen atoms or hydrocarbon groups with 1 to 50 carbon atoms, and X is an anionic group. ]

The hydrocarbon group may have an oxygen atom, and may be, for example, an oxyalkylene group such as a polyoxyalkyl group (the number of carbon atoms in the alkylene group is, for example, 2 to 5). R ²¹ , R ²² , R ²³ and R ²⁴ are preferably hydrocarbon groups having 1 to 30 carbon atoms (such as aliphatic hydrocarbons, aromatic hydrocarbons or aromatic aliphatic hydrocarbons).

Specific examples of R ²¹ , R ²² , R ²³ and R ²⁴ are alkyl (such as methyl, butyl, stearyl, palmityl), aryl (such as phenyl), aralkyl (such as benzyl ( phenylmethyl), phenethyl (phenylethyl)).

Specific examples of X are halogens (such as chlorine), acids (such as inorganic acids such as hydrochloric acid, organic acids such as acetic acid (especially fatty acids)).

The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (the number of carbon atoms in the alkyl group is 4 to 30).

Cationic surfactants are preferably ammonium salts, particularly preferably quaternary ammonium salts. The cationic surfactant may be an ammonium salt represented by the formula: R ³¹ _p -N ⁺ R ³² _q X ^- .

[wherein, R ³¹ are independently, the same or different, and are linear and/or branched aliphatic (saturated and/or unsaturated) groups of C12 or more (for example, C ₁₂ to C ₅₀ ),

R ³² are independently identical or different, and are H or C1-4 alkyl, benzyl, polyoxyethylene (the number of oxyethylene groups is, for example, 1 (especially 2, more particularly 3) to 50) (especially preferably CH ₃ , C ₂ H ₅ ),

X is a halogen atom (such as chlorine and bromine), C ₁ ~ C ₄ fatty acid base,

p is 1 or 2, q is 2 or 3, and p+q=4. ]

The number of carbon atoms of R ³¹ may be 12-50, for example, 12-30.

Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, cetyltrimethylammonium bromide, trimethyloctadecyl Ammonium, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride , Benzyl dodecyl di(hydrogen polyoxyethylene) ammonium chloride.

Examples of amphoteric surfactants include alanines, imidazoline betaines, amide betaines, and acetate betaines. Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazoline betaine, lauryl dimethyl glycine betaine, fatty amidopropyl dimethyl glycine betaine, etc.

Nonionic surfactants, cationic surfactants, and amphoteric surfactants may each be one type or a combination of two or more.

With respect to the total amount of nonionic surfactant and cationic surfactant, the amount of cationic surfactant is preferably 15% by weight or more, more preferably 20% by weight or more, particularly preferably 22% by weight or more, for example, 25% by weight or more, especially 30% by weight or more, more specifically 35% by weight or more. The upper limit of the amount of cationic surfactant is, for example, 60% by weight, especially 50% by weight, more particularly 45% by weight. The weight ratio of the nonionic surfactant to the cationic surfactant is preferably 85:15 to 20:80, more preferably 80:20 to 40:60. The amount of surfactants other than ionic surfactants and cationic surfactants may be 50% by weight or less, for example, 20% by weight or less, and may be 0.1% by weight relative to the total amount of surfactants. above.

The quantity of a cationic surfactant can be 0.05-10 weight part with respect to 100 weight part of polymers, for example, it may be 0.1-8 weight part. The total amount of surfactants may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight, relative to 100 parts by weight of the polymer.

(3) Liquid medium

The liquid medium may be water alone or a mixture of water and a (water-miscible) organic solvent. The amount of the organic solvent may be 30% by weight or less, for example, 10% by weight or less (preferably 0.1% or more) with respect to the liquid medium. The liquid medium is preferably water alone.

The water and oil repellent composition of the present invention may contain only the above-mentioned non-fluoropolymer as the polymer (active ingredient), or may contain a fluorine-containing polymer in addition to the above-mentioned non-fluoropolymer. Usually, in a water and oil repellent composition (especially an aqueous emulsion), particles made of a non-fluoropolymer and particles made of a fluoropolymer exist separately. That is, it is preferable to mix the non-fluoropolymer and the fluoropolymer after producing the non-fluoropolymer and the fluoropolymer separately. Usually, it is preferable to mix the non-fluoropolymer emulsion and the fluoropolymer emulsion after separately producing the non-fluoropolymer emulsion (particularly aqueous emulsion) and the fluoropolymer emulsion (particularly aqueous emulsion).

Fluoropolymers are polymers having repeat units derived from fluoromonomers. The fluorine-containing monomer is preferably acrylate or acrylamide represented by the following general formula (I).

CH ₂ =C(-X)-C(=O)-Y-Z-Rf (I)

[wherein, X is a hydrogen atom, a linear or branched alkyl group with 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² base (wherein, X ¹ and X2 is a ^hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group with 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, Substituted or unsubstituted phenyl;

Y is -O- or -NH-;

Z is an aliphatic group with 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group with 6 to 18 carbon atoms, a -CH ₂ CH ₂ N(R ¹ )SO ₂ - group (wherein, R ¹ is an alkyl group with 1 to 4 carbon atoms), -CH ₂ CH(OZ ¹ )CH ₂ - group (wherein, Z ¹ is a hydrogen atom or acetyl group), -(CH ₂ ) _m -SO ₂ -( CH ₂ ) _n -group or -(CH ₂ ) _m -S-(CH ₂ ) _n -group (where m is 1-10, n is 0-10);

Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms.

The number of carbon atoms of the Rf group is preferably 1-6, particularly 4-6.

The fluorine-containing polymer may have repeating units derived from at least one non-fluorine monomer selected from the group consisting of halogenated olefin monomers, non-fluorine non-crosslinkable monomers, and non-fluorine crosslinkable monomers.

The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. Specific examples of halogenated olefin monomers include vinyl halides such as vinyl chloride, vinyl bromide, and vinyl iodide; and vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide.

A preferred non-fluorine non-crosslinking monomer is a compound represented by the formula: CH ₂ =CA-T.

[wherein, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (such as a chlorine atom, a bromine atom, and an iodine atom),

T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 20 carbon atoms, or a chain or cyclic organic group having 1 to 20 carbon atoms having an ester bond. ]

Specific examples of non-fluorine non-crosslinking monomers include: alkyl (meth)acrylate, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth)acrylate, polypropylene glycol (methyl) ) acrylates, methoxypolyethylene glycol (meth)acrylates, methoxypolypropylene glycol (meth)acrylates and vinyl alkyl ethers.

The non-fluorinated cross-linking monomer can be a compound with at least 2 carbon-carbon double bonds (such as (meth)propenyl), or a compound with at least 1 carbon-carbon double bond and at least 1 reactive group .

The weight ratio of the non-fluorine polymer to the fluorine-containing polymer in the water and oil repellent composition can be 100:0 to 10:90, for example 90:10 to 20:80, preferably 80:20 to 30:70 .

The non-fluorine polymer and the fluorine-containing polymer may each be one type of polymer, or may be a combination of two or more types of polymers.

When using a combination of non-fluorinated polymers and fluorinated polymers, it is possible to obtain performances (especially water and oil repellency) equivalent to or better than those obtained when only fluorinated polymers are used

The polymers (non-fluorine polymers and fluorine-containing polymers) in the present invention can be produced by any usual polymerization method, and the conditions of the polymerization reaction can also be selected arbitrarily. Examples of such a polymerization method include solution polymerization, suspension polymerization, and emulsion polymerization. Emulsion polymerization is preferred.

The method for producing the polymer is not limited as long as the treatment agent of the present invention is an aqueous emulsion. For example, a polymer can be produced by solution polymerization, and then the solvent can be removed, and a surfactant and water can be added to obtain an aqueous emulsion.

In the solution polymerization, a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, followed by nitrogen substitution, followed by heating and stirring in a range of 30 to 120° C. for 1 to 10 hours. As the polymerization initiator, for example, azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumyl hydroperoxide, peroxypivalic acid tert-butyl ester, diisopropyl peroxydicarbonate, etc. A polymerization initiator can be used in the range of 0.01-20 weight part with respect to 100 weight part of monomers, for example, the range of 0.01-10 weight part.

The organic solvent is a solvent that is inactive and capable of dissolving the monomers, such as esters (such as esters with 2 to 30 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (such as carbon atoms Ketones with 2 to 30 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (such as alcohols with 1 to 30 carbon atoms, specifically isopropanol). Specific examples of organic solvents include acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4 -Dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane alkanes, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, etc. The organic solvent can be used in the range of 10 to 2000 parts by weight, for example, in the range of 50 to 1000 parts by weight with respect to 100 parts by weight in total of the monomers.

In the emulsion polymerization, a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, it is a method of stirring at 50 to 80° C. for 1 to 10 hours to polymerize. The polymerization initiator can use benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisiso Butylamidine-dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate and other water-soluble initiators or azobisisobutyronitrile, benzoyl peroxide, ditertiary Oil-soluble initiators such as butyl peroxide, lauryl peroxide, cumyl hydroperoxide, tert-butyl peroxypivalate, and diisopropyl peroxydicarbonate. A polymerization initiator can be used in the range of 0.01-10 weight part with respect to 100 weight part of monomers.

In order to obtain an aqueous polymer dispersion excellent in standing stability, it is preferable to use an emulsification device capable of imparting strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer to micronize and polymerize monomers in water. Moreover, as an emulsifier, various emulsifiers of anionic type, cationic type, or nonionic type can be used, and can be used in the range of 0.5-20 weight part with respect to 100 weight part of monomers. Preference is given to using anionic and/or nonionic and/or cationic emulsifiers. When the monomers are not completely compatible, it is preferable to add a compatibilizing agent that makes these monomers fully compatible, for example, add a water-soluble organic solvent or a low molecular weight monomer. By adding a compatibilizer, emulsifiability and copolymerizability can be improved.

As the water-soluble organic solvent, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc. can be cited, relative to 100 parts by weight of water, it can be in the range of 1 to It is used in the range of 50 parts by weight, for example, in the range of 10 to 40 parts by weight. In addition, examples of low-molecular weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate, etc., based on 100 parts by weight of the total amount of monomers , can be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight.

Chain transfer agents can be used in the polymerization. The molecular weight of the polymer can be varied according to the amount of the chain transfer agent used. Examples of chain transfer agents are thiol group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (especially (for example, alkyl mercaptans with 1 to 30 carbon atoms)), sodium hypophosphite, sulfurous acid, etc. Inorganic salts such as sodium hydrogen, etc. The chain transfer agent can be used in the range of 0.01 to 10 parts by weight, for example, in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomers.

The treating agent composition of the present invention may be in the form of a solution, an emulsion (especially an aqueous dispersion) or an aerosol, and is preferably an aqueous dispersion. The treatment agent composition contains a polymer (active ingredient of a surface treatment agent) and a medium (especially a liquid medium such as an organic solvent and/or water). The amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight relative to the treatment agent composition.

In the treatment composition, the concentration of the polymer may be 0.01 to 95% by weight, for example 5 to 50% by weight.

The treatment agent composition of the present invention can be applied to a treatment object by a conventionally known method. Usually, the treatment agent composition is dispersed in an organic solvent or water, diluted, and applied to the surface of the object to be treated by a known method such as dip coating, spray coating, and foam coating, and then dried. . In addition, it can be applied together with a suitable crosslinking agent (such as blocked isocyanate) for curing (curing) when required. It is also possible to add insect repellent, softener, antibacterial agent, flame retardant, antistatic agent, paint fixing agent, anti-wrinkle agent, etc. to the treatment agent composition of the present invention. The concentration of the polymer in the treatment liquid in contact with the substrate may be 0.01 to 10% by weight (especially during dip coating), for example, 0.05 to 10% by weight.

As the object to be treated with the treatment agent composition (such as water and oil repellent) of the present invention, fiber products, stone materials, filters (such as electrostatic filters), dust masks, parts of fuel cells (such as gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metal and oxide, ceramics, plastics, coated surfaces and plaster, etc. Various examples can be given as fiber products. Examples include natural animal and vegetable fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, rayon, and acetate fibers. Semi-synthetic fibers such as glass fibers, carbon fibers, asbestos fibers and other inorganic fibers, or their mixed fibers.

The fiber product may be in any form such as fiber or cloth.

The treatment composition of the present invention can be used as an internal release agent or an external release agent.

The polymer can be applied to a fibrous substrate (eg, a fibrous product, etc.) by any known method of treating a fibrous product with a liquid. When the fiber product is cloth, the cloth may be dipped in the solution, or the solution may be attached or sprayed onto the cloth. The treated fiber product is preferably dried, for example, heated at 100°C to 200°C in order to express oil repellency.

Alternatively the polymer may be applied to the fibrous product by laundering, for example by laundering application or dry cleaning or the like.

The fibrous product to be treated is typically a cloth, this includes textiles, woven and non-woven fabrics, cloth in the form of clothing and blankets, but may also be fibres, threads or intermediate fibrous products such as slivers or thick threads Wait). Fiber product materials can be natural fibers (such as cotton or wool, etc.), chemical fibers (such as viscose rayon (viscose rayon) or lyocell, etc.) or synthetic fibers (such as polyester, polyamide or acrylic fibers, etc.) ), or it can also be a mixture of fibers (such as a mixture of natural fibers and synthetic fibers, etc.). The polymers of manufacture of the present invention are particularly effective in imparting oleophobicity and oil repellency to cellulosic fibers such as cotton or rayon and the like. Also, the inventive method generally imparts hydrophobicity and water repellency to fibrous articles.

Alternatively, the fibrous substrate may also be leather. In order to render the leather hydrophobic and oleophobic, the manufacturing polymers are applied to the leather from aqueous solutions or aqueous emulsions at various stages of leather processing, for example during wet processing of the leather or during the finishing of the leather.

Alternatively, the fibrous substrate may also be paper. The making polymer can be applied to pre-formed paper, or it can be applied to various stages of paper making, such as during drying of the paper.

The term "treatment" refers to applying a treatment agent to an object to be treated by dipping, spraying, coating, or the like. Through the treatment, the polymer as an active ingredient of the treatment agent penetrates into the inside of the object to be treated and/or adheres to the surface of the object to be treated.

The zeta potential of the aqueous emulsion treatment agent is preferably +30 mV or more. The zeta potential was measured by the laser Doppler method (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.).

The dynamic surface tension of the aqueous emulsion treatment agent is preferably 55 mN/m or less. The dynamic surface tension was measured by the maximum bubble pressure method (BP-D5 manufactured by Kyowa Surface Science Co., Ltd.).

Example

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, these descriptions do not limit the present invention.

Hereinafter, unless otherwise specified, parts, %, or ratios represent parts by weight, % by weight, or ratio by weight.

The procedure of the test is described below.

Spray water repellency

According to JIS-L-1092, the spray water repellency test was carried out. The spray water repellency test (as shown in the table below) is indicated by the water repellency No.

Water repellency No. state 100 No wetting or attachment of water droplets to the surface 90 The surface is not wet, but exhibits the attachment of small water droplets 80 Wetting of the surface in the form of small individual water droplets 70 Half of the surface appears wet, in the form of small individual wet-soaked cloths 50 The overall surface is wet 0 The surface and the back are generally wet

Use a glass funnel with a volume of at least 250ml and a nozzle capable of spraying 250ml of water in 20-30 seconds. The test piece frame is a metal frame with a diameter of 15 cm. Three test pieces having a size of about 20 cm x 20 cm were prepared, and the sheets were fixed to the test piece holder so that the sheets had no wrinkles. Center the spray on the center of the sheet. Water (250 mL) at room temperature was put into the glass funnel, and sprayed on the test sheet (for 25 seconds to 30 seconds). Remove the holding frame from the table, grasp one end of the holding frame so that the front surface is the lower side, and lightly tap the opposite end with a hard object. Then make the retaining frame rotate 180°, repeat the same steps, and make the excess water drop down. In order of water repellency from poor to excellent, the wet test pieces were given a score of 0, 50, 70, 80, 90 and 100, compared to the wet comparison standard. Results are obtained as the mean of 3 determinations.

Water-repellent washing durability

According to the JIS L-0217-103 method, washing was repeated 5 and 20 times, and the water and oil repellency after evaluation was evaluated (HL5, 20).

Feel evaluation

The sensory evaluation of the following 5 grades was carried out by 5 inspectors, and the average value was taken.

5: very soft

4: soft

3: Same as untreated cloth

2: hard

1: very hard

Mechanical Stability Test

mechanical stability

The aqueous dispersion was diluted to 1% with tap water, stirred with a homomixer at 3,000 rpm for 10 minutes, and the resulting scum was filtered onto a black cotton cloth.

○: There is no scum at all

△: Slight scum

×: Much scum

Peel strength

Peel Strength of Synthetic Film

The aqueous polymer dispersion was diluted with water so that the solid content concentration became 1% by weight to prepare a treatment liquid. The nylon cloth was dipped in the treatment solution, and squeezed at 4 kg/cm ² and 4 m/min with a mangle. After heat treatment at 170°C for 1 minute, a polyurethane resin-based adhesive (manufactured by DIC Corporation, CRISVON 4010FT) with a concentration of 50% of MEK and ethyl acetate as solvents was coated on a single sheet of nylon cloth in dots. After crimping the polyurethane synthetic film on the surface, heat treatment at 120°C for 2 minutes. The obtained nylon cloth was repeatedly washed 20 times with AATCC 88B(1)(III), and then the peeling state of the synthetic film was visually observed, and the state was evaluated according to the following criteria.

◎: No peeling at all

○: Very little peeling

×: Significant peeling was observed

Manufacturing example 1

Add stearyl acrylate = 50g, pure water = 145g, tripropylene glycol = 15g, sorbitan monooleate = 1.5g, polyoxyethylene (EO: 18) secondary alkane into a 500mL autoclave Base (C12-14) ether = 2 g, di-octadecyl dimethyl ammonium chloride = 1.5 g, and ultrasonically emulsify and disperse at 60° C. for 15 minutes while stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing example 2

Add stearyl acrylate = 50g, pure water = 145g, tripropylene glycol = 15g, acetylene glycol polyoxyethylene adduct = 1g, polyoxyethylene (EO: 18) into a 500mL autoclave Isotridecyl ether = 2 g, dioctadecyl dimethyl ammonium chloride = 2 g, ultrasonic emulsification and dispersion at 60° C. for 15 minutes while stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing example 3

Add stearyl acrylate = 50g, pure water = 145g, tripropylene glycol = 15g, acetylene glycol polyoxyethylene adduct = 1g, polyoxyethylene (EO: 18) into a 500mL autoclave Lauryl ether = 2.9 g, octadecyltrimethylammonium chloride = 1.1 g, and was dispersed by ultrasonic emulsification at 60° C. for 15 minutes while stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing Example 4

In a 500mL autoclave, add behenyl acrylate = 47.5g, glycidyl methacrylate = 2.5g, pure water = 145g, tripropylene glycol = 15g, acetylene glycol polyoxyethylene adduct = 1 g, polyoxyethylene (EO: 18) isotridecyl ether = 2 g, dioctadecyl dimethyl ammonium chloride = 2 g, ultrasonic emulsification and dispersion at 60° C. for 15 minutes while stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing Example 5

Add stearyl acrylate=47.5g, glycidyl methacrylate=2.5g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=1.5g, Polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether = 2g, di-octadecyldimethylammonium chloride = 1.5g, ultrasonic emulsification and dispersion at 60°C for 15 minutes under stirring . After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing example 6

Add stearyl acrylate = 20g, behenyl acrylate = 15g, behenyl methacrylate = 12.5g, glycidyl methacrylate = 2.5g, pure water = 145g, di Tripropylene glycol = 15g, acetylene glycol polyoxyethylene adduct = 1g, polyoxyethylene (EO: 18) isotridecyl ether = 2g, di-octadecyldimethyl chloride Ammonium = 2 g, ultrasonic emulsification and dispersion at 60° C. for 15 minutes with stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing example 7

Add stearyl acrylate = 20g, lauryl acrylate = 30g, pure water = 145g, tripropylene glycol = 15g, acetylene glycol polyoxyethylene adduct = 1g, polyoxyethylene Ethyl (EO: 18) isotridecyl ether = 2 g, dioctadecyl dimethyl ammonium chloride = 2 g, and were dispersed by ultrasonic emulsification at 60° C. for 15 minutes while stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing example 8

Add behenyl acrylate = 20g, lauryl acrylate = 27.5g, hydroxyethyl methacrylic acid = 2.5g, pure water = 145g, tripropylene glycol = 15g, acetylene glycol polyoxyethylene Ethyl adduct = 1g, polyoxyethylene (EO: 18) isotridecyl ether = 2g, di-octadecyldimethylammonium chloride = 2g, under stirring at 60°C with ultrasonic Emulsify and disperse for 15 minutes. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing Example 9

Add stearyl acrylate = 10g, behenyl acrylate = 10g, cetyl acrylate = 27.5g, hydroxyethyl methacrylic acid = 2.5g, pure water = 145g, tripropylene glycol in a 500mL autoclave = 15g, acetylene glycol polyoxyethylene adduct = 1g, polyoxyethylene (EO: 18) lauryl ether = 2.9g, octadecyltrimethylammonium chloride = 1.1g, stirring Disperse by ultrasonic emulsification at 60°C for 15 minutes. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing example 10

Add stearyl acrylate = 35g, glycidyl methacrylate = 2.5g, pure water = 145g, tripropylene glycol = 15g, acetylene glycol polyoxyethylene adduct = 1g in a 500mL autoclave , Polyoxyethylene (EO: 18) isotridecyl ether = 2 g, di-octadecyl dimethyl ammonium chloride = 2 g, ultrasonic emulsification and dispersion at 60° C. for 15 minutes while stirring. After nitrogen substitution in the autoclave, 12.5 g of vinyl chloride was added by pressing, and 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the reaction was carried out at 60°C for 3 hours. An aqueous dispersion of the polymer is obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing example 11

Add stearyl acrylate=17.5g, behenyl acrylate=17.5g, hydroxyethyl methacrylic acid=5g, pure water=145g, tripropylene glycol=15g, sorbitan mono Oleic acid ester=1.5g, polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether=2g, di-octadecyl dimethyl ammonium chloride=1.5g, under stirring at 60 ℃ and use ultrasonic emulsification to disperse for 15 minutes. After nitrogen substitution in the autoclave, 10 g of vinyl chloride was added by pressing, and 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the reaction was carried out at 60° C. for 3 hours. An aqueous dispersion of the polymer is obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing example 12

Add stearyl acrylate = 30g, lauryl acrylate = 10g, glycidyl methacrylate = 2.5g, pure water = 145g, tripropylene glycol = 15g, acetylene glycol polyoxyethylene Ethyl adduct = 1g, polyoxyethylene (EO: 18) lauryl ether = 2.9g, octadecyltrimethylammonium chloride = 1.1g, and was dispersed by ultrasonic emulsification at 60°C under stirring for 15 minute. After nitrogen substitution in the autoclave, 7.5 g of vinyl chloride was added by pressing, and 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the reaction was carried out at 60°C for 3 hours , to obtain an aqueous dispersion of the polymer. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing Example 13

Add stearyl acrylate = 35g, glycidyl methacrylate = 2.5g, pure water = 145g, tripropylene glycol = 15g, acetylene glycol polyoxyethylene adduct = 1g in a 500mL autoclave , Polyoxyethylene (EO: 18) isotridecyl ether = 2 g, di-octadecyl dimethyl ammonium chloride = 2 g, ultrasonic emulsification and dispersion at 60° C. for 15 minutes while stirring. After nitrogen substitution in the autoclave, 12.5 g of vinylidene chloride was added by pressing, and 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and the reaction was carried out at 60°C for 3 hours, an aqueous dispersion of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing Example 14

Add stearyl acrylate = 20g, lauryl acrylate = 17.5g, glycidyl methacrylate = 2.5g, pure water = 145g, tripropylene glycol = 15g, sorbitan mono Oleic acid ester=1.5g, polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether=2g, di-octadecyl dimethyl ammonium chloride=1.5g, under stirring at 60 ℃ and use ultrasonic emulsification to disperse for 15 minutes. After nitrogen substitution in the autoclave, 10 g of vinyl chloride was added by pressing, and 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the reaction was carried out at 60° C. for 3 hours. An aqueous dispersion of the polymer is obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing example 15

In a 500mL autoclave, add behenyl acrylate=20g, lauryl acrylate=17.5g, glycidyl methacrylate=2.5g, pure water=145g, tripropylene glycol=15g, sorbitan mono Oleic acid ester=1.5g, polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether=2g, di-octadecyl dimethyl ammonium chloride=1.5g, under stirring at 60 ℃ and use ultrasonic emulsification to disperse for 15 minutes. After nitrogen substitution in the autoclave, 10 g of vinyl chloride was added by pressing, and 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the reaction was carried out at 60° C. for 3 hours. An aqueous dispersion of the polymer is obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Comparative Manufacturing Example 1

In a 500mL autoclave, add lauryl acrylate = 50g, pure water = 145g, tripropylene glycol = 15g, sorbitan monooleate = 1.5g, polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether = 2 g, di-octadecyl dimethyl ammonium chloride = 1.5 g, ultrasonic emulsification and dispersion at 60° C. for 15 minutes while stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Comparative Manufacturing Example 2

Add cetyl acrylate = 50g, pure water = 145g, tripropylene glycol = 15g, sorbitan monooleate = 1.5g, polyoxyethylene (EO: 18) secondary alkane into a 500mL autoclave Base (C12-14) ether = 2 g, di-octadecyl dimethyl ammonium chloride = 1.5 g, and ultrasonically emulsify and disperse at 60° C. for 15 minutes while stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Comparative Manufacturing Example 3

Add stearyl acrylate = 15g, lauryl acrylate = 35g, pure water = 145g, tripropylene glycol = 15g, sorbitan monooleate = 1.5g, polyoxyethylene (EO: 18) Secondary alkyl (C12-14) ether = 2 g, di-octadecyl dimethyl ammonium chloride = 1.5 g, ultrasonic emulsification and dispersion at 60° C. for 15 minutes while stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Comparative Manufacturing Example 4

In a 500mL autoclave, add stearyl acrylate=50g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=2g, polyoxyethylene (EO: 18) stearyl Ether = 2 g, dioctadecyldimethylammonium chloride = 1 g, and was dispersed by ultrasonic emulsification at 60° C. for 15 minutes while stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Comparative Manufacturing Example 5

In a 500mL autoclave, add stearyl acrylate=50g, pure water=145g, tripropylene glycol=15g, acetylene glycol polyoxyethylene adduct=0.25g, polyoxyethylene (EO: 18 ) lauryl ether = 3 g, octadecyltrimethylammonium chloride = 0.75 g, and was dispersed by ultrasonic emulsification at 60° C. for 15 minutes while stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Comparative Manufacturing Example 6

Add stearyl acrylate = 35g, glycidyl methacrylate = 2.5g, pure water = 145g, tripropylene glycol = 15g, sorbitan monooleate = 2g, polyoxygen Ethylene (EO: 18) stearyl ether = 2 g, di-octadecyl dimethyl ammonium chloride = 1 g, and were dispersed by ultrasonic emulsification at 60° C. for 15 minutes while stirring. After nitrogen substitution in the autoclave, 12.5 g of vinyl chloride was added by pressing, 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the reaction was carried out at 60° C. for 3 hours. An aqueous dispersion of the polymer is obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Comparative Manufacturing Example 7

Add stearyl acrylate=35g, glycidyl methacrylate=2.5g, pure water=145g, tripropylene glycol=15g, acetylene glycol polyoxyethylene adduct=0.25 into a 500mL autoclave g. Polyoxyethylene (EO: 18) lauryl ether = 3 g, octadecyltrimethylammonium chloride = 0.75 g, and ultrasonically emulsify and disperse at 60° C. for 15 minutes while stirring. After nitrogen substitution in the autoclave, 12.5 g of vinyl chloride was added by pressing, 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g, and reacted at 60° C. for 3 hours, An aqueous dispersion of the polymer is obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Table 1 shows raw materials used in Production Examples and Comparative Production Examples.

Reference Example 1 (Manufacture of Fluorine-based Removal Agent)

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ (n=2.0) 14.9g, stearyl acrylate 43, 46g, pure water into a 500ml reaction flask 110g, dipropylene glycol monomethyl ether 18.62g, distearyl dimethyl ammonium chloride 3.08g, stearyl trimethyl ammonium chloride 0.87g, polyoxyethylene lauryl ether (EO: 18, 2.1 g of EO represents the number of ethylene oxide units) and 0.65 g of polyoxyethylene isotridecyl ether (EO: 3) were ultrasonically emulsified and dispersed at 60° C. for 15 minutes while stirring. After nitrogen substitution in the reaction flask, a solution of 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride and 9 g of water was added, and the reaction was carried out at 60° C. for 5 hours. An aqueous dispersion of the polymer (fluorine-based repellant) was obtained. The composition of the polymer is basically the same as that of the added monomers.

Example 1

50 g of the aqueous liquid prepared in Production Example 1 was diluted with tap water to prepare a test liquid (1000 g). A cloth (510 mm×205 mm) was dipped in the test solution, passed through a cloth mandrel, and treated with a pin tenter at 160° C. for 2 minutes. For the fabric, PET taffeta, nylon taffeta, and denim are used. The various cloths were divided into unwashed cloths and cloths washed 5 times, and a shower water repellency test (washing durability test) was implemented. About the hand feeling test and the mechanical stability test, it was carried out with an unwashed cloth. The results are shown in Table 2.

Embodiment 2～9 and comparative example 1～5

After processing in the same manner as in Example 1, a shower water repellency test (washing durability test), a texture test, and a mechanical stability test were implemented. The results are shown in Table 2.

Examples 10-15 and Comparative Examples 6-7

50 g of the aqueous liquid and 10 g of the MDI-based blocked isocyanate (solid content concentration: 20%) prepared in each production example were diluted with tap water to prepare a test solution (1000 g). Thereafter, it was treated in the same manner as in Example 1, and a shower water repellency test (washing durability test), a mechanical stability test, and a peel strength test were performed. The results are shown in Table 2.

Example 16

25 g of the aqueous liquid prepared in Production Example 1 and 25 g of the fluorine-based dialing agent prepared in Reference Example 1 were diluted with tap water to prepare a test solution (1000 g). Thereafter, it was treated in the same manner as in Example 1, and a shower water repellency test (washing durability test), hand feeling, and mechanical stability test were implemented. The results are shown in Table 1.

Example 17

Dilute 25 g of the aqueous liquid obtained in Production Example 10, 25 g of the fluorine-based dialing agent obtained in Reference Example 1, and 10 g of blocked isocyanate (solid content concentration 20%) of the MDI system with tap water to prepare a test solution (1000 g) . Thereafter, it was treated in the same manner as in Example 1, and a shower water repellency test (washing durability test), a mechanical stability test, a peel strength test, and a washing durability test were performed. The results are shown in Table 2.

[Table 1]

Note)

Emulsifier 1: Sorbitan monooleate/polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether/dioctadecyldimethylammonium chloride=3/4/ 3 (weight ratio)

Emulsifier 2: Acetylene glycol polyoxyethylene adduct/polyoxyethylene (EO: 18) isotridecyl ether/di-octadecyldimethylammonium chloride=2/4/ 4 (weight ratio)

Emulsifier 3: Acetylene glycol polyoxyethylene adduct/polyoxyethylene (EO: 18) lauryl ether/octadecyltrimethylammonium chloride=2/5.8/2.2 (weight ratio)

Emulsifier 4: Sorbitan monooleate/polyoxyethylene (EO: 18) stearyl ether/dioctadecyldimethylammonium chloride=4/4/2 (weight ratio)

Emulsifier 5: Acetylene glycol polyoxyethylene adduct/polyoxyethylene (EO: 18) lauryl ether/octadecyltrimethylammonium chloride=0.5/6/1.5 (weight ratio)

[Table 2]

Industrial availability

The treating agent of the present invention is suitably applied to substrates such as fiber products and masonry, and imparts excellent water and oil repellency to the substrates.

Other aspects of the present invention are as follows.

<1> An aqueous emulsion treatment agent comprising:

(1) A polymer having 40% by weight or more of a long chain (methyl group) represented by the formula: CH ₂ =CA ¹¹ -C(=O)-OA ¹² derived from (a) relative to the polymer. ) repeating units of acrylate monomers,

In the formula, ^A11 is a hydrogen atom or a methyl group, and A12 is a straight-chain or branched aliphatic hydrocarbon group with ¹⁸ to 30 carbon atoms;

(2) Surfactant, which contains nonionic surfactant and cationic surfactant, the amount of cationic surfactant is more than 15% by weight; and

(3) Aqueous liquid medium.

<2> The aqueous emulsion treatment agent according to <1>, wherein the polymer (1) further has a formula derived from (b): CH ₂ =CA ²¹ -C(=O)-OA ²² represented by Repeating units of short-chain (meth)acrylate monomers,

In the formula, ^A21 is a hydrogen atom or a methyl group, and ^A22 is a linear or branched aliphatic hydrocarbon group with less than 18 carbon atoms.

<3> The aqueous emulsion treatment agent according to <1> or <2>, wherein the polymer (1) further has a repeating unit derived from (c) a non-fluorinated crosslinkable monomer.

<4> The aqueous emulsion treatment agent according to <3>, wherein the non-fluorinated crosslinkable monomer (c) is a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond. Compounds with saturated double bonds and at least 1 reactive group.

<5> The aqueous emulsion treatment agent according to any one of <1> to <4>, wherein the polymer (1) has a repeating unit derived from (d) a halogenated olefin monomer.

<6> The aqueous emulsion treatment agent according to any one of <1> to <4>, wherein the polymer (1) does not have a repeating unit derived from (d) a halogenated olefin monomer.

<7> The aqueous emulsion treatment agent according to <5> or <6>, wherein the halogenated olefin monomer (d) is at least one selected from vinyl chloride and vinylidene chloride.

<8> The aqueous emulsion treatment agent according to any one of <1> to <7>, wherein the polymer (1) is a monomer-free homopolymer having a glass transition temperature of 50° C. or higher (forma Both base) acrylate monomers and (meth)acrylate monomers having a cyclic hydrocarbon group.

<9> The aqueous emulsion treatment agent according to any one of <1> to <8>, wherein the polymer (1) does not contain a fluorine atom.

<10> The aqueous emulsion treatment agent according to any one of <1> to <9>, wherein, in the polymer (1), the repeating unit (b) is The amount is 0 to 150 parts by weight, the amount of the repeating unit (c) is 0 to 50 parts by weight, and the amount of the repeating unit (d) is 0 to 100 parts by weight.

<11> The aqueous emulsion treatment agent according to any one of <1> to <10>, wherein the nonionic surfactant has the formula: R ¹ O-(CH ₂ CH ₂ O) _p -(R ² O) the compound shown in _q -R ³ ,

In the formula, R ¹ is an alkyl group with 1 to 22 carbon atoms, an alkenyl group or an acyl group with 2 to 22 carbon atoms, and R ² are independently, the same or different, and are those with 3 or more carbon atoms (for example, 3 to 10) An alkylene group, ^R3 is a hydrogen atom, an alkyl group with 1 to 22 carbon atoms, or an alkenyl group with 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more.

<12> The aqueous emulsion treatment agent according to any one of <1> to <10>, wherein the nonionic surfactant is an acetylenic alcohol selected from acetylenic alcohols and oxyethylene adducts of acetylenic alcohols compound.

<13> The aqueous emulsion treatment agent according to <12>, wherein the acetylenic alcohol compound has the formula: HO-CR ¹¹ R ¹² -C≡C-CR ¹³ R ¹⁴ -OH or HO-CR ¹⁵ R ¹⁶ -C≡ Compounds represented by C－H,

In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are independently the same or different, and represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms.

<14> The aqueous emulsion treatment agent according to any one of <1> to <13>, wherein the cationic surfactant has the formula: R ²¹ -N ⁺ (-R ²² )(-R ²³ )(- R ²⁴ ) Compounds represented by X ^- ,

In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ are independently the same or different, and are hydrocarbon groups having 1 to 30 carbon atoms, and X is an anionic group.

<15> The aqueous emulsion treatment agent according to any one of <1> to <14>, wherein the fiber treatment agent further contains a fluoropolymer.

<16> The water-based emulsion treatment agent according to any one of <1> to <15>, wherein the water-based emulsion has a zeta potential of +30 mV or more.

<17> The water-based emulsion treatment agent according to any one of <1> to <16>, wherein the dynamic surface tension of the water-based emulsion is 55 mN/m or less.

<18> The aqueous emulsion treatment agent according to any one of <1> to <17>, which is a fiber treatment agent.

<19> The water-based emulsion treatment agent according to any one of <1> to <18>, which is a water and oil repellent or an antifouling agent.

<20> A method of treating a fiber product, including the step of treating the fiber product with the aqueous emulsion treatment agent according to any one of <1> to <19>.

<21> A fiber product treated with the aqueous emulsion treatment agent according to any one of <1> to <19>.

Claims (8)

1. A surface treatment agent, which is an aqueous emulsion, is characterized in that it contains: (1) A non-fluoropolymer having a repeating unit derived from a long-chain (meth)acrylate monomer represented by the formula (a): CH ₂ ═CA ¹¹ -C(=O)—O—A ¹² , In the formula, ^A11 is a hydrogen atom or a methyl group, and A12 is a straight-chain or branched aliphatic hydrocarbon group with ¹⁸ to 30 carbon atoms; (2) A surfactant containing both a nonionic surfactant and a cationic surfactant, and the amount of the cationic surfactant relative to the total amount of the nonionic surfactant and the cationic surfactant is 22 to 60% by weight; and (3) Aqueous liquid medium. 2. surface treatment agent as claimed in claim 1, is characterized in that: The non-fluoropolymer (1) does not contain a (meth)acrylate monomer having a cyclic hydrocarbon group. 3. surface treatment agent as claimed in claim 1 or 2, is characterized in that: The nonionic surfactant is at least one selected from ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, The cationic surfactant is at least one selected from the group consisting of amines, amine salts, quaternary ammonium salts, imidazolines, and imidazolinium salts. 4. surface treatment agent as claimed in claim 1 or 2, is characterized in that: Surface treatment does not contain fluoropolymers. 5. surface treatment agent as claimed in claim 1 or 2, is characterized in that: The surface treatment agent contains fluoropolymer. 6. surface treatment agent as claimed in claim 1 or 2, is characterized in that: The surface treatment agent is water and oil repellent or antifouling agent, In the surface treatment agent, the concentration of the non-fluoropolymer (1) is 0.01 to 95% by weight, and the total amount of the surfactant (2) is 0.1 to 20 parts by weight relative to 100 parts by weight of the polymer, The non-ionic surfactant is a compound represented by the formula: R ¹ O-(CH ₂ CH ₂ O) _p- (R ² O) _q -R ³ , In the formula, R is an alkyl group with ¹ to 22 carbon atoms or an alkenyl or acyl group with 2 to 22 carbon atoms, R ² are independently identical or different, and are alkylene groups having 3 or more carbon atoms, ^R3 is a hydrogen atom, an alkyl group with 1 to 22 carbon atoms or an alkenyl group with 2 to 22 carbon atoms, p is a number greater than 2, q is a number of 0 or more than 1, The cationic surfactant is a compound represented by the formula: R ²¹ -N ⁺ (-R ²² )(-R ²³ )(-R ²⁴ )X ^- , In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ are independently, the same or different, and are hydrogen atoms or hydrocarbon groups with 1 to 50 carbon atoms, X is an anionic group. 7. A method for processing fiber products, characterized in that: It includes the step of treating fiber products with the surface treatment agent described in any one of claims 1-6. 8. A fiber product treated with the surface treatment agent according to any one of claims 1 to 6.