TW201529824A - Surface treatment agent - Google Patents

Abstract

Provided is an aqueous emulsion surface treatment agent without using any fluorine-containing monomer, especial the fluoroalkyl-containing monomer. Disclosed is a surface treatment agent containing the following components: (1) a nonfluoropolymer having (i) a repeating unit derived from a long chain (metha)acrylte ester monomer represented by the following formula CH2 = CA11-C(= O)-O-A12 [wherein, A11 is a hydrogen atom or a methyl group, A12 is a straight or branched C18-30 aliphatic hydrocarbon group] (ii) a repeating unit derived from a (metha)acrylte monomer having a cyclic hydrocarbon group, (2) a surface active agent containing one or both nonionic surface active agent and cationic surface active agent, (3) a liquid medium containing water.

Description

Surface treatment agent

This invention relates to a surface treatment agent, particularly to water and oil repellents and antifouling agents.

Conventionally, a fluorine-containing water-repellent oil-repellent agent composed of a fluorine-containing compound has been known. When the water-repellent oil-repellent agent is used for processing a substrate such as a fiber product, it exhibits good water repellency.

According to recent research results [EPA report "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS" (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)] Concerns about the environmental load of PFOA (perfluorooctanoic acid), one of the long-chain fluorocarbon compounds, was published on April 14, 2003 by the EPA (US Environmental Protection Agency) to strengthen the scientific investigation of 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) and EPA Environmental News FOR RELEASE: MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (http://www.epa.gov/ Opptintr/pfoa/pfoaprs.pdf) and EPA OPPT FACT SHEET April 14, 2003 (http://www.epa.gov/opp tintr/pfoa/pfoafacts.pdf), publicly published short-chain polymers (telomer) are decomposed or The possibility of metabolism to form PFOA (short-chain polymer means long-chain fluoroalkyl). Further, various products in which a short-chain polymer is used for a foam fire extinguishing agent, a care product, a cleaning product, a carpet, a textile, a paper, a leather, and the like which impart water repellency and antifouling properties are also disclosed. Concerned about the accumulation of fluorochemicals in the environment.

Further, in order to exhibit water repellency and oil repellency, the fluorine-containing water-repellent oil-repellent agent containing a fluoropolymer needs to be heat-treated at a high temperature (for example, 100 ° C or higher) after adhering to a substrate such as a fiber product. High energy is required in high temperature heat treatment.

Furthermore, fluoropolymers are expensive.

Therefore, there is a need to use no fluoropolymer or to reduce the amount of fluoropolymer.

In JP-A-2006-328624, a water-repellent agent containing a non-fluorine-based polymer having an ester group having a carbon number of 12 or more and a (meth) acrylate as a monomer unit is described, and (meth) The composition ratio of the acrylate is from 80 to 100% by mass based on the total amount of the monomer units constituting the non-fluorine-based polymer.

However, the water repellent has poor water repellency.

[Previous Technical Literature]

[Patent Document 1] JP-A-2006-328624

SUMMARY OF THE INVENTION An object of the present invention is to provide a surface treatment agent which can impart excellent water repellency and oil repellency without using a fluorine-containing monomer, particularly a monomer containing a fluoroalkyl group.

The present invention relates to a treatment agent comprising the following aqueous emulsions of (1), (2) and (3), (1) a polymer comprising: (i) a long-chain (meth) acrylate monomer a repeating unit derived, and (ii) having a repeating unit derived from a long-chain (meth) acrylate monomer having a cyclic hydrocarbon group; (2) a surfactant, and (3) a liquid medium containing water .

The ideal aspect of the invention is as follows.

[1]

A surface treatment agent comprising the aqueous emulsions of the following (1), (2) and (3), and (1) a non-fluoropolymer comprising: (i) a (meth) group represented by the following formula Repeating unit derived from acrylate monomer, CH ₂ =CA ¹¹ -C(=O)-OA ¹²

[wherein A ¹¹ is a hydrogen atom or a methyl group, A ¹² is a linear or branched aliphatic hydrocarbon group having a carbon number of 18 to 30], and (ii) is a (meth) acrylate single having a cyclic hydrocarbon group; a repeating unit derived from a body; (2) a surfactant comprising one or both of a nonionic surfactant and a cationic surfactant, and (3) a liquid medium containing water.

[2]

The surface treatment agent according to [1], wherein the acrylate monomer (ii) having a cyclic hydrocarbon group is a compound represented by the following formula: CH ₂ = CA ²¹ -C(=O)-OA ²²

[In the formula, A ²¹ is a hydrogen atom or a methyl group, and A ²² is a cyclic hydrocarbon group having a carbon number of 4 to 30].

[3]

The surface treatment agent according to [1] or [2] wherein the surfactant (2) comprises both a nonionic surfactant and a cationic surfactant, relative to the nonionic surfactant and cationic The total amount of the surfactants is 22% by weight or more based on the amount of the cationic surfactant.

[4]

The surface treatment agent according to any one of [1] to [3] wherein the nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamines, polyols, and amine oxides. At least one of the group, the cationic surfactant is at least one selected from the group consisting of an amine, an amine salt, a 4-grade ammonium salt, an imidazoline, and an imidazolinium salt.

[5]

The surface treatment agent according to any one of [1] to [4] wherein The agent comprises an interfacially active compound having both a guanamine group and an amine group.

[6]

The surface treatment agent according to any one of [1] to [5] wherein the surface treatment agent does not contain a fluoropolymer.

[7]

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

[8]

The surface treatment agent according to any one of [1] to [7], which is a water-repellent oil-repellent agent or an anti-fouling agent.

[9]

A method of treating a fibrous product, which comprises treating a fibrous product with a surface treating agent according to any one of [1] to [8].

[10]

A fiber product treated by the surface treatment agent according to any one of [1] to [8].

Since the surface treatment agent of the present invention does not use a monomer having a fluorine-containing alkyl group, there is no concern that the fluorine-containing compound accumulates in the environment. The surface treating agent of the present invention can impart excellent water repellency to the substrate, in particular, a strong water repellent. Furthermore, it is not necessary to perform heat treatment at a high temperature, and water treatment is exhibited at a low temperature.

The stability of the treatment agent of the present invention (the stability of the emulsion) is good. The treating agent of the present invention has a strong water repellency for those including heavy rain.

A treatment agent containing only a non-fluoropolymer as an active ingredient can obtain a performance equal to or higher than that of a treatment agent containing only a fluorine-containing polymer having a fluorine-containing alkyl group as a constituent unit as an active ingredient (in particular, Including the initial water and oil repellency of water and oil.

The copolymer (preferably, non-fluoropolymer) in the present invention is a repeating unit containing the following (i) and (ii): (i) derived from a long-chain (meth) acrylate monomer, and Ii) a repeating unit derived from a (meth) acrylate monomer having a cyclic hydrocarbon group.

The copolymer may further comprise one or both of (iii), (iv): (iii) a repeating unit derived from a short chain (meth) acrylate monomer, and (iv) a derivative derived from a non-fluorinated bridging monomer. Repeat unit.

The copolymer may also have a fluorine atom, but is preferably a fluorine-free atom. That is, the copolymer is preferably a non-fluoropolymer.

(i) long chain (meth) acrylate monomer

The long chain (meth) acrylate monomer is a compound represented by the formula: CH ₂ =CA ¹¹ -C(=O)-OA ¹²

[In the formula, A ¹¹ is a hydrogen atom or a methyl group, and A ¹² is a linear or branched aliphatic hydrocarbon group having a carbon number of 18 to 30. ].

The long chain (meth) acrylate monomer has no fluoroalkyl group. The long-chain (meth) acrylate monomer preferably contains a fluorine atom, but is preferably a fluorine-free atom.

A ¹¹ is particularly desirable for methyl groups.

A ¹² is a linear or branched hydrocarbon group. The linear or branched hydrocarbon group may specifically be a linear hydrocarbon group. The linear or branched hydrocarbon group has a carbon number of 18 to 30. The linear or branched hydrocarbon group preferably has a carbon number of 18 to 28, particularly preferably 18 or 22, and is usually a saturated aliphatic hydrocarbon group, particularly preferably an alkyl group.

Particularly preferred specific examples of the long-chain (meth) acrylate monomer are stearyl (meth) acrylate and behenyl (meth) acrylate. Stearyl ester (meth) acrylate is particularly preferred.

Due to the presence of the long chain (meth) acrylate monomer, the water repellency and oil repellency imparted by the polymer are improved.

(ii) acrylate monomer having a cyclic hydrocarbon group

The acrylate single system containing a cyclic hydrocarbon group is preferably a compound represented by the following formula: CH ₂ =CA ²¹ -C(=O)-OA ²² [wherein A ²¹ hydrogen atom or methyl group, A ²² system A cyclic hydrocarbon-containing group having 4 to 30 carbon atoms. ]

The acrylate monomer having a cyclic hydrocarbon group is a monomer having a high glass transition point of a homopolymer (for example, 50 ° C or more, particularly 80 ° C or more).

The acrylate monomer having a cyclic hydrocarbon group has no fluoroalkyl group. The acrylate monomer having a cyclic hydrocarbon group may contain a fluorine atom, but is preferably a fluorine-free atom.

A ²¹ is particularly desirable as a methyl group.

A ²² is a cyclic hydrocarbon group which may have a chain group (for example, a linear or branched chain hydrocarbon group). The cyclic hydrocarbon group may, for example, be a saturated or unsaturated monocyclic group, a polycyclic group or a bridged cyclic group. The cyclic hydrocarbon group is preferably a saturated one. The cyclic hydrocarbon group has a carbon number of 4 to 30 and is preferably 6 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an aromatic aliphatic group having 7 to 20 carbon atoms. The carbon number of the cyclic hydrocarbon group is preferably 15 or less, particularly preferably 12 or less. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group are cyclohexyl, tert-butylcyclohexyl, isobornyl, dicyclopentanyl, dicyclopentenyl, adamantyl.

Specific examples of the acrylate monomer having a cyclic hydrocarbon group include cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, and benzyl (meth)acrylate. Isobornyl acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, Adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and the like.

Due to the presence of the acrylate monomer containing a cyclic hydrocarbon group, the water repellency and oil repellency imparted by the copolymer are improved.

(iii) short chain (meth) acrylate monomer

The copolymer may also have repeating units derived from short chain (meth) acrylate monomers.

The short chain (meth) acrylate single system is preferably a compound represented by the following formula: CH ₂ =CA ³¹ -C(=O)-OA ³² [wherein A ³¹ is a hydrogen atom or a methyl group, A ³² A linear or branched aliphatic hydrocarbon group having a carbon number of less than 18. ]

The short chain (meth) acrylate monomer has no fluoroalkyl group. The short-chain (meth) acrylate monomer may contain a fluorine atom, but is preferably a fluorine-free atom.

A ³¹ is particularly desirable for methyl groups.

A ³² is a linear or branched hydrocarbon group. The linear or branched hydrocarbon group may specifically be a linear hydrocarbon group. The linear or branched hydrocarbon group has a carbon number of 1 to 17. The linear or branched hydrocarbon group has a carbon number of 1 to 14 and is particularly preferably a saturated aliphatic hydrocarbon group.

Specific examples of the short-chain (meth) acrylate monomer are methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and tertiary butyl (meth) acrylate. Lauryl (meth)acrylate, myristyl (meth)acrylate, and cetyl (meth)acrylate. Particularly preferable specific examples of the short-chain (meth) acrylate monomer are lauryl (meth) acrylate and cetyl (meth) acrylate.

Due to the presence of the short chain (meth) acrylate monomer, the water repellency and feel of the polymer will be better.

(iv) non-fluorinated bridging monomer

The copolymer may or may not have repeating units derived from non-fluorinated bridging monomers.

The non-fluorinated bridging monomer is a monomer having no fluorine atom. The non-fluorinated bridging monomer may be a compound having at least two reactive groups and/or an olefinic carbon-carbon double bond (ideally, a (meth) acrylate group) and containing no fluorine. Non-fluorine bridged single The compound may be a compound having at least two olefinic carbon-carbon double bonds (ideally, a (meth) acrylate group), or a compound having at least one olefinic carbon-carbon double bond and at least one reactive group. . Examples of the reactive group are a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amine group, a carboxyl group and the like.

The non-fluorinated bridging monomer may be a mono (meth) acrylate having a reactive group, di(meth) acrylate or mono (meth) acrylamide. Alternatively, the non-fluorinated bridging monomer can be a di(meth)acrylate.

One example of the non-fluorine bridging monomer is an ethylene monomer having a hydroxyl group.

As the non-fluorinated bridging monomer, for example, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, (methyl) can be exemplified. Hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-ethoxyethyloxyethyl (meth) acrylate, butadiene, isoprene, chloroprene , monochlorovinyl acetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc. But not limited to these.

Due to the presence of non-fluorinated bridging monomers, the washfastness imparted by the polymer is increased.

(v) other monomers

As the monomer (v) other than the monomers (i) to (iv), for example, a non-fluorine non-bridged monomer can be used.

Examples of other monomers include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth)acrylate, poly(meth)acrylic acid propylene glycol, methoxy poly(methyl). Ethylene glycol acrylate, methoxy poly(meth) acrylate, and vinyl alkyl ether. Other monomers are not limited In these cases.

The other monomer may be a halogen olefin (preferably free of fluorine atoms).

The haloolefin is preferably an olefin having 2 to 20 carbon atoms which is substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The haloolefin is preferably a chloroolefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Desirable specific examples of the haloolefin are vinyl halide such as vinyl chloride, vinyl bromide, iodoethylene, and dihaloethylene such as dichloroethylene, dibromoethylene, and diiodoethylene.

In the present specification, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylic acid amide" means acrylamide or methacrylamide.

Since the water repellency is improved, it is desirable that each monomer is an acrylate.

The monomers (i) to (v) may each be used singly or in a mixture of two or more kinds.

The amount of the monomer (i) is 40% by weight or more, and preferably 50% by weight or more based on the copolymer. The amount of the monomer (i) is 95% by weight or less based on the copolymer, and may be, for example, 80% by weight or less, or 75% by weight or less, or 70% by weight or less.

In the copolymer, the amount of the repeating unit (ii) may be 1 to 150 parts by weight, desirably 1 to 30 parts by weight, and the amount of the repeating unit (iii) may be 0 to 100 with respect to 100 parts by weight of the monomer (i). Parts by weight, ideally 1 to 30 weight The amount of the repeating unit (iv) may be from 0 to 50 parts by weight, desirably from 1 to 10 parts by weight, and the amount of the repeating unit (v) is from 0 to 100 parts by weight, desirably from 1 to 30 parts by weight.

The number average molecular weight (Mn) of the copolymer may generally be from 1,000 to 1,000,000, for example from 5,000 to 500,000, particularly from 3,000 to 200,000. The number average molecular weight (Mn) of the copolymer is generally 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, the monomers are copolymerized to obtain a treating agent composition in which the copolymer is dispersed or dissolved in a medium.

The monomers used in the present invention are as follows.

Monomer (i) + (ii), monomer (i) + (ii) + (iii), monomer (i) + (ii) + (iv), or monomer (i) + (ii) + ( Iii) + (iv).

In addition to the above, the monomer (v) can be used.

It is desirable to use a non-fluorinated bridging monomer (iv). The single system is preferably a combination of monomer (i) + monomer (ii) + monomer (iv) or a combination of monomer (i) + monomer (ii) + monomer (iv) + haloolefin. The water repellency of these combinations is high.

(2) Surfactant

In the treatment agent of the present invention, the surfactant contains a nonionic surfactant and a cationic surfactant. The surfactant may be formed only of a nonionic surfactant and a cationic surfactant, or may contain other surfactants other than the nonionic surfactant and the cationic surfactant. Examples of other surfactants are amphoteric surfactants. The surfactant is preferably free of an anionic surfactant.

(2-1) Nonionic surfactant

Examples of the nonionic surfactant include ethers, esters, ester ethers, alkanolamines, polyhydric alcohols, and amine oxides.

An example of an ether is a compound having an oxyalkylene group (ideally, a polyoxyethylene ester).

Examples of esters are esters of alcohols and fatty acids. The alcohol is exemplified by 1 to 6 members (particularly 2 to 5 members) of an alcohol having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, an aliphatic alcohol). The fatty acid is exemplified by a carbon number of 2 to 50, particularly a saturated or unsaturated fatty acid having 5 to 30 carbon atoms.

Examples of the ester ethers are esters of an alcohol and a fatty acid, and an alkylene oxide (particularly ethylene oxide) addition compound. The alcohol is exemplified by 1 to 6 members (particularly 2 to 5 members) of an alcohol having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, an aliphatic alcohol). The fatty acid is exemplified by a carbon number of 2 to 50, particularly a saturated or unsaturated fatty acid having 5 to 30 carbon atoms.

Examples of the alkanolamines are formed from fatty acids and alkanolamines. The alkanolamine can be a monoalkanolamine or a dialkanolamine. The fatty acid is exemplified by a carbon number of 2 to 50, particularly a saturated or unsaturated fatty acid having 5 to 30 carbon atoms. The alkanolamine may have an amine group of 1 to 3 and a hydroxyl group of 1 to 5 having a carbon number of 2 to 50. Do not be an alkanol of 5 to 30.

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

The amine oxide is an oxide (e.g., a carbon number of 5 to 50) which may be an amine (a secondary amine or preferably a tertiary amine).

The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene (preferably polyoxyethylene). The carbon number of the alkylene group in the oxygen alkyl group is preferably from 2 to 10. The number of oxygen alkyl groups in the molecule of the nonionic surfactant is generally from 2 to 100.

The nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamines, polyhydric alcohols, and amine oxides, and is preferably a nonionic surfactant having an oxygen alkyl group.

The nonionic surfactant may be a linear and/or branched aliphatic (saturated and/or unsaturated) alkylene oxide adduct, a linear and/or branched fatty acid (saturated and / or unsaturated) polyalkylene glycol ester, polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), acetylene glycol alkylene oxide adduct, etc. . Among these, the alkylene oxide addition moiety and the polyalkylene glycol moiety are constructed as polyoxyethylene (POE) or polyoxypropylene (POP) or POE/POP copolymers (which may be random copolymers or blocks). Copolymer) is ideal.

Further, the nonionic surfactant is preferably a structure containing no aromatic group from the viewpoint of environmental problems (biodegradability, environmental hormone, etc.).

The nonionic surfactant may be a compound represented by the following formula: R ¹ O-(CH ₂ CH ₂ O) _p -(R ² O) _q -R ³ wherein R ¹ is a carbon number of 1 to 22 alkyl group or a C2-4 alkylene group (alkenyl) 2 to 22 or acyl (acyl), the individual R ² each independently may be the same or different, 3 or more carbon atoms (e.g., 3 to 10) extending in the alkyl Further, R ³ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or more. ].

R ¹ is preferably from 8 to 20 carbon atoms, particularly from 10 to 18 carbon atoms. A specific specific example of R ^{1 may} , for example, be a lauryl group, a tridecyl group or an oil group.

The example of R ² is a propyl group and a butyl group.

In the nonionic surfactant, 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 also form a polyoxyalkylene chain.

The nonionic surfactant may be a polyoxyalkylene alkyl alkyl ether having a hydrophilic polyoxyalkylene chain and a hydrophobic oxygen alkyl chain (particularly a polyoxyalkylene chain) in the center. . The hydrophobic oxygen-extended alkyl chain may, for example, be an oxypropyl group, an oxygen-extended butyl chain, a styrene chain or the like, and particularly preferably an oxygen-extended propyl chain.

An ideal nonionic surfactant is a surfactant represented by the following formula: R ¹ O-(CH ₂ CH ₂ O) _p -H [wherein R ¹ and p have the same meanings as defined above. ].

Specific examples of the nonionic surfactant are as follows.

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 [wherein, p and q have the same meanings as described above. ]Wait.

Specific examples of the nonionic surfactant include ethylene oxide and hexylphenol, isooctylphenol, cetyl alcohol, oleic acid, alkyl (C ₁₂ -C ₁₆ ) thiol, sorbitan mono-fatty acid A condensation product of (C ₇ -C ₁₉ ) or an alkyl (C ₁₂ -C ₁₈ )amine or the like.

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

The average molecular weight of the nonionic surfactant is generally from 300 to 5,000, for example, from 500 to 3,000.

Nonionic surfactants can be used alone or in combination the above.

The nonionic surfactant is preferably a combination of two or more kinds. A combination of two or more thereof, at least one kind of nonionic surfactant may be the R ¹ group (and / or R ³ groups) is a branched alkyl group (e.g., isotridecyl) R ¹ O- ( CH ₂ CH ₂ O) _p -(R ² O) _q -R ³ [Specifically, a compound represented by R ¹ O-(CH ₂ CH ₂ O) _p -H]. The R ¹ group is a branched alkyl group of the nonionic surfactant amount with respect to the 8 to 50 parts by weight of a nonionic surfactant (B 2) a total of 100 parts by weight of 5 to 100 parts by weight, for example, may be Especially 10 to 40 parts by weight. In the combination of two or more kinds, the remaining nonionic surfactant may be a linear alkyl group (saturated and/or unsaturated) of the R ¹ group (and/or R ³ group) (for example, lauryl (n) -Lauryl)) of R ¹ O-(CH ₂ CH ₂ O) _p -(R ² O) _q -R ³ [in particular, R ¹ O-(CH ₂ CH ₂ O) _p -H] Compound.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene water-free pear. Alcohol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid glycerides, polyoxyethylene glycerin fatty acid esters, polyglycerol fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty decylamines, Fatty acid alkylol amide, alkyl alkanolamide, acetylene glycol, oxygen extended ethyl adduct of acetylene glycol, polyethylene glycol polypropylene glycol block copolymer, etc. .

The dynamic surface tension of the aqueous emulsion is reduced (ie, the aqueous emulsion easily penetrates into the substrate), so for nonionic surfactants, acetylenic alcohol (especially, acetylene glycol), or acetylenic alcohol (especially, acetylene glycol) The oxygen-extended ethyl adduct is ideal.

An ideal nonionic surfactant is an alcohol having an unsaturated triple bond or an alkylene oxide adduct of the alcohol (both of which is referred to as an "alkynol compound"). It is particularly desirable that the nonionic surfactant is an alkylene oxide adduct of a monohydric or polyhydric alcohol having an unsaturated triple bond.

The acetylenic alcohol compound is a compound containing one or more triple bonds and one or more hydroxyl groups. The acetylenic compound can be a compound containing a polyoxyalkylene moiety. Examples of the polyoxyalkylene moiety include a random addition structure of a polyoxyethylene group, a polyoxyalkylene group, a polyoxyalkylene group, and a polyoxyalkylene group, and a polyoxyalkylene group and a polyoxygen group. A block addition structure of a propyl group.

The acetylenic compound may be a compound represented by the formula: HO-CR ¹¹ R ¹² -C≡C-CR ¹³ R ¹⁴ -OH, or HO-CR ¹⁵ R ¹⁶ -C≡CH [wherein, 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 compound can be an alkylene oxide adduct of the compound of the 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. Further, the alkylene oxide is preferably an alkylene oxide having 1 to 20 (especially 2 to 5) carbon atoms such as ethylene oxide or propylene oxide, and the alkylene oxide is preferably 1 to 50. .

Specific examples of the acetylenic alcohol compound include acetylene glycol, propynyl alcohol, 2,5-dimethyl-3-hexyne-2,5-diol, and 3,6-dimethyl-4-octane. Alkyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl 1-hexynyne-3-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3-hexyne-2,5-diol 2-butyne-1,4-diol and the like. Polyethoxylated alcohols and ethylene oxide adducts of the specific example compounds can also be mentioned.

The nonionic surfactant may be one that does not have a triple bond or may have a triple bond. The nonionic surfactant may be one of a nonionic surfactant having no triple bond or a nonionic surfactant having a triple bond, but may be a nonionic surfactant having no triple bond and a non-three-bond non-surfactant. A combination of ionic surfactants. A nonionic surfactant having no triple bond (for example, a nonionic surfactant having an oxygen alkyl group) in a combination of a nonionic surfactant having no triple bond and a nonionic surfactant having a triple bond The weight ratio of the nonionic surfactant (e.g., acetylene alcohol compound) having a triple bond may be from 10:90 to 90:10, such as from 20:80 to 80:20.

(2-2) Cationic surfactant

The cationic surfactant is preferably a compound having no guanamine group.

Examples of the cationic surfactant include amines, amine salts, quaternary ammonium salts, imidazolines, and imidazolinium salts.

The cationic surfactant is preferably an amine salt, a quaternary ammonium salt, or an ethylene oxide addition ammonium salt. Specific examples of the cationic surfactant are not particularly limited, and examples thereof include an alkylamine salt, an amine alcohol fatty acid derivative, a polyamine fatty acid derivative, an amine salt type surfactant such as an imidazoline, and an alkyl group. 4-ammonium salt such as methylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzothonium chloride Salt type surfactants, etc.

An example of a cationic surfactant is a compound represented by the following formula: R ²¹ -N ⁺ (-R ²² )(-R ²³ )(-R ²⁴ )X ^- [wherein R ²¹ , R ²² , R ²³ and R ²⁴ are each independently the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms, and X is an anionic group. ]

The hydrocarbon group may have an oxygen atom, for example, an oxygen alkyl group which may be a polyoxyalkylene group or the like (the carbon number of the alkyl group is, for example, 2 to 5). It is preferred that R ²¹ , R ²² , R ²³ and R ²⁴ are a hydrocarbon group having 1 to 30 carbon atoms (for example, an aliphatic hydrocarbon, an aromatic hydrocarbon or an aromatic aliphatic hydrocarbon).

Specific examples of R ²¹ , R ²² , R ²³ and R ²⁴ are alkyl (for example, methyl, butyl, stearyl, palmityl), aryl (for example, phenyl), aralkyl (for example, benzyl) Base (benzyl), phenethyl (phenethyl).

Specific examples of X include a halogen (for example, chlorine), an acid (for example, an inorganic acid such as hydrochloric acid, an organic acid such as acetic acid (particularly, a fatty acid)).

The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (having an alkyl group having 4 to 30 carbon atoms).

Cationic surfactants are preferably ammonium salts, especially grade 4 ammonium salts. The cationic surfactant may be an ammonium salt represented by the following formula: R ³¹ _p -N ⁺ R ³² _q X ^- [wherein R ^{31 is} independently the same or different, and is C12 or more (for example, C ₁₂ to C) ₅₀ ) a linear and/or branched aliphatic (saturated and/or unsaturated) group, R ³² each independently or the same or different, being H or a C ₁ to C ₄ alkyl group, a benzyl group, Polyoxyethylene (the number of oxygen-extended ethyl groups is, for example, 1 (particularly 2, particularly 3) to 50) (CH ₃ , C ₂ H ₅ is particularly desirable), and X is a halogen atom (for example, chlorine and bromine) ), a fatty acid salt group of C ₁ to C ₄ , p is 1 or 2, q is 2 or 3, and p + q = 4. ].

R ^{31 has} a carbon number of 12 to 50, and may be, for example, 12 to 30.

Specific examples of the cationic surfactant include dodecyltrimethylammonium acetate, trimethyltetradecyl ammonium chloride, cetyltrimethylammonium bromide, and trimethyl chloride. Octadecyl ammonium, chloro(dodecylmethylbenzyl)trimethylammonium chloride, benzyl dodecyldimethylammonium chloride, methyldodecyl chloride (hydrogen polyoxygen) Ethyl ammonium, benzyl dodecyl bis(hydrogen oxide extended ethyl) ammonium chloride.

The amphoteric surfactant may, for example, be an alanine, an imidazolinium betaine, a guanamine betain, or a betaine acetate, and specifically, a lauryl betaine, a stearyl betaine, or a lauryl carboxamide. Hydroxyethyl imidazolinium betaine, lauryl dimethylamine acetic acid betaine, fatty amidoxime dimethylamine acetic acid betaine, and the like.

The surfactant is an interfacially active compound having a mercaptoamine group and an amine group, that is, a surfactant containing a mercaptoamine, or may be omitted.

The amidoxime surfactant is preferably a compound represented by the formula: R ¹¹ -C(=O)(R ¹² -)N-(CH ₂ ) _n -N(-R ¹³ )(-R ¹⁴ ) [wherein, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and n is 0 to 10. ].

R ¹¹ is preferably an alkyl group or an alkenyl group. R ^{11 may have} a carbon number of 8 to 30, for example, 12 to 24. R ¹² , R ¹³ and R ¹⁴ are preferably a hydrogen atom or an alkyl group. The carbon number of R ¹² , R ¹³ and R ¹⁴ is preferably from 1 to 6, especially from 1 to 4. n is from 0 to 10, such as from 1 to 10, especially from 2 to 5.

Specific examples of the guanamine-based amine surfactant include diethylaminoethyl decyl stearate, dimethylaminoethyl decyl oleate, and dimethylaminopropyl oleate. Indamine, diethylaminoethyl oleate, oleic acid diethylaminopropyl decylamine, diethylaminoethyl decyl stearate, diethylaminopropyl stearate Indoleamine, dibutylaminoethyl decylamine stearate, dibutylaminopropyl decylamine stearate, dipropylaminopropyl decylamine stearate, dipropylaminoethyl stearate Indoleamine, dimethylaminoethyl decylamine stearate, dimethylaminopropyl decylamine stearate, diethylaminoethyl decyl palmitate, diethylaminopropyl palmitate Indamine, dimethylaminoethyl decyl palmitate, dimethylaminopropyl decyl palmitate, diethylaminoethyl phthalate, behenic acid diethylamino Propylguanamine, behenic acid dimethylaminopropyl decylamine and the like.

The guanamine amine surfactant can be a salt, for example, an acid salt or a quaternary ammonium salt. In the salt, the cationic group is a nitrogen atom of an amine group, and the anionic group is various. Examples of the anionic group include a halogen ion, a sulfate ion, a carboxylic acid ion having 1 to 4 carbon atoms which may be substituted by a hydroxyl group, or an alkyl sulfate ion having 1 to 4 carbon atoms.

The acid salt is an acid, such as a mineral acid and / Or neutralized with organic acids. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid. The organic acid may, for example, be a short-chain monocarboxylic acid such as acetic acid or propionic acid; lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid or erucic acid; Long-chain monocarboxylic acid; dicarboxylic acid such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, citric acid; glycolic acid, lactic acid, hydroxyacrylic acid, glycerin a hydroxycarboxylic acid such as acid, malic acid, tartaric acid or citric acid; a polycarboxylic acid such as polyglutamic acid; an acidic amino acid such as glutamic acid or aspartic acid; an alkyl sulfate or an alkyl sulfonate; Alkyl phosphate and the like. Among these, inorganic acids, short-chain monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, acidic amino acids, and further hydrochloric acid, sulfuric acid, acetic acid, succinic acid, glycolic acid, lactic acid, malic acid, citric acid and the like are used. Gluten is especially suitable.

The quaternary ammonium salt can be obtained by leveling the guanamine amine.

The guanylamine surfactant can be nonionic or ionic (cationic), but is preferably nonionic. In the case of nonionicity, it is preferably used by ionizing an ionic compound such as an acid.

The nonionic surfactant, the cationic surfactant, and the amphoteric surfactant may be used alone or in combination of two or more.

The amount of the cationic surfactant is preferably 15% by weight or more, more preferably 20% by weight or more, particularly preferably 22% by weight or more, based on the total amount of the nonionic surfactant and the cationic surfactant, for example, It may be 25% by weight or more, particularly 30% by weight or more, and more specifically 35% by weight or more. The upper limit of the amount of the cationic surfactant is, for example, 60% by weight, particularly 50% by weight. Nonionic surfactants and The weight ratio of the cationic surfactant is desirably from 85:15 to 20:80, more desirably from 80:20 to 40:60. The amount of the surfactant other than the nonionic surfactant and the cationic surfactant is 50% by weight or less based on the total amount of the surfactant, and may be, for example, 20% by weight or less, and may be 0.1% by weight. %the above.

The amount of the cationic surfactant is 0.05 to 10 parts by weight, based on 100 parts by weight of the polymer, and may be, for example, 0.1 to 8 parts by weight. The total amount of the surfactant is 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight based on 100 parts by weight of the polymer.

The amount of the guanamine-based surfactant is 80% by weight or less based on the total amount of the surfactant, and may be, for example, 5 to 70% by weight, particularly 10 to 60% by weight.

(3) Liquid medium

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

The polymer (active ingredient) of the water- and oil-repellent composition of the present invention may contain only the above-mentioned non-fluoropolymer, but may contain a fluorine-containing polymer in addition to the above-mentioned non-fluoropolymer. In general, in the water-repellent oil-repellent composition (particularly, an aqueous emulsion), particles formed of a non-fluoropolymer and particles formed of a fluoropolymer are individually present. That is, after the non-fluoropolymer and the fluoropolymer are separately produced, it is preferred to mix a non-fluoropolymer and a fluoropolymer. In general, a non-fluoropolymer emulsion (especially, an aqueous emulsion) After the emulsion of the fluoropolymer (especially, the aqueous emulsion) is separately produced, it is preferred to mix the emulsion of the non-fluoropolymer and the emulsion of the fluoropolymer.

The fluoropolymer is a polymer having a repeating unit derived from a fluorine-containing monomer. The fluorine-containing single system is preferably an acrylate or decylamine represented by the following formula: CH ₂ =C(-X)-C(=O)-YZ-Rf (I) [wherein the X-based hydrogen atom a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (however, X ¹ and X ² hydrogen atoms, fluorine atoms, a chlorine atom, a bromine atom or an iodine atom.), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group; Y Is -O- or -NH-; Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group, -CH ₂ CH ₂ N(R ¹ )SO ₂ - a group (however, R ¹ is an alkyl group having 1 to 4 carbon atoms) or a -CH ₂ CH(OZ ¹ )CH ₂ - group (however, Z ¹ is a hydrogen atom or an ethylidene group) or -(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n -yl or -(CH ₂ ) _m -S-(CH ₂ ) _n -yl (but m is 1 to 10, n is 0 to 10), Rf is a carbon number A linear or branched fluoroalkyl group of 1 to 20. ].

The carbon number of the Rf group is preferably from 1 to 6, especially from 4 to 6.

The fluoropolymer may have a repeating unit derived from at least one non-fluorine monomer selected from the group consisting of a halogenated olefin monomer, a non-fluorine non-bridged monomer, and a non-fluorine bridged monomer.

The halogenated olefin monomer is one to ten chlorine atoms, bromine atoms or iodine Atom-substituted olefins having 2 to 20 carbon atoms are preferred. A specific example of the halogenated olefin monomer is a vinyl halide such as vinyl chloride, vinyl bromide, iodoethylene, divinylidene such as dichloroethylene, dibromoethylene, and diiodoethylene.

An ideal non-fluorine non-bridged monomer is a compound represented by the following formula: CH ₂ =CA-T [wherein, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, chlorine) An atom, a bromine atom, and an iodine atom), a T-based 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 the non-fluorine non-bridged monomer include alkyl (meth)acrylate, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (methyl Acrylate, methoxypolyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate and vinyl alkyl ether.

The non-fluorinated bridging monomer may be a compound having at least two carbon-carbon double bonds (for example, (meth)acrylic groups), or at least one carbon-carbon double bond and having at least one reactive group. Compound.

The weight ratio of the non-fluoropolymer and the fluoropolymer in the water-repellent composition may be from 100:0 to 10:90, for example from 90:10 to 20:80, and desirably from 80:20 to 30: 70.

The individual non-fluoropolymer and the fluoropolymer may be one type of polymer or a combination of two or more types of polymers.

Available with non-fluoropolymer and fluoropolymer combinations Only fluoropolymers are equivalent or equivalent in performance (especially, water repellency).

The polymer (non-fluoropolymer and fluoropolymer) in the present invention can be produced by any of the usual polymerization methods, and the conditions of the polymerization reaction can also be arbitrarily selected. As such a polymerization method, solution polymerization, suspension polymerization, and emulsion polymerization can be mentioned. It is ideal for emulsion polymerization.

When the treatment agent of the present invention is an aqueous emulsion, the method for producing the polymer is not limited. For example, after the polymer is produced by solution polymerization, an aqueous emulsion can be obtained by removing the solvent and adding the surfactant and water.

In the solution polymerization, a method in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator and substituted with nitrogen is heated and stirred in the range of 30 to 120 ° C for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzammonium peroxide, di-tertiary butyl peroxide, lauryl peroxide, cumene hydroperoxide, and peroxidation. Tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. The use range of the polymerization initiator is 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.

The organic solvent is inactive to the monomer and can be dissolved, for example, it can be an ester (for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (for example, A ketone having 2 to 30 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone, an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCFC 225, isopropyl alcohol, and 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, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotri Fluoroethane and the like. The range of use of the organic solvent is 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by weight of the total of the monomers.

In the emulsion polymerization, a method in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after being substituted by nitrogen, it is stirred at 50 to 80 ° C for 1 to 10 hours to be copolymerized. The polymerization initiator can be used: benzammonium peroxide, laurel peroxide, tert-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropene peroxide Base, acetohydrazide, azobisbis(isobutyramidine)-dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate Water-soluble compounds such as azobisisobutyronitrile, benzammonium peroxide, di-tertiary butyl peroxide, lauryl peroxide, cumene hydroperoxide, tertiary butyl peroxybutyrate (Tert-Butyl Peroxypivalate), an oil-soluble compound such as diisopropyl peroxydicarbonate. The use range of the polymerization initiator is 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.

In order to obtain an excellent aqueous dispersion of polymer which is stable in stability, an emulsifying device capable of imparting strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer is used, and it is desirable to granulate and polymerize the monomer in water. Further, as the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and the use range is 0.5 with respect to 100 parts by weight of the monomer. Up to 20 parts by weight. It is preferred to use an anionic and/or nonionic and/or cationic emulsifier. In the case where the monomers are completely incompatible, it is preferred to add a compatibilizing agent capable of sufficiently intermingling the monomers, for example, a water-soluble organic solvent or a low molecular weight monomer. Emulsifying properties and copolymerization properties can be improved by the addition of a compatibilizing agent.

The water-soluble organic solvent may, for example, be acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol or the like, in an amount of from 1 to 50 parts by weight based on 100 parts by weight of water. Parts, for example, in the range of 10 to 40 parts by weight. Further, examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and the like, and 100 parts by weight based on the total amount of the monomers. The fraction may be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight.

A chain transfer agent can be used in the polymerization. The molecular weight of the polymer can be varied depending on the amount of chain transfer agent used. Examples of the chain transfer agent are a thiol group-containing compound such as lauryl mercaptan, sulfuric acid, or thioglycerol (particularly, (for example, a carbon number of 1 to 30) alkanethiol), sodium hypophosphite, and hydrogensulfite. An inorganic salt such as sodium. The chain transfer agent is used in an amount of 0.01 to 10 parts by weight, based on 100 parts by weight of the total amount of the monomers, and may be used, for example, in the range of 0.1 to 5 parts by weight.

The treatment agent composition of the present invention may be in the form of a solution, an emulsion (particularly, an aqueous dispersion) or a gas gel, but is preferably an aqueous dispersion. The treatment composition contains a polymer (active ingredient of a surface treatment agent) and a medium (particularly, a liquid medium such as an organic solvent and/or water). The amount of the medium, for example, may be from 5 to 99.9% by weight relative to the treatment composition, Do not be 10 to 80% by weight.

The concentration of the polymer in the treatment composition is from 0.01 to 95% by weight, for example from 5 to 50% by weight.

The treatment agent composition of the present invention can be applied to the object to be treated by a conventionally known method. In general, a method in which the treatment agent composition is dispersed in an organic solvent or water and diluted, and adhered to the surface of the workpiece to be dried by a known method such as dip coating, spray coating, or bubble coating. Further, if necessary, it is used together with a suitable bridging agent (for example, a blocked isocyanate) to effect curing. Further, an anti-insecticide, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent, or the like may be added to the treatment agent composition of the present invention in combination. The concentration of the polymer in the treatment liquid in contact with the substrate is 0.01 to 10% by weight (particularly, in the case of dip coating), and may be, for example, 0.05 to 10% by weight.

The object to be treated which is treated with the treatment agent composition of the present invention (for example, a water-repellent oil-repellent agent) may be a fiber product, a stone material, a filter (for example, an electrostatic filter), a dust cover, or a fuel cell. (for example, gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metal and oxide, kiln products, plastics, coated surfaces, and gypsum. Examples of the fiber product can be exemplified. For example, animal and plant natural fibers such as cotton, hemp, wool, silk, synthetic fibers of polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, etc., rayon, acetic acid Semi-synthetic fibers such as esters, inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers, or mixed fibers thereof.

The fibrous product may be any of fibers, cloth, and the like.

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

The polymer is such that the fibrous product can be applied to a fibrous substrate (for example, a fibrous product or the like) by any of the known liquid processing methods. When the fibrous product is a cloth, the cloth may be immersed in the solution, or the solution may be attached or sprayed onto the cloth. The treated fibrous product is dried to exhibit oil repellency, and is preferably heated, for example, at 100 ° C to 200 ° C.

Alternatively, the polymer may be applied to the fibrous product by a cleaning method, for example, it may be applied to a fibrous product in a laundry or dry cleaning method or the like.

The treated fibrous product, typically a cloth, comprises a woven fabric, a woven fabric and a non-woven fabric, a cloth and a carpet in the form of a garment, and may also be a fiber or a thread or an intermediate fiber product (for example, a card or roving). Wait). The fibrous product material may be natural fiber (such as cotton or wool, etc.), chemical fiber (for example, 嫘萦-viscose rayon (viscose-rayon or Rheocell, etc.), or synthetic fiber (for example, polyester, polyamide). Or acrylic fibers, etc., or a mixture of fibers (for example, a mixture of natural fibers and synthetic fibers, etc.). The polymer of the present invention is obtained by making cellulose fibers (for example, cotton or ruthenium) oleophobic. It is particularly effective in oil repellency. Moreover, the method of the present invention generally makes the fibrous product hydrophobic and water repellency.

Alternatively, the fibrous substrate can be leather. The polymer will be produced, and in order to make the leather hydrophobic and oleophobic, an aqueous solution or an aqueous emulsion can be applied at various stages of leather processing, for example, during the wet processing of the leather, or during the completion of the leather. In leather.

Alternatively, the fibrous substrate can also be paper. Manufacturing polymers can be applied to pre- The paper that is formed first, or at various stages of papermaking, for example, can be applied during the drying of the paper.

"Treatment" means the application of a treatment agent to a treated object by dipping, spraying, coating, or the like. Through the treatment, the polymer of the 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 仄 other 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 Interface Science Co., Ltd.).

[Examples]

Next, the present invention will be specifically described by way of examples and comparative examples. However, the description is not intended to limit the invention.

Hereinafter, parts or % or ratios are expressed by weight or by weight or by weight unless otherwise specified.

The steps of the test are as follows.

Bundesman water repellency test

The water repellency was evaluated in accordance with the method described in JIS L1092 (C) (Bondi's door test) with a rainfall setting of 80 cc/min, a rainfall water temperature of 20 ° C, and a rainfall time of 5 minutes or 10 minutes. Water repellency is expressed in 6-stage grades (0, 50, 70, 80, 90, and 100) from 0 to 100. Minute The larger the number, the better the water repellency. The attachment +(-) at each level indicates that it is slightly better or worse than each of the levels.

Manufacturing example 1

In a 500 mL autoclave, stearyl acrylate = 45 g, isobornyl methacrylate = 5 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan monooleate = 1.5 g, polyoxyethylene (EO: 18) A 2-stage alkyl (C12-14) ether = 2 g, di(octadecyl)dimethylammonium chloride = 1.5 g, and was ultrasonically dispersed by ultrasonication at 60 ° C for 15 minutes. After replacing the inside of the autoclave with nitrogen, 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is roughly identical to the composition of the charged monomer.

Manufacturing Example 2

In a 500 mL autoclave, stearyl acrylate = 40 g, isobornyl methacrylate = 10 g, pure water = 145 g, tripropylene glycol = 15 g, acetylene glycol polyoxyethylene adduct = 1 g, polyoxyethylene (EO: 18) Isotridecyl ether = 2 g, di(octadecyl)dimethylammonium chloride = 2 g, which was ultrasonically dispersed by ultrasonic wave stirring at 60 ° C for 15 minutes. After replacing the inside of the autoclave with nitrogen, 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is roughly identical to the composition of the charged monomer.

Manufacturing Example 3

In a 500 mL autoclave, stearyl acrylate = 40 g, adamantyl acrylate = 10 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan monooleate Ester = 1.5g, polyoxyethylene (EO: 18) 2nd alkyl (C12-14) ether = 2g, di(octadecyl) dimethyl ammonium chloride = 1.5g, stirred at 60 ° C The sonic emulsion was dispersed for 15 minutes. After replacing the inside of the autoclave with nitrogen, 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is roughly identical to the composition of the charged monomer.

Manufacturing Example 4

In a 500 mL autoclave, stearyl acrylate = 30 g, lauryl acrylate = 5 g, benzyl methacrylate = 15 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan monooleate = 1.5 g, charged Oxyethylene (EO: 18) 2 alkyl (C12-14) ether = 2 g, di(octadecyl)dimethylammonium chloride = 1.5 g, and was ultrasonically dispersed by ultrasonication at 60 ° C for 15 minutes. After replacing the inside of the autoclave with nitrogen, 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is roughly identical to the composition of the charged monomer.

Manufacturing Example 5

In a 500 mL autoclave, stearyl acrylate = 25 g, behenyl acrylate = 15 g, isobornyl methacrylate = 10 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan monooleate = 1.5 g, polyoxyethylene (EO: 18) 2 alkyl (C12-14) ether = 2 g, di(octadecyl) dimethyl ammonium chloride = 1.5 g, ultrasonically emulsified at 60 ° C with stirring Disperse for 15 minutes. After replacing the inside of the autoclave with nitrogen, 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. Pure water Adjust the solids concentration to 30%. The monomer composition of the resulting polymer is roughly identical to the composition of the charged monomer.

Manufacturing Example 6

In a 500 mL autoclave, stearyl acrylate = 35 g, isobornyl methacrylate = 10 g, glycidyl methacrylate = 5 g, pure water = 145 g, tripropylene glycol = 15 g, acetylene glycol polyoxyethylene adduct =1 g, polyoxyethylene (EO: 18) isotridecane ether = 2 g, di(octadecyl)dimethylammonium chloride = 2 g, and ultrasonically dispersed for 15 minutes while stirring at 60 ° C. After replacing the inside of the autoclave with nitrogen, 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is roughly identical to the composition of the charged monomer.

Manufacturing Example 7

In a 500 mL autoclave, stearyl acrylate = 37.5 g, isobornyl methacrylate = 10 g, hydroxyethyl methyl acrylate = 2.5 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan monooleate Ester = 1.5g, polyoxyethylene (EO: 18) 2nd alkyl (C12-14) ether = 2g, di(octadecyl) dimethyl ammonium chloride = 1.5g, stirred at 60 ° C The sonic emulsion was dispersed for 15 minutes. After replacing the inside of the autoclave with nitrogen, 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is roughly identical to the composition of the charged monomer.

Manufacturing Example 8

In a 500 mL autoclave charged with stearyl acrylate = 35 g, methacrylic acid Benzyl ester = 10g, pure water = 145g, tripropylene glycol = 15g, sorbitan monooleate = 1.5g, polyoxyethylene (EO: 18) 2 alkyl (C12-14) ether = 2g, chlorinated Di(octadecyl)dimethylammonium = 1.5 g, which was ultrasonically dispersed by ultrasonication at 60 ° C for 15 minutes. After replacing the inside of the autoclave with nitrogen, vinyl chloride was charged into 5 g of vinyl chloride, and 2,2-azobis(2-amidinopropane) 2 hydrochloride was added to 0.5 g, and the reaction was carried out at 60 ° C for 3 hours. An aqueous dispersion of the polymer is obtained. The solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is roughly identical to the composition of the charged monomer.

Manufacturing Example 9

In a 500 mL autoclave, stearyl acrylate = 25 g, adamantyl acrylate = 15 g, glycidyl methacrylate = 2.5 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan monooleate = 1.5 g, polyoxyethylene (EO: 18) 2 alkyl (C12-14) ether = 2g, di(octadecyl) dimethyl ammonium chloride = 1.5g, ultrasonically dispersed by ultrasonic wave at 60 ° C 15 minutes. After replacing the inside of the autoclave with nitrogen, 7.5 g of dichloroethylene oxide was charged under pressure, and 2,2-azobis(2-amidinopropane) 2 hydrochloride was added = 0.5 g, and the reaction was carried out at 60 ° C. An aqueous dispersion of the polymer was obtained in an hour. The solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is roughly identical to the composition of the charged monomer.

Comparative manufacturing example 1

In a 500 mL autoclave, stearyl acrylate = 50 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan oleate = 1.5 g, polyoxyethylene (EO: 18) 2 alkyl (C12-14) Ether = 2 g, di(octadecyl)dimethylammonium chloride = 1.5 g, which was ultrasonically dispersed by ultrasonication at 60 ° C for 15 minutes. Will be high pressure After replacing the inside of the autoclave with nitrogen, 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is roughly identical to the composition of the charged monomer.

Comparative manufacturing example 2

In a 500 mL autoclave, stearyl acrylate = 40 g, lauryl acrylate = 10 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan monooleate = 1.5 g, polyoxyethylene (EO: 18) 2 The alkyl group (C12-14) ether = 2 g, di(octadecyl)dimethylammonium chloride = 1.5 g, and was ultrasonically dispersed by ultrasonic wave stirring at 60 ° C for 15 minutes. After replacing the inside of the autoclave with nitrogen, 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is roughly identical to the composition of the charged monomer.

Comparative Manufacturing Example 3

In a 500 mL autoclave, stearyl acrylate = 25 g, behenyl acrylate = 25 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan monooleate = 1.5 g, polyoxyethylene (EO: 18) A 2-stage alkyl (C12-14) ether = 2 g, di(octadecyl)dimethylammonium chloride = 1.5 g, and was ultrasonically dispersed by ultrasonication at 60 ° C for 15 minutes. After replacing the inside of the autoclave with nitrogen, 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid concentration was adjusted to 30% with pure water. The composition of the resulting polymer is roughly identical to the composition of the charged monomer.

Comparative Manufacturing Example 4

In a 500mL autoclave charged with stearyl acrylate = 20g, acrylic laurel Ester = 25 g, glycidyl methacrylate = 5 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan monooleate = 1.5 g, polyoxyethylene (EO: 18) 2 alkyl (C12- 14) Ether = 2 g, di(octadecyl)dimethylammonium chloride = 1.5 g, which was ultrasonically dispersed by ultrasonication at 60 ° C for 15 minutes. After replacing the inside of the autoclave with nitrogen, 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is roughly identical to the composition of the charged monomer.

Comparative Manufacturing Example 5

In a 500 mL autoclave, stearyl acrylate = 35 g, glycidyl methacrylate = 2.5 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan monooleate = 1.5 g, polyoxyethylene (EO) : 18) 2nd alkyl (C12-14) ether = 2 g, di(octadecyl)dimethylammonium chloride = 1.5 g, and ultrasonically dispersed for 15 minutes under stirring at 60 °C. After replacing the inside of the autoclave with nitrogen, 12.5 g of vinyl chloride ester was charged under pressure, and 2,2-azobis(2-amidinopropane) 2 hydrochloride was added = 0.5 g, and reacted at 60 ° C for 3 hours. An aqueous dispersion of the polymer is obtained. The solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is roughly identical to the composition of the charged monomer.

The raw materials used in the production examples and comparative production examples are shown in Table 1.

Reference Example 1 (Manufacture of fluorine-based detergent)

In a 500 ml reaction flask, 14.3 g of CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ (n=2.0), 43.46 g of stearyl acrylate, and 110 g of pure water were charged. Dipropylene glycol monomethyl ether 18.62g, distearyl dimethyl ammonium chloride 3.08g, stearyl trimethyl ammonium 0.87g, polyoxyethylene lauryl ether (EO: 18. EO represents epoxy B The number of alkane units was 2.1 g, and polyoxyethylene isotridecyl ether (EO: 3) was 0.65 g, which was ultrasonically dispersed by ultrasonic wave stirring at 60 ° C for 15 minutes. After replacing the inside of the reaction flask with nitrogen, 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 a polymer (fluorine-based detergent) was obtained. The composition of the resulting polymer is roughly identical to the composition of the charged monomer.

Example 1

50 g of the aqueous liquid produced in Production Example 1 was diluted with tap water to prepare a test liquid (1000 g). The cloth (510 mm x 205 mm) was immersed in the test liquid, and passed through a mangle and treated with a pin stenter at 160 ° C for 2 minutes. The test cloth was subjected to a water repellency test. The PET taffeta fabric and the nylon taffeta silk fabric were repeatedly carried out in the same manner as the above steps. After that, the Bondis door test was carried out. The results are shown in Table 2.

Examples 2 to 9 and Comparative Examples 1 to 5

The Bondisch test was carried out in the same manner as in Example 1. The results are shown in Table 2.

Examples 10 to 11

25 g of the individual aqueous liquid (non-fluorine-based detergent) produced in Production Examples 1 and 4 and 25 g of the fluorine-based detergent produced in Reference Example 1 were diluted with tap water to prepare a test liquid (1000 g), and Example 1 was prepared. The same treatment, the implementation of the Bondi door test. The results are shown in Table 2.

[Industry use possibility]

The treatment agent of the present invention can be suitably used for a substrate such as a fiber product or a masonry, and imparts excellent water repellency (especially, water repellency) to the substrate.

<1>

An aqueous emulsion treatment agent comprising: (1) a polymer comprising: (i) 40% by weight or more of a long-chain (meth) acrylate monomer represented by the following formula with respect to a polymer; Recurring unit derived: CH ₂ =CA ¹¹ -C(=O)-OA ¹²

[wherein A ¹¹ is a hydrogen atom or a methyl group, A ¹² is a linear or branched aliphatic hydrocarbon group having 18 to 30 carbon atoms], and (ii) a long-chain (meth) acrylate having a cyclic hydrocarbon group; The repeating unit derived from the monomer, and (2) a surfactant comprising a nonionic surfactant and a cationic surfactant, and (3) a liquid medium containing water.

<2>

The aqueous emulsion treatment agent according to <1>, wherein the acrylate monomer (ii) having a cyclic hydrocarbon group is a compound represented by the following formula: CH ₂ =CA ²¹ -C(=O)-OA ²²

[In the formula, A ²¹ is a hydrogen atom or a methyl group, and A ²² is a group having a carbon number of 4 to 30 cyclic hydrocarbon groups].

<3>

The aqueous emulsion treatment agent according to <1> or <2>, wherein the polymer (1) further has (iii) a repeating unit derived from a short-chain (meth) acrylate monomer represented by the following formula: CH ₂ =CA ³¹ -C(=O)-OA ³²

[In the formula, A ²¹ is a hydrogen atom or a methyl group, and A ³² is a linear or branched aliphatic hydrocarbon group having a carbon number of less than 18].

<4>

The aqueous emulsion treatment agent according to any one of <1> to <3>, wherein the polymer (1) further comprises (iv) a repeating unit derived from a non-fluorine bridging monomer.

<5>

An aqueous emulsion treatment agent as described in <4>, The non-fluorine-bridgeable monomer (iv) is a compound having at least two ethylenically unsaturated double bonds or a compound having at least one ethylenically unsaturated double bond and at least one reactive group.

<6>

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

<7>

The aqueous emulsion treatment agent according to <6>, wherein at least one of the halogenated olefin monomers (v) is selected from the group consisting of vinyl chloride and dichloroethylene.

<8>

The aqueous emulsion treatment agent according to any one of <1> to <7>, wherein the polymer (1) is a fluorine-free atom.

<9>

The aqueous emulsion treatment agent according to any one of <1> to <8> wherein, in the polymer (1), the amount of the repeating unit (ii) is from 1 to 150 with respect to 100 parts by weight of the repeating unit (i). The amount of the repeating unit (iii) is 0 to 100 parts by weight, the amount of the repeating unit (iv) is 0 to 100 parts by weight, and the amount of the repeating unit (v) is 0 to 100 parts by weight.

<10>

The aqueous emulsion treatment agent according to any one of <1>, wherein the amount of the cationic surfactant in the surfactant is 15% by weight or more.

<11>

The aqueous emulsion treatment agent according to any one of <1>, wherein the nonionic surfactant is a compound represented by the following formula: R ¹ O-(CH ₂ CH ₂ O) _p -(R ² O) _q -R ³

Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or a fluorenyl group having 2 to 22 carbon atoms, and each R ² is independently the same or different and is a carbon number of 3 or more (for example, 3 to The alkenyl group of 10), R ³ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 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 <11>, wherein the nonionic surfactant is an alkyne compound selected from the group consisting of an acetylene alcohol and an oxyethylene adduct of an alkyne alcohol.

<13>

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

[wherein, each of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is independently the same or different and is 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 is a compound represented by the following formula: R ²¹ -N ⁺ (-R ²² )(-R ²³ ) (-R ²⁴ )X ^-

[wherein, each of R ²¹ , R ²² , R ²³ and R ²⁴ is independently the same or different and is a hydrocarbon group 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>, The fiber treating agent further contains a fluoropolymer.

<16>

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

<17>

The aqueous emulsion treatment agent according to any one of <1>, wherein the aqueous emulsion has a dynamic surface tension of 55 mN/m or less.

<18>

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

<19>

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

<20>

A method of treating a fibrous product, comprising treating the fibrous product with the aqueous emulsion treating agent according to any one of <1> to <19>.

<21>

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

Claims (10)

A surface treatment agent comprising the following aqueous emulsions of (1), (2) and (3), and (1) a non-fluoropolymer comprising: (i) a long chain represented by the following formula (A) a repeating unit derived from an acrylate monomer, CH ₂ =CA ¹¹ -C(=O)-OA ¹² [wherein, A ¹¹ is a hydrogen atom or a methyl group, and A ¹² is a linear chain having a carbon number of 18 to 30 Or a branched aliphatic hydrocarbon group], and (ii) a repeating unit derived from a (meth) acrylate monomer having a cyclic hydrocarbon group; (2) a surfactant containing a nonionic surfactant and a cationic property One or both of the surfactants; (3) a liquid medium containing water. The surface treatment agent according to claim 1, wherein the cyclic hydrocarbon group-containing acrylate monomer (ii) is a compound represented by the following formula: CH ₂ = CA ²¹ -C(=O)-OA ²² [wherein A ²¹ is a hydrogen atom or a methyl group; and A ²² is a group having a cyclic hydrocarbon having 4 to 30 carbon atoms]. The surface treatment agent according to claim 1 or 2, wherein the surfactant (2) comprises both a nonionic surfactant and a cationic surfactant, relative to the nonionic surfactant and the cation. The total amount of surfactants, the amount of cationic surfactants in 22% by weight or more. The surface treatment agent according to claim 1 or 2, wherein the nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamines, polyols, and amine oxides. At least one of the cationic surfactants is at least one selected from the group consisting of an amine, an amine salt, a quaternary ammonium salt, an imidazoline, and an imidazolinium salt. The surface treatment agent according to claim 1 or 2, wherein the surfactant comprises an interface active compound having both a guanamine group and an amine group. The surface treatment agent according to claim 1 or 2, wherein the surface treatment agent does not contain a fluoropolymer. The surface treatment agent according to claim 1 or 2, wherein the surface treatment agent contains a fluoropolymer. The surface treatment agent according to claim 1 or 2, which is a water-repellent oil-repellent agent or an anti-fouling agent. A method of treating a fibrous product, which comprises treating a fibrous product with a surface treating agent according to any one of claims 1 to 8. A fiber product which is treated by a surface treatment agent as described in any one of claims 1 to 8.