KR101851086B1 - Surface treatment agent - Google Patents

Abstract

[식 중, A¹¹은, 수소 원자 또는 메틸기이며, A¹²는, 탄소수 18 내지 30의 직쇄 또는 분지의 지방족 탄화수소기이다.]로 표시되는 장쇄 (메트)아크릴레이트 에스테르 단량체로부터 유도된 반복 단위, 및 (ii) 환상 탄화수소기를 갖는 (메트)아크릴레이트 단량체로부터 유도된 반복 단위를 갖는 비불소 중합체, 및 (2) 비이온성 계면 활성제 및 양이온성 계면 활성제의 한쪽 또는 양쪽을 포함하는 계면 활성제, 및 (3) 물을 포함하는 액상 매체를 포함하는 수계 에멀전인 표면 처리제가 개시되어 있다.There is provided a surface treatment agent which does not use a fluorine-containing monomer, particularly a fluoroalkyl group-containing monomer. (1) (i) Formula:

(Meth) acrylate ester monomer represented by the following general formula (1): wherein 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, And (ii) a non-fluorine polymer having repeating units derived from a (meth) acrylate monomer having a cyclic hydrocarbon group, and (2) a surfactant comprising one or both of a nonionic surfactant and a cationic surfactant, and 3) an aqueous emulsion containing a liquid medium containing water.

Description

SURFACE TREATMENT AGENT

The present invention relates to a surface treating agent, particularly a water-repellent oil-repellent agent and an antifouling agent.

Conventionally, a fluorine-containing water and oil repellent agent containing a fluorine compound is known. This water and oil repellent agent exhibits good water and oil repellency when treated with a substrate such as a textile product.

From a recent study [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 environmental burden on PFOA (perfluorooctanoic acid), a type of roalkyl compound, became clear and on April 14, 2003, the US Environmental Protection Agency (EPA) announced that it would strengthen scientific research on PFOA.

The 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) or EPA OPPT FACT SHEET April 14, 2003 (http: // www. epa.gov/opptintr/pfoa/pfoafacts.pdf) is known to be capable of producing PFOA by degradation or metabolism of telomers (telomeres means long chain fluoroalkyl groups). It has also been disclosed that telomers are used in many products such as water-repellent, oil-repellent, antifouling-imparted foam extinguishing agents, care products, cleaning products, carpets, textiles, paper and leather. There is a concern that a fluorine-containing compound may accumulate in the environment.

The fluorine-containing water- and oil-repellent agent containing a fluorine-containing polymer must be subjected to heat treatment at a high temperature (for example, 100 ° C or higher) after adhering to a base material such as a fiber product in order to develop water and oil repellency. The heat treatment at high temperature requires high energy.

Further, the fluorine-containing polymer is expensive.

Therefore, there is a case where it is desired not to use the fluorine-containing polymer or to reduce the amount of the fluorine-containing polymer.

Japanese Patent Application Laid-Open No. 2006-328624 discloses a water repellent agent comprising a non-fluorinated polymer having a (meth) acrylate ester having a carbon number of 12 or more in the ester portion as a monomer unit, wherein the constituent ratio of the (meth) Is 80 to 100% by mass based on the total amount of the monomer units constituting the water repellent agent.

However, this water repellent agent is poor in water and oil repellency.

Japanese Patent Application Laid-Open No. 2006-328624

An object of the present invention is to provide a surface treatment agent which imparts good water and oil repellency and does not preferably use a fluorine-containing monomer, particularly a fluoroalkyl group-containing monomer.

According to the present invention,

(1) a repeating unit derived from (i) a long chain (meth) acrylate ester monomer, and

(ii) a repeating unit derived from a (meth) acrylate monomer having a cyclic hydrocarbon group

/ RTI >

(2) a surfactant, and

(3) a liquid medium containing water

Based emulsion treatment agent.

Preferred embodiments of the invention are as follows.

[One]

(1) (i) Formula:

Wherein A ¹¹ is a hydrogen atom or a methyl group,

A ¹² is a straight-chain or branched aliphatic hydrocarbon group having 18 to 30 carbon atoms.]

A repeating unit derived from a long-chain (meth) acrylate ester monomer represented by the following formula

(ii) a repeating unit derived from a (meth) acrylate monomer having a cyclic hydrocarbon group

A fluorine-containing polymer,

(2) a surfactant comprising one or both of a nonionic surfactant and a cationic surfactant, and

(3) a liquid medium containing water

Wherein the surface treatment agent is an aqueous emulsion.

[2]

The cyclic hydrocarbon group-containing acrylate ester monomer (ii)

Wherein A ²¹ is a hydrogen atom or a methyl group,

A ²² is a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms.]

Is a compound represented by the following formula (1).

[3]

Wherein the surfactant (2) comprises 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 at least 22 wt% 2].

[4]

The nonionic surfactant is at least one selected from the group consisting of ether, ester, ester ether, alkanolamide, polyhydric alcohol and amine oxide,

The surface treatment agent according to any one of [1] to [3], wherein the cationic surfactant 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.

[5]

The surface treatment agent according to any one of [1] to [4], wherein the surfactant comprises a surfactant compound having both an amide group and an amino group.

[6]

The surface treatment agent according to any one of [1] to [5], wherein the surface treating agent does not contain a fluorine-containing polymer.

[7]

The surface treatment agent according to any one of [1] to [5], wherein the surface treating agent contains a fluorine-containing polymer.

[8]

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

[9]

A method for treating a fiber product, comprising treating the fiber product with the 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 fluororesin group-containing monomer is not used in the surface treatment agent of the present invention, there is no fear of accumulation of the fluorine-containing compound in the environment. The surface treatment agent of the present invention gives an excellent water and oil-repellent, especially a water-repellent agent, to the substrate. Further, it is not necessary to carry out the heat treatment at a high temperature, and the water and oil repellency is exhibited by the low temperature treatment.

The stability (emulsion stability) of the treatment agent of the present invention is good. The treatment agent of the present invention is excellent in water repellency of steel represented by heavy rain.

A treatment agent containing only a fluorine-containing polymer as an effective component has the same or equivalent performance as a treatment agent containing only a fluorine-containing polymer containing a fluoroalkyl group-containing monomer as a constituent unit (in particular, Oil) is obtained.

In the present invention, the copolymer (preferably, a non-fluorine polymer)

(i) a repeating unit derived from a long-chain (meth) acrylate ester monomer, and

(ii) a repeating unit derived from a (meth) acrylate monomer having a cyclic hydrocarbon group

.

The copolymer may also contain,

(iii) a repeating unit derived from a short chain (meth) acrylate ester monomer, and

(iv) a repeating unit derived from a non-fluorine-crosslinkable monomer

Or both of them.

The copolymer may have a fluorine atom, but preferably has no fluorine atom. That is, the copolymer is preferably a non-fluorine polymer.

(i) a long chain (meth) acrylate ester monomer

The long chain (meth) acrylate ester monomer has the formula:

Wherein A ¹¹ is a hydrogen atom or a methyl group,

A ¹² is a straight-chain or branched aliphatic hydrocarbon group having 18 to 30 carbon atoms.]

≪ / RTI >

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

It is particularly preferable that A ¹¹ is a methyl group.

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

Particularly preferred specific examples of long chain (meth) acrylate ester monomers are stearyl (meth) acrylate, behenyl (meth) acrylate. Stearyl (meth) acrylate is particularly preferred.

The presence of the long-chain (meth) acrylate ester monomer increases the water repellency and oil repellency imparted by the polymer.

(ii) an acrylate ester monomer having a cyclic hydrocarbon group

The cyclic hydrocarbon group-containing acrylate ester monomer may be,

expression:

Wherein A ²¹ is a hydrogen atom or a methyl group,

A ²² is a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms.]

Is preferable.

The cyclic hydrocarbon group-containing acrylate ester monomer is a monomer whose homopolymer has a high glass transition point (for example, 50 ° C or more, particularly 80 ° C or more).

The cyclic hydrocarbon group-containing acrylate ester monomer does not have a fluoroalkyl group. The cyclic hydrocarbon group-containing acrylate ester monomer may contain a fluorine atom, but preferably contains no fluorine atom.

It is particularly preferable that A ²¹ is a methyl group.

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

Specific examples of cyclic hydrocarbon group-containing acrylate ester monomers include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl -Adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate and the like.

The presence of the cyclic hydrocarbon group-containing acrylate ester monomer increases the water repellency and oil repellency imparted by the copolymer.

(iii) a short chain (meth) acrylate ester monomer

The copolymer may have repeating units derived from a short-chain (meth) acrylate ester monomer.

The short-chain (meth) acrylate ester monomer has the formula:

Wherein A ³¹ is a hydrogen atom or a methyl group,

A ³² is a linear or branched aliphatic hydrocarbon group having less than 18 carbon atoms.]

Is preferable.

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

It is particularly preferable that A ³¹ is a methyl group.

A ³² is a linear or branched hydrocarbon group. The linear or branched hydrocarbon group may be a linear hydrocarbon group in particular. The linear or branched hydrocarbon group has 1 to 17 carbon atoms. The linear or branched hydrocarbon group preferably has 1 to 14 carbon atoms, and is preferably a saturated aliphatic hydrocarbon group, particularly an alkyl group.

Specific examples of the short chain (meth) acrylate ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, Myristyl (meth) acrylate, cetyl (meth) acrylate. Particularly preferred specific examples of the short chain (meth) acrylate ester monomers are lauryl (meth) acrylate and cetyl (meth) acrylate.

The presence of the short-chain (meth) acrylate ester monomer improves the water repellency and texture imparted by the polymer.

(iv) a non-fluorine-crosslinkable monomer

The copolymer may or may not have repeating units derived from non-fluorine-crosslinkable monomers.

The non-fluorine-crosslinkable monomer is a monomer not containing a fluorine atom. The non-fluorine-crosslinkable monomer may be a compound having at least two reactive groups and / or olefinic carbon-carbon double bonds (preferably, a (meth) acrylate group) and not containing fluorine. The non-fluorine crosslinking monomer is a compound having at least two olefinic carbon-carbon double bonds (preferably, 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 include a hydroxyl group, an epoxy group, a chloromethyl group, a block isocyanate group, an amino group, a carboxyl group, and the like.

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

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

Examples of the nonfluorine-crosslinkable monomer include diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl Acrylate, 2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl , 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like, but are not limited thereto.

The presence of the non-fluorine-crosslinkable monomer improves the durability of washing given by the polymer.

(v) other monomers

Monomers (v) other than the monomers (i) to (iv), for example, non-fluorine-free cross-linking monomers may be used.

Examples of other monomers include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) Polypropylene glycol (meth) acrylate, and vinyl alkyl ethers. Other monomers are not limited to this example.

The other monomer may be a halogenated olefin (preferably having no fluorine atom).

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

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

Since water and oil repellency are increased, it is preferable that each of the monomers is an acrylate ester.

Each of the monomers (i) to (v) may be a single monomer or a mixture of two or more monomer.

The amount of the monomer (i) is not less than 40% by weight, preferably not less than 50% by weight, based on the copolymer. The amount of the monomer (i) may be 95 wt% or less, for example, 80 wt% or less, or 75 wt% or less, or 70 wt% or less based on the copolymer.

In the copolymer, it is preferable that, relative to 100 parts by weight of the monomer (i)

The amount of the repeating unit (ii) is 1 to 150 parts by weight, preferably 1 to 30 parts by weight,

The amount of the repeating unit (iii) is 0 to 100 parts by weight, preferably 1 to 30 parts by weight,

The amount of the repeating unit (iv) is 0 to 50 parts by weight, preferably 1 to 10 parts by weight,

The amount of the repeating unit (v) may be 0 to 100 parts by weight, preferably 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, in particular from 3,000 to 200,000. The number average molecular weight (Mn) of the copolymer is generally measured by GPC (gel permeation chromatography).

The polymer may be one kind of polymer, but may be a combination of two or more kinds of polymers.

In the present invention, a treating agent composition in which monomers are copolymerized and a copolymer is dispersed or dissolved in a medium is obtained.

The monomers used in the present invention are as follows.

The monomer (i) + (ii),

The monomer (i) + (ii) + (iii),

The monomer (i) + (ii) + (iv), or

Monomers (i) + (ii) + (iii) + (iv).

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

It is preferable to use a non-fluorine-crosslinkable monomer (iv). The monomer is preferably a combination of a monomer (i) + a monomer (ii) + a monomer (iv) or a combination of a monomer (i) + a monomer (ii) + a monomer (iv) + a halogenated olefin. In this combination, water repellency and washing durability are high.

(2) Surfactants

In the treatment agent of the present invention, the surfactant includes a nonionic surfactant and a cationic surfactant. The surfactant may consist solely of a nonionic surfactant and a cationic surfactant or may include other surfactants (other than a nonionic surfactant and a cationic surfactant). Examples of other surfactants are amphoteric surfactants. It is preferred that the surfactant does not contain an anionic surfactant.

(2-1) Nonionic surfactant

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

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

Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are alcohols having 1 to 6 carbon atoms (especially 2 to 5 carbon atoms) and 1 to 50 carbon atoms (particularly 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 ester ethers are compounds obtained by adding an alkylene oxide (particularly, ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols having 1 to 6 carbon atoms (especially 2 to 5 carbon atoms) and 1 to 50 carbon atoms (particularly 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 with fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolino. 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 1 to 3 amino groups and 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 5 hydroxyl groups.

The polyhydric alcohol may be an alcohol having from 2 to 5 carbon atoms and having from 3 to 30 carbon atoms.

The amine oxides may be oxides of amines (secondary amines or preferably tertiary amines) (for example, 5 to 50 carbon atoms).

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

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

The nonionic surfactant is selected from alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, polyalkylene glycols of linear and / or branched fatty acids (saturated and / or unsaturated) Esters, polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), and alkylene oxide adducts of acetylene glycol. Of these, polyoxyethylene (POE), polyoxypropylene (POP), or POE / POP copolymer (which may be a random copolymer or a block copolymer) may be used as the structure of the alkylene oxide addition moiety and polyalkylene glycol moiety desirable.

The nonionic surfactant is preferably a structure free from aromatic groups from environmental problems (biodegradability, environmental hormones, etc.).

The nonionic surfactant has the formula:

Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or an acyl group having 2 to 22 carbon atoms,

Each of R < ² > is independently an alkylene group having 3 or more carbon atoms (e.g., 3 to 10 carbon atoms)

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,

q is 0 or a number of 1 or more.]

May be used.

R ^{1 preferably} has 8 to 20 carbon atoms, and more preferably 10 to 18 carbon atoms. Specific preferred examples of R ¹ include a lauryl group, a tridecyl group and an oleyl group.

Examples of R ² are a propylene group and a butylene group.

In the nonionic surfactant, p may be 3 or more (e.g., 5 to 200). q may be 2 or more (for example, 5 to 200). That is, - (R ² O) q- may form a polyoxyalkylene chain.

The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether having a hydrophilic polyoxyethylene chain at the center and a hydrophobic oxyalkylene chain (particularly, a polyoxyalkylene chain). Examples of the hydrophobic oxyalkylene chain include oxypropylene chain, oxybutylene chain and styrene chain. Of these, oxypropylene chain is preferable.

Preferred nonionic surfactants have the formula:

Wherein R ¹ and p are as defined above.

Lt; / RTI >

Examples of nonionic surfactants include,

Wherein p and q are as defined above.

.

Specific examples of the nonionic surfactant include a mixture of ethylene oxide and at least one of hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkane (C ₁₂ -C ₁₆ ) thiol, sorbitan mono fatty acid (C ₇ -C ₁₉ ) (C ₁₂ -C ₁₈ ) amine, and the like.

The proportion of the polyoxyethylene block may be from 5 to 80% by weight, for example from 30 to 75% by weight, in particular from 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer).

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

The nonionic surfactants may be used alone or in combination of two or more.

[특히,

]로 표시되는 화합물이어도 된다. R¹기가 분지의 알킬기인 비이온성 계면 활성제의 양은, 비이온성 계면 활성제 (B2) 합계 100중량부에 대하여 5 내지 100중량부, 예를 들어 8 내지 50중량부, 특히 10 내지 40중량부여도 된다. 2종 이상의 조합에 있어서, 나머지의 비이온성 계면 활성제는, R¹기(및/또는 R³기)가 (포화 및/또는 불포화의) 직쇄의 알킬기(예를 들어, 라우릴기(n-라우릴기))인

[특히,

]로 표시되는 화합물이어도 된다.The nonionic surfactant is preferably a combination of two or more. In the combination of two or more kinds, at least one kind of nonionic surfactant is a compound wherein the R ¹ group (and / or R ³ group) is a branched alkyl group (for example, isotridecyl group)

[Especially,

] May be used. The amount of the nonionic surfactant in which the R ¹ group is an alkyl group in the branch may be 5 to 100 parts by weight, for example, 8 to 50 parts by weight, particularly 10 to 40 parts by weight per 100 parts by weight of the total amount of the nonionic surfactant (B2) . In the combination of two or more kinds, the remaining nonionic surfactants are those in which the R ¹ group (and / or the R ³ group) is a linear alkyl group (for example, saturated or unsaturated) )

[Especially,

] May be used.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin Fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, fatty acid alkylolamides, alkylalkanolamides, acetylene glycols, oxyethylene adducts of acetylene glycols Water, polyethylene glycol polypropylene glycol block copolymer, and the like.

As the nonionic surfactant, acetyl alcohol (particularly, acetylene glycol), or acetyl alcohol (particularly, acetylene glycol) oxy (meth) acrylate is preferable because the dynamic surface tension of the aqueous emulsion is low Ethylene adducts are preferred.

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

An acetylene alcohol compound is a compound containing at least one triple bond and at least one hydroxyl group. The acetylene alcohol compound may be a compound containing a polyoxyalkylene moiety. Examples of polyoxyalkylene moieties include random addition structures of polyoxyethylene, polyoxypropylene, polyoxyethylene and polyoxypropylene, and block addition structures of polyoxyethylene and polyoxypropylene.

The acetylene alcohol compound has the formula:

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.

May be used. The acetylene alcohol compound may be an alkylene oxide adduct of a compound represented by the formula. The alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, 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, and an isobutyl group. The alkylene oxide is preferably an alkylene oxide having 1 to 20 carbon atoms (particularly 2 to 5 carbon atoms) such as ethylene oxide or propylene oxide, and the addition number of the alkylene oxide is preferably 1 to 50.

Specific examples of the acetylene alcohol compound include acetylene diol, propargyl alcohol, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl- , 7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyn- 3-ol, 3-hexyne-2,5-diol, 2-butene-1,4-diol and the like. Polyethoxylates and ethylene oxide adducts of these specific example compounds are also enumerated.

The nonionic surfactant may not have a triple bond, or may have a triple bond. The nonionic surfactant may be either a nonionic surfactant having no triple bond or a nonionic surfactant having a triple bond, but a combination of a nonionic surfactant having no triple bond and a nonionic surfactant having a triple bond . In the combination of a nonionic surfactant having no triple bond and a nonionic surfactant having a triple bond, a combination of a nonionic surfactant having no triple bond (for example, a nonionic surfactant having an oxyalkylene group) The weight ratio of the nonionic surfactant (e.g. acetylenic alcohol compound) having a weight average molecular weight of 20,000 to 20,000 may be 10:90 to 90:10, for example, 20:80 to 80:20.

(2-2) Cationic surfactant

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

Examples of cationic surfactants 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 oxyethylene addition type ammonium salt. Specific examples of the cationic surfactant include, but are not limited to, alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, Quaternary ammonium salt type surfactants such as pyridinium salts, alkylisoquinolinium salts and benzethonium chloride, and the like.

Examples of cationic surfactants include,

Wherein each of R ²¹ , R ²² , R ²³ and R ²⁴ is independently the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms,

X is an anionic group.]

≪ / RTI > The hydrocarbon group may have an oxygen atom, and for example, oxyalkylene such as a polyoxyalkylene group (the number of carbon atoms of the alkylene is, for example, 2 to 5) may be used. R ²¹ , R ²² , R ²³ and R ²⁴ are preferably 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 include an alkyl group (e.g., methyl group, butyl group, stearyl group, palmity group), an aryl group (e.g., phenyl group) For example, benzyl group (phenylmethyl group), phenethyl group (phenylethyl group)).

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

It is particularly preferred that the cationic surfactant is a monoalkyltrimethylammonium salt (alkyl having 4 to 30 carbon atoms).

The cationic surfactant is preferably an ammonium salt, particularly a quaternary ammonium salt. The cationic surfactant has the formula:

^Wherein each R ³¹ is independently a linear or branched aliphatic (saturated and / or unsaturated) group which is the same or different and is C ₁₂ or more (for example, C ₁₂ to C ₅₀ )

Each of R ³² is independently the same or different and is H or an alkyl group having 1 to 4 carbon atoms, a benzyl group, a polyoxyethylene group (e.g., 1, particularly 2, particularly 3, ₃ , and C ₂ H ₅ are particularly preferred)

X is a halogen atom (e.g., chlorine and bromine), a C ₁ to C ₄ fatty acid base,

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

May be an ammonium salt. The carbon number of R ³¹ may be 12 to 50, for example, 12 to 30.

Specific examples of the cationic surfactant include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, Methyldodecyldi (hydropolyoxyethylene) ammonium chloride, benzyldodecyldi (hydropolyoxyethylene) ammonium chloride.

Examples of the amphoteric surfactant include alanine, imidazolinium betaine, amide betaine, and betaine acetate. Specific examples thereof include laurylbetaine, stearylbetaine, laurylcarboxymethylhydroxyethyl Imidazolium betaine, lauryldimethylaminoacetic acid betaine, fatty acid amidopropyl dimethylaminoacetate betaine, and the like.

The surfactant may or may not contain a surfactant compound having an amide group and an amino group, that is, an amideamine surfactant.

The amide amine surfactant has the formula:

Wherein each of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is independently the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms,

and n is 0 to 10.]

Is preferable.

R ¹¹ is preferably an alkyl group or an alkenyl group. The carbon number of R < ¹¹ > may be 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 1 to 6, especially 1 to 4. n is from 0 to 10, for example from 1 to 10, in particular from 2 to 5.

Specific examples of the amide amine surface active agent include diethylaminoethylamide isostearate, dimethylaminoethylamide oleate, dimethylaminopropylamide oleate, diethylaminoethylamide oleate, diethylaminopropylamide oleate, diethylaminoethylamide stearate, But are not limited to, diethylaminopropylamide, diethylaminopropylamide, stearic acid, dibutylaminopropylamide, stearic acid, diethylaminopropylamide, stearic acid, But are not limited to, diethylaminoethylamide, diethylaminopropylamide palmitate, dimethylaminoethylamide palmitate, dimethylaminopropylamide palmitate, diethylaminoethylamide behenate, diethylaminopropylamide behenate, Heptanoic acid dimethylaminopropylamide and the like.

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

Acid salts are obtained by neutralizing an amide amine with an acid, such as an inorganic acid and / or an organic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid and phosphoric acid. Examples of the organic acid include short-chain monocarboxylic acids such as acetic acid and propionic acid; Long-chain monocarboxylic acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and erucic acid; Dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid and phthalic acid; Hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid, and citric acid; Polycarboxylic acids such as polyglutamic acid; Acidic amino acids such as glutamic acid and aspartic acid; Alkyl sulfates, alkyl sulfonates, and alkyl phosphate esters. Of these, inorganic acids, short chain monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids and acidic amino acids are generally used, and hydrochloric acid, sulfuric acid, acetic acid, succinic acid, glycolic acid, lactic acid, malic acid, do.

The quaternary ammonium salt can be obtained by quaternizing an amide amine.

The amide amine surfactant may be nonionic or ionic (cationic), but it is preferably nonionic. In the case of nonionic, it is preferable to add an ionic compound such as an acid and ionize it.

The nonionic surfactant, the cationic surfactant, and the amphoteric surfactant may each 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, for example, 25% by weight or more based on the total amount of the nonionic surfactant and the cationic surfactant By weight, especially not less than 30% by weight, in particular not less than 35% by weight. The upper limit of the amount of the cationic surfactant may be, for example, 60% by weight, in particular 50% 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 the surfactant other than the nonionic surfactant and the cationic surfactant may be 50 wt% or less, for example, 20 wt% or less, or 0.1 wt% or more, based on the total amount of the surfactant.

The amount of the cationic surfactant may be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight per 100 parts by weight of the polymer. The total amount of the surfactant may be 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 amide amine surfactant may be 80 wt% or less, for example, 5 to 70 wt%, particularly 10 to 60 wt%, based on the total amount of the surfactant.

(3) Liquid media

The liquid medium may be water alone or a mixture of water and (water-miscible) organic solvent. The amount of the organic solvent may be 30 wt% or less, for example, 10 wt% or less (preferably 0.1 wt% 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 non-fluorine polymer as a polymer (active component), but may contain a fluorine-containing polymer in addition to the non-fluorine polymer. Generally, in a water and oil repellent composition (particularly, an aqueous emulsion), particles formed by a non-fluorine polymer and particles formed by a fluorine-containing polymer are present separately. That is, it is preferable to prepare the non-fluorine polymer and the fluorine-containing polymer separately and then mix the non-fluorine polymer and the fluorine-containing polymer. Generally, it is preferable to prepare an emulsion of a non-fluorine polymer (in particular, an aqueous emulsion) and an emulsion of a fluorine-containing polymer (in particular, an aqueous emulsion) separately and then mix an emulsion of a non-fluorine polymer and an emulsion of the fluorine- .

The fluorine-containing polymer is a polymer having a repeating unit derived from a fluorine-containing monomer. The fluorine-containing monomer is represented by the general formula:

Wherein X represents a 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, a CFX ¹ X ² group (provided that X ¹ and X ² are, A fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a straight 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 represents an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms,

-CH ₂ CH ₂ N (R ¹ ) SO ₂ - group (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms) or

-CH ₂ CH (OZ ¹ ) CH ₂ - group (wherein Z ¹ is a hydrogen atom or an acetyl group) or

- (CH ₂ ) _m --SO ₂ - (CH ₂ ) _n - group or - (CH ₂ ) _m -S- (CH ₂ ) _n- group wherein m is 1 to 10 and n is 0 to 10, ,

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

Is preferably an acrylate ester or acrylamide represented by the following formula

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

The fluorine-containing polymer may have a repeating unit derived from at least one non-fluorine monomer selected from the group consisting of halogenated olefin monomers, non-fluorine-free cross-linking monomers and non-fluorine cross-linking monomers.

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

Preferred non-fluorine non-crosslinkable monomers are those having the formula:

[Wherein A is a hydrogen atom, a methyl group, or a halogen atom (e.g., a chlorine atom, a bromine atom and an iodine atom) other than a fluorine atom,

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

≪ / RTI > Specific examples of the non-fluorine-incompatible monomer include alkyl (meth) acrylate esters, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (Meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and vinyl alkyl ether.

The non-fluorine-crosslinkable monomer may be a compound having at least two carbon-carbon double bonds (e.g., (meth) acrylic groups), or a compound having at least one carbon-carbon double bond and at least one reactive group.

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

Each of the non-fluorine polymer and the fluorine-containing polymer may be one kind of polymer, but may be a combination of two or more kinds of polymers.

When a combination of a non-fluorine polymer and a fluorine-containing polymer is used, a performance equivalent to or equivalent to that in the case of using only the fluorine-containing polymer (particularly, water and oil repellency) is obtained.

The polymer (non-fluorine polymer and fluorine-containing polymer) in the present invention can be produced by any of ordinary polymerization methods, and the conditions of the polymerization reaction can be arbitrarily selected. Such polymerization methods include solution polymerization, suspension polymerization and emulsion polymerization. Emulsion polymerization is preferred.

If the treating agent of the present invention is an aqueous emulsion, the production method of the polymer is not limited. For example, after a polymer is prepared by solution polymerization, an aqueous emulsion can be obtained by removing the solvent and adding a surfactant and water.

In the solution polymerization, a method of dissolving the monomer in an organic solvent in the presence of a polymerization initiator, substituting with nitrogen, and heating and stirring at 30 to 120 캜 for 1 to 10 hours is employed. As the polymerization initiator, for example, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicar And the like. The polymerization initiator is used in an amount of 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 inert to the monomers and dissolves them, and includes, for example, esters (for example, esters having 2 to 30 carbon atoms, specifically ethyl acetate, butyl acetate), ketones (for example, 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, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, , Methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichlorethylene, perchlorethylene, tetrachlorodi Fluoroethane, trichlorotrifluoroethane, and the like. The organic solvent is used in an amount of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by weight of the total amount of the monomers.

In the emulsion polymerization, a method of emulsifying monomers in water in the presence of a polymerization initiator and an emulsifier, replacing nitrogen, and stirring at a temperature in the range of 50 to 80 ° C for 1 to 10 hours, is employed. The polymerization initiator may be at least one selected from the group consisting of benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine- Examples of the organic peroxides include water-soluble ones such as isobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate, and azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t -Butyl peroxypivalate, diisopropyl peroxydicarbonate and the like can be used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.

In order to obtain a copolymer aqueous dispersion having excellent stability in storage, it is preferable to polymerize monomers in water by using an emulsifying apparatus capable of imparting strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. As the emulsifier, various emulsifiers such as anionic, cationic or nonionic emulsifiers can be used, and they are used in the range of 0.5 to 20 parts by weight based on 100 parts by weight of the monomers. It is preferred to use anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not used at all, it is preferable to add a compatibilizing agent sufficiently compatible with these monomers, for example, a water-soluble organic solvent or a low molecular weight monomer. By the addition of the compatibilizing agent, it is possible to improve emulsification and copolymerization.

Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc. and 1 to 50 parts by weight , For example, 10 to 40 parts by weight. Examples of the monomer having a low molecular weight include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate and the like. The amount of the monomer is preferably 1 to 50 For example, 10 to 40 parts by weight.

In the polymerization, a chain transfer agent may be used. Depending on the amount of chain transfer agent used, the molecular weight of the copolymer can be varied. Examples of the chain transfer agent include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, thioglycerol and the like (particularly alkyl mercaptans (for example, having 1 to 30 carbon atoms)), sodium hypophosphite, sodium hydrogen sulfite Inorganic salts and the like. The chain transfer agent may be used in an amount of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the monomers.

The treatment composition of the present invention may be in the form of a solution, an emulsion (particularly an aqueous dispersion) or an aerosol, but is preferably an aqueous dispersion. The treating composition comprises a copolymer (active component of the surface treatment agent) and a medium (particularly 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, especially 10 to 80% by weight, based on the treating composition.

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

The treating composition of the present invention can be applied to a subject to be treated by a conventional method. Usually, a method of dispersing and diluting the treating composition in an organic solvent or water, and adhering it to the surface of the material to be treated by a known method such as immersion coating, spray coating, or air bubble coating and drying is employed. Further, if necessary, curing may be performed by applying with a suitable crosslinking agent (for example, block isocyanate). It is also possible to add a repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixer, an anti-wrinkle agent, etc. to the treatment composition of the present invention. The concentration of the copolymer in the treatment liquid to be brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of immersion coating), for example, 0.05 to 10% by weight.

Examples of the object to be treated with the treating composition of the present invention (e.g., water and oil repellent agent) include a fiber product, a stone, a filter (e.g., electrostatic filter), a dustproof mask, Glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramics, plastics, plaster, and plaster. There are many examples of fiber products. For example, synthetic vegetable natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi- Inorganic fibers such as fibers, glass fibers, carbon fibers and asbestos fibers, and mixed fibers thereof.

The fiber product may be in the form of fiber, cloth or the like.

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

The copolymers can be applied to fibrous substrates (e.g., textile products) by any of the methods known for treating textile products with liquids. When the fiber product is a cloth, the cloth may be immersed in the solution, or the solution may be attached or sprayed on the cloth. The treated fiber product is dried and preferably heated, for example, at 100 ° C to 200 ° C to develop oil repellency.

Alternatively, the copolymer may be applied to a fiber product by a cleaning method. For example, the copolymer may be applied to a fiber product in laundry application or dry cleaning.

The textile product to be treated is typically a fabric, which includes fabrics, knits and nonwovens, garments in the form of garments, and carpets, while fibers or yarns or intermediate fiber products (e.g., slivers, . The fiber product material may be selected from the group consisting of natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or leucel), or synthetic fibers (such as polyester, polyamide or acrylic fibers Etc.), or a mixture of fibers (e.g., a mixture of natural fibers and synthetic fibers, etc.). The production polymer of the present invention is particularly effective in making cellulose-based fibers (for example, cotton or rayon) to be oleophobic and oil repellent. In addition, the process of the present invention generally makes the textile product hydrophobic and water repellent.

Alternatively, the fibrous base material may be a leather. The preparation polymer may also be applied to the leather as an aqueous solution or an aqueous emulsion during various stages of leather processing, for example during the wet processing period of the leather, or during the finish period of the leather, in order to make the leather hydrophobic and oleophobic do.

Alternatively, the fibrous substrate may be paper. The preparation polymer may be applied to preformed paper, or it may be applied during various stages of paper making, for example during the drying of paper.

By " treatment " is meant applying the treating agent to the material to be treated by immersion, spraying, coating, or the like. By the treatment, the copolymer which is an effective component of the treatment agent penetrates into the inside of the treatment subject and / or is adhered to the surface of the treatment subject.

The zeta potential of the aqueous emulsion treatment agent is preferably +30 mV or higher. The zeta potential is measured by a laser Doppler method (ELS-8000 manufactured by Otsuka Denshi Kabushiki Kaisha).

The dynamic surface tension of the water-based 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 Chemical Industry Co., Ltd.).

Example

EXAMPLES Next, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the description does not limit the present invention.

In the following, parts or percentages or percentages refer to parts by weight or weight percentages or weight ratios, unless otherwise specified.

The procedure of the test is as follows.

Water repellency test

The water repellency was evaluated according to the method described in JIS L1092 (C) (Bundesman test) under the conditions of a rainfall of 80 cc / min, a rainfall water temperature of 20 캜, a rainfall time of 5 minutes or 10 minutes. The water repellency was expressed as a six-step grade (0, 50, 70, 80, 90 and 100) of 0 to 100. The larger the score, the better the water repellency. A + (-) in the grade indicates that each property is slightly better (bad).

Production Example 1

A 500 ml autoclave was charged with 45 g of stearyl acrylate, 5 g of isobornyl methacrylate, 145 g of pure water, 15 g of tripropylene glycol, 1.5 g of sorbitan monooleate, 1.5 g of polyoxyethylene (EO: 18) 2 g of alkyl (C12-14) ether and 1.5 g of dioctadecyldimethylammonium chloride were added and emulsified and dispersed by ultrasonic wave at 60 DEG C for 15 minutes under stirring. After the inside of the autoclave was replaced with nitrogen, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid content was adjusted to 30% with pure water. The monomer composition of the resulting polymer was almost matched to the monomer loading composition.

Production Example 2

A 500 mL autoclave was charged with 40 g of stearyl acrylate, 10 g of isobornyl methacrylate, 145 g of pure water, 15 g of tripropylene glycol, 1 g of acetylene glycol polyoxyethylene adduct, 1 g of polyoxyethylene (EO: 18) iso 2 g of tridecyl ether and 2 g of dioctadecyldimethylammonium chloride were put and emulsified and dispersed by ultrasonic wave at 60 캜 for 15 minutes under stirring. After the inside of the autoclave was replaced with nitrogen, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid content was adjusted to 30% with pure water. The monomer composition of the resulting polymer was almost matched to the monomer loading composition.

Production Example 3

A 500 mL autoclave was charged with 40 g of stearyl acrylate, 10 g of adamantyl acrylate, 145 g of pure water, 15 g of tripropylene glycol, 1.5 g of sorbitan monooleate, 1.5 g of polyoxyethylene (EO: 18) C12-14) ether and 1.5 g of dioctadecyldimethylammonium chloride were added and emulsified and dispersed by ultrasonic wave at 60 占 폚 for 15 minutes under stirring. After the inside of the autoclave was replaced with nitrogen, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid content was adjusted to 30% with pure water. The monomer composition of the resulting polymer was almost matched to the monomer loading composition.

Production Example 4

A 500 mL autoclave was charged with 30 g of stearyl acrylate, 5 g of lauryl acrylate, 15 g of benzyl methacrylate, 145 g of pure water, 15 g of tripropylene glycol, 1.5 g of sorbitan monooleate, 18) Secondary alkyl (C12-14) ether = 2 g and dioctadecyldimethylammonium chloride = 1.5 g were added and emulsified and dispersed by ultrasonic wave at 60 DEG C for 15 minutes under stirring. After the inside of the autoclave was replaced with nitrogen, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid content was adjusted to 30% with pure water. The monomer composition of the resulting polymer was almost matched to the monomer loading composition.

Production Example 5

A 500 mL autoclave was charged with 25 g of stearyl acrylate, 15 g of behenyl acrylate, 10 g of isobornyl methacrylate, 145 g of pure water, 15 g of tripropylene glycol, 1.5 g of sorbitan monooleate, (EO: 18) secondary alkyl (C12-14) ether = 2 g and dioctadecyldimethylammonium chloride = 1.5 g were added and emulsified and dispersed in an ultrasonic wave at 60 DEG C for 15 minutes under stirring. After the inside of the autoclave was replaced with nitrogen, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid content was adjusted to 30% with pure water. The monomer composition of the resulting polymer was almost matched to the monomer loading composition.

Production Example 6

A 500 ml autoclave was charged with 35 g of stearyl acrylate, 10 g of isobornyl methacrylate, 5 g of glycidyl methacrylate, 145 g of pure water, 15 g of tripropylene glycol, 1 g of acetylene glycol polyoxyethylene adduct, 2 g of polyoxyethylene (EO: 18) isotridecyl ether and 2 g of dioctadecyldimethylammonium chloride were added and emulsified and dispersed by ultrasonic wave at 60 ° C. for 15 minutes under stirring. After the inside of the autoclave was replaced with nitrogen, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid content was adjusted to 30% with pure water. The monomer composition of the resulting polymer was almost matched to the monomer loading composition.

Production Example 7

A 500 mL autoclave was charged with 37.5 g of stearyl acrylate, 10 g of isobornyl methacrylate, 2.5 g of hydroxyethyl methacrylate, 145 g of pure water, 15 g of tripropylene glycol, 1.5 g of sorbitan monooleate , 2 g of polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether and 1.5 g of dioctadecyldimethylammonium chloride were added and emulsified and dispersed by ultrasonic wave at 60 DEG C for 15 minutes under stirring. After the inside of the autoclave was replaced with nitrogen, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid content was adjusted to 30% with pure water. The monomer composition of the resulting polymer was almost matched to the monomer loading composition.

Production Example 8

A 500 mL autoclave was charged with 35 g of stearyl acrylate, 10 g of benzyl methacrylate, 145 g of pure water, 15 g of tripropylene glycol, 1.5 g of sorbitan monooleate, 1.5 g of polyoxyethylene (EO: 18) -14) 2 g of ether and 1.5 g of dioctadecyldimethylammonium chloride were added and emulsified and dispersed by ultrasonic wave at 60 캜 for 15 minutes under stirring. After the inside of the autoclave was replaced with nitrogen, 5 g of vinyl chloride was introduced thereinto, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added, and the mixture was reacted at 60 ° C for 3 hours to obtain an aqueous dispersion ≪ / RTI > The solid content was adjusted to 30% with pure water. The monomer composition of the resulting polymer was almost matched to the monomer loading composition.

Production Example 9

A 500 mL autoclave was charged with 25 g of stearyl acrylate, 15 g of adamantyl acrylate, 2.5 g of glycidyl methacrylate, 145 g of pure water, 15 g of tripropylene glycol, 1.5 g of sorbitan monooleate, 2 g of ethylene (EO: 18) secondary alkyl (C12-14) ether and 1.5 g of dioctadecyldimethylammonium chloride were added and emulsified and dispersed by ultrasonic wave at 60 DEG C for 15 minutes under stirring. After the inside of the autoclave was purged with nitrogen, 7.5 g of vinylidene chloride was introduced thereinto, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added, and the mixture was allowed to react at 60 DEG C for 3 hours to obtain a polymer To obtain an aqueous dispersion. The solid content was adjusted to 30% with pure water. The monomer composition of the resulting polymer was almost matched to the monomer loading composition.

Comparative Preparation Example 1

(C12-14) ether = 2 g of polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether, 50 g of stearyl acrylate, 145 g of pure water, 15 g of tripropylene glycol, 1.5 g of sorbitan monooleate, And 1.5 g of dioctadecyldimethylammonium chloride were added and emulsified and dispersed by ultrasonic wave at 60 캜 for 15 minutes under stirring. After the inside of the autoclave was replaced with nitrogen, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid content was adjusted to 30% with pure water. The monomer composition of the resulting polymer was almost matched to the monomer loading composition.

Comparative Production Example 2

A 500 mL autoclave was charged with 40 g of stearyl acrylate, 10 g of lauryl acrylate, 145 g of pure water, 15 g of tripropylene glycol, 1.5 g of sorbitan monooleate, 1.5 g of polyoxyethylene (EO: 18) -14) 2 g of ether and 1.5 g of dioctadecyldimethylammonium chloride were added and emulsified and dispersed by ultrasonic wave at 60 캜 for 15 minutes under stirring. After the inside of the autoclave was replaced with nitrogen, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid content was adjusted to 30% with pure water. The monomer composition of the resulting polymer was almost matched to the monomer loading composition.

Comparative Production Example 3

A 500 mL autoclave was charged with 25 g of stearyl acrylate, 25 g of behenyl acrylate, 145 g of pure water, 15 g of tripropylene glycol, 1.5 g of sorbitan monooleate, 1.5 g of polyoxyethylene (EO: 18) -14) 2 g of ether and 1.5 g of dioctadecyldimethylammonium chloride were added and emulsified and dispersed by ultrasonic wave at 60 캜 for 15 minutes under stirring. After the inside of the autoclave was replaced with nitrogen, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid content was adjusted to 30% with pure water. The monomer composition of the resulting polymer was almost matched to the monomer loading composition.

Comparative Production Example 4

A 500 ml autoclave was charged with 20 g of stearyl acrylate, 25 g of lauryl acrylate, 5 g of glycidyl methacrylate, 145 g of pure water, 15 g of tripropylene glycol, 1.5 g of sorbitan monooleate, EO: 18) Secondary alkyl (C12-14) ether = 2 g and dioctadecyldimethylammonium chloride = 1.5 g were added and emulsified and dispersed by ultrasonic wave at 60 DEG C for 15 minutes under stirring. After the inside of the autoclave was replaced with nitrogen, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The solid content was adjusted to 30% with pure water. The monomer composition of the resulting polymer was almost matched to the monomer loading composition.

Comparative Preparation Example 5

A 500 mL autoclave was charged with 35 g of stearyl acrylate, 2.5 g of glycidyl methacrylate, 145 g of pure water, 15 g of tripropylene glycol, 1.5 g of sorbitan monooleate, 2 g of polyoxyethylene (EO: 18) 2 g of alkyl (C12-14) ether and 1.5 g of dioctadecyldimethylammonium chloride were added and emulsified and dispersed by ultrasonic wave at 60 DEG C for 15 minutes under stirring. After the inside of the autoclave was purged with nitrogen, 12.5 g of vinyl chloride was injected thereinto, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added, and the mixture was reacted at 60 DEG C for 3 hours to obtain an aqueous To obtain a dispersion. The solid content was adjusted to 30% with pure water. The monomer composition of the resulting polymer was almost matched to the monomer loading composition.

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

Reference Example 1 (Preparation of fluorine-based repellent)

_{(CF 2 CF 2) n -CH} 2 CH 2 OCOC (CH 3) = CH 2 (n = 2.0) 14.9g, stearyl acrylate 43.46g, pure 110g, dipropylene glycol - CF ₃ CF ₂ in 500ml reaction flask 18.82 g of monomethyl ether, 3.08 g of distearyldimethylammonium chloride, 0.87 g of stearyltrimethylammonium chloride, 2.1 g of polyoxyethylene lauryl ether (EO: 18. EO represents the number of ethylene oxide units) 0.45 g of isotridecyl ether (EO: 3) was added and emulsified and dispersed by ultrasonic wave at 60 캜 for 15 minutes under stirring. After the inside of the reaction flask was replaced with nitrogen, a solution of 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis (2-amidinopropane) dihydrochloride and 9 g of water was added and reacted at 60 ° C for 5 hours to obtain a polymer To obtain an aqueous dispersion (fluororespactant). The composition of the polymer almost matched the composition of the input 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 x 205 mm) was immersed in this test solution, passed through a mangle, and treated with a pin tenter at 160 캜 for 2 minutes. The test cloth was subjected to a water repellency test. The same procedure as the above procedure was repeated for PET tapestry and nylon tapestry. Thereafter, the Bundesman test was conducted. The results are shown in Table 2.

Examples 2 to 9 and Comparative Examples 1 to 5

Treated in the same manner as in Example 1, and subjected to the Bundesman test. The results are shown in Table 2.

Examples 10 to 11

25 g of each of the aqueous liquids (non-fluorine type repellant) prepared in Production Examples 1 and 4 and 25 g of the fluorine type repellent prepared in Reference Example 1 were diluted with tap water to prepare a test liquid (1000 g) And subjected to the Bundesman test. The results are shown in Table 2.

week)

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 / dioctadecyldimethylammonium chloride = 2/4/4 (weight ratio)

The treating agent of the present invention can be suitably used for a substrate such as a fiber product and a stoneware, and imparts superior water-repellence and oil-repellency to the substrate.

Another aspect of the present invention is as follows.

<1>

(1) A polymer composition comprising (i) at least 40 wt%

Wherein A ¹¹ is a hydrogen atom or a methyl group,

A ¹² is a straight-chain or branched aliphatic hydrocarbon group having 18 to 30 carbon atoms.]

A repeating unit derived from a long-chain (meth) acrylate ester monomer represented by the following formula

(ii) a repeating unit derived from a (meth) acrylate monomer having a cyclic hydrocarbon group

&Lt; / RTI &gt;

(2) a surfactant comprising a non-ionic surfactant and a cationic surfactant, and

(3) a liquid medium containing water

Based on the weight of the water-based emulsion.

&Lt; 2 &

The cyclic hydrocarbon group-containing acrylate ester monomer (ii)

Wherein A ²¹ is a hydrogen atom or a methyl group,

A ²² is a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms.]

Lt; 1 &gt;.

&Lt; 3 &

Polymer (1)

(iii) Formula:

Wherein A ²¹ is a hydrogen atom or a methyl group,

A ³² is a linear or branched aliphatic hydrocarbon group having less than 18 carbon atoms.]

(Meth) acrylate ester monomer represented by the following formula

&Lt; 1 > or < 2 >.

&Lt; 4 &

Polymer (1)

(iv) a repeating unit derived from a non-fluorine-crosslinkable monomer

1 &gt; to &lt; 3 &gt;.

&Lt; 5 &

The aqueous emulsion treatment agent according to < 4 >, wherein the non-fluorine-crosslinkable 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.

&Lt; 6 &

Polymer (1)

(v) repeating units derived from halogenated olefin monomers

To < 5 >, wherein the water-based emulsion treatment agent is a water-based emulsion.

&Lt; 7 &

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

&Lt; 8 &

The aqueous emulsion treatment agent according to any one of <1> to <7>, wherein the polymer (1) contains no fluorine atom.

&Lt; 9 &

With respect to 100 parts by weight of the repeating unit (i) in the polymer (1)

The amount of the repeating unit (ii) is 1 to 150 parts by weight,

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,

When the amount of the repeating unit (v) is 0 to 100 parts by weight

The aqueous emulsion treatment agent according to any one of <1> to <8>.

&Lt; 10 &

The aqueous emulsion treatment agent according to any one of <1> to <9>, wherein the amount of the cationic surfactant in the surfactant is 15% by weight or more.

&Lt; 11 &

Wherein the nonionic surfactant has the formula:

Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or an acyl group having 2 to 22 carbon atoms, each of R ² is independently the same or different and is an alkyl group having 3 or more carbon atoms (for example, 3 to 10 carbon atoms) an alkylene group, R ³ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group of 2 to 22, p is a number of 2 or more, q is a number of 0 or 1 or more.]

Wherein the water-based emulsion treatment agent is a compound represented by the following formula (1).

&Lt; 12 &

Wherein the nonionic surfactant is an acetylene alcohol compound selected from the group consisting of acetylene alcohol and an oxyethylene adduct of acetylene alcohol.

&Lt; 13 &

The acetylene alcohol compound has the formula:

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.

&Lt; 12 >, wherein R &lt; 1 &gt;

&Lt; 14 &

Wherein the cationic surfactant has the formula:

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,

X is an anionic group.]

To < 13 >, wherein R < 1 >

<15>

The aqueous emulsion treatment agent according to any one of <1> to <14>, wherein the fiber treatment agent further contains a fluorine-containing polymer.

&Lt; 16 &

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

&Lt; 17 &

The aqueous emulsion treatment agent according to any one of < 1 > to < 16 >, wherein the dynamic surface tension of the aqueous 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 / oil repellent agent or antifouling agent.

<20>

A method for treating a fiber product, comprising treating the fiber product with the water-based emulsion treating agent according to any one of <1> to <19>.

&Lt; 21 &

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

Claims (10)

(1) (i) Formula:
CH ₂ = CA ¹¹ -C (= O) -OA ¹²
Wherein A ¹¹ is a hydrogen atom or a methyl group,
A ¹² is a straight-chain or branched aliphatic hydrocarbon group having 18 to 30 carbon atoms.]
A repeating unit derived from a long-chain (meth) acrylate ester monomer represented by the following formula
(ii) a repeating unit derived from a (meth) acrylate monomer having a cyclic hydrocarbon group as a saturated or unsaturated crosslinking ring
A fluorine-containing polymer,
(2) a surfactant comprising a nonionic surfactant, a cationic surfactant or both, and
(3) a liquid medium containing water
Wherein the surface treatment agent is an aqueous emulsion. The cyclic hydrocarbon group-containing acrylate ester monomer (ii), which is a saturated or unsaturated crosslinking group, is represented by the formula:
CH ₂ = CA ²¹ -C (= O) -OA ²²
Wherein A ²¹ is a hydrogen atom or a methyl group,
A ²² is a cyclic hydrocarbon-containing group which is a saturated or unsaturated, bridging group having 4 to 30 carbon atoms.]
Is a compound represented by the formula The composition according to claim 1, wherein the surfactant (2) comprises 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 less than 22% Or more. The composition according to claim 1, wherein the nonionic surfactant is at least one selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides,
Wherein the cationic surfactant 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, wherein the surfactant (2) comprises a surfactant compound having both an amide group and an amino group. The surface treatment agent according to claim 1, wherein the surface treating agent contains no fluorine-containing polymer. The surface treatment agent according to claim 1, wherein the surface treating agent contains a fluorine-containing polymer. The non-fluoropolymer (1) according to claim 1, wherein the amount of the long chain (meth) acrylate ester monomer (i) is 40 to 95%
The amount of the cyclic hydrocarbon group-containing acrylate ester monomer (ii), which is a saturated or unsaturated crosslinking group, is 1 to 150 parts by weight based on 100 parts by weight of the long-chain (meth) acrylate ester monomer (i)
The concentration of the non-fluoropolymer (1) is 0.01 to 95% by weight with respect to the surface treatment agent,
The amount of the surfactant (2) is 0.1 to 20 parts by weight based on 100 parts by weight of the non-fluoropolymer (1)
A surface treating agent wherein the surface treating agent is a water-repellent or emulsifying agent. 9. A method for treating a fiber product, comprising treating the fiber product with the surface treating agent according to any one of claims 1 to 8. 9. A fiber product treated by the surface treatment agent according to any one of claims 1 to 8.