JP6107921B2 - Surface treatment agent - Google Patents

Description

  The present invention relates to an aqueous surface treatment agent, particularly a water / oil repellent and an antifouling agent.

Conventionally, a fluorine-containing water and oil repellent containing a fluorine compound is known. This water / oil repellent exhibits good water / oil repellency when treated on a substrate such as a textile product.
From 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 impact of PFOA (perfluorooctanoic acid), a type of fluoroalkyl compound, have become apparent, and on April 14, 2003, EPA (US Environmental Protection Agency) will strengthen scientific research on PFOA Announced.
Meanwhile, 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/opptintr/pfoa/pfoafacts.pdf) publishes that telomers can produce PFOA by degradation or metabolism (telomers mean long chain fluoroalkyl groups). We also announced that telomers are used in many products such as foam, water- and oil-repellent and antifouling foams, care products, cleaning products, carpets, textiles, paper and leather. Yes. There is concern about the accumulation of fluorine-containing compounds in the environment.
In addition, the fluorine-containing water / oil repellent containing the fluorine-containing polymer is subjected to heat treatment at a high temperature (for example, 100 ° C. or more) after being attached to a substrate such as a textile product in order to exhibit water / oil repellency. Must be given. High energy is required for heat treatment at high temperature.
Furthermore, the fluoropolymer is expensive.

Therefore, it may be desired not to use a fluoropolymer or to reduce the amount of the fluoropolymer.
JP 2006-328624 A is a water repellent comprising a non-fluorine polymer containing a (meth) acrylic acid ester having 12 or more carbon atoms in the ester moiety as a monomer unit, the (meth) acrylic acid ester Discloses a water repellent that is 80 to 100% by mass with respect to the total amount of monomer units constituting the non-fluorine polymer.
However, this water repellent is inferior in water and oil repellency.

JP 2006-328624

  An object of the present invention is to provide a surface treating agent that gives excellent water and oil repellency and preferably does not use a fluorine-containing monomer, particularly a fluoroalkyl group-containing monomer.

The present invention
(1) a polymer having a repeating unit derived from a long-chain (meth) acrylate ester monomer,
The present invention relates to (2) a surfactant, and (3) an aqueous emulsion treating agent containing a liquid medium containing water.

Aspects of the present invention are as follows.
[1]
(1) (a) Formula:
^{_{CH 2 = CA 11 -C (=}} O) -O-A 12
[In the formula, A ¹¹ represents a hydrogen atom or a methyl group;
A ¹² is a linear or branched aliphatic hydrocarbon group having 18 to 30 carbon atoms. ]
A non-fluorine polymer having a repeating unit derived from a long-chain (meth) acrylate ester monomer represented by:
(2) Including both nonionic surfactant and cationic surfactant, the amount of the cationic surfactant is 22% by weight or more based on the total amount of the nonionic surfactant and the cationic surfactant. A surface treatment agent which is a water-based emulsion containing a surfactant and (3) a liquid medium containing water.

[2]
The surface treatment agent according to [1], wherein the non-fluoropolymer (1) does not contain a (meth) acrylate monomer having a cyclic hydrocarbon group.
[3]
The nonionic surfactant is at least one selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides;
The surface treating agent according to [1] or [2], 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.

[4]
The surface treatment agent according to any one of [1] to [3], wherein the surface treatment agent does not contain a fluoropolymer.
[5]
The surface treatment agent according to any one of [1] to [3], wherein the surface treatment agent contains a fluoropolymer.
[6]
The surface treating agent according to any one of [1] to [5], which is a water / oil repellent or an antifouling agent.
[7]
A method for treating a textile product, comprising treating the textile product with the surface treatment agent according to any one of [1] to [6].

Since the treatment agent of the present invention does not use a fluoroalkyl group-containing monomer, there is no concern about accumulation of fluorine-containing compounds in the environment. The treatment agent of the present invention gives excellent water and oil repellency to the substrate. Furthermore, water / oil repellency is exhibited by low temperature treatment without the need for heat treatment at high temperature.
The treatment agent of the present invention has good stability (emulsion stability). The treatment agent of the present invention is excellent in durability (particularly washing durability) of water and oil repellency (particularly water repellency). Furthermore, the feel of the substrate is good.
Performance equal to or greater than or equal to that of a processing agent containing only a fluoropolymer containing a fluoroalkyl group-containing monomer as an active ingredient by a processing agent containing only a non-fluorine polymer as an active component (especially the initial Water / oil repellency including water / oil repellency).

In the present invention, the polymer (preferably a non-fluorine polymer) is
(A) having a repeating unit derived from a long-chain (meth) acrylate ester monomer.
The polymer may be a copolymer, and
(B) a repeating unit derived from a short chain (meth) acrylate ester monomer,
(C) having at least one repeating unit selected from the group consisting of repeating units derived from non-fluorine crosslinkable monomers, and (d) repeating units derived from halogenated olefin monomers. May be.
The polymer may have a fluorine atom, but preferably does not have a fluorine atom. That is, the polymer is preferably a non-fluorine polymer.

(A) long chain (meth) acrylate ester monomer long chain (meth) acrylate ester monomer has the formula:
^{_{CH 2 = CA 11 -C (=}} O) -O-A 12
[In the formula, A ¹¹ represents a hydrogen atom or a methyl group;
A ¹² is a linear or branched aliphatic hydrocarbon group having 18 to 30 carbon atoms. ]
It is a compound shown by these.
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.
A ¹¹ is particularly preferably a methyl group.
A ¹² is a linear or branched hydrocarbon group. The linear or branched hydrocarbon group may in particular be a linear hydrocarbon group. The linear or branched hydrocarbon group has 18 to 30 carbon atoms. The linear or branched hydrocarbon group preferably has 18 to 28 carbon atoms, particularly 18 or 22, and is generally a saturated aliphatic hydrocarbon group, particularly preferably an alkyl group.

Preferred specific examples of the long-chain (meth) acrylate ester monomer are stearyl (meth) acrylate and 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 provided by the polymer.

(B) short chain (meth) acrylate ester monomer polymer may have the repeating units derived from short-chain (meth) acrylate ester monomer.
The short chain (meth) acrylate ester monomer has the formula:
^{_{CH 2 = CA 21 -C (=}} O) -O-A 22
[In the formula, A ²¹ represents a hydrogen atom or a methyl group;
A ²² is a linear or branched aliphatic hydrocarbon group having less than 18 carbon atoms. ]
It is preferable that it is a compound shown by these.

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.
A ²¹ is particularly preferably a methyl group.
A ²² is a linear or branched hydrocarbon group. The linear or branched hydrocarbon group may in particular be a linear hydrocarbon group. 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 generally a saturated aliphatic hydrocarbon group, particularly preferably an alkyl group.

Specific examples of short chain (meth) acrylate ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) ) Acrylate, cetyl (meth) acrylate. Particularly preferred specific examples of the short chain (meth) acrylate ester monomer 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.

(C) a non-fluorinated crosslinking monomer polymer may have the repeating units derived from fluorine-free crosslinkable monomer, or may not possess.
A non-fluorine crosslinkable monomer is a monomer which does not contain 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 (meth) acrylate groups) and not containing fluorine. The non-fluorine crosslinkable monomer is a compound having at least two olefinic carbon-carbon double bonds (preferably a (meth) acrylate group), or at least one olefinic carbon-carbon double bond and at least one It may be a compound having a reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, 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 a non-fluorine crosslinkable monomer is a vinyl monomer having a hydroxyl group.
Examples of non-fluorine crosslinkable monomers include diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) ) Acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di ( Examples include, but are not limited to, (meth) acrylate.
The presence of the non-fluorine crosslinkable monomer increases the washing durability imparted by the polymer.

(D) Halogenated olefin monomer The halogenated olefin preferably has no fluorine atom.
The halogenated olefin is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms 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, vinylidene iodide. Vinyl chloride is preferred.
The presence of the halogenated olefin increases the washing durability provided by the polymer.

(E) Other monomers (e) other than the monomer monomers (a) to (d), for example, non-fluorine non-crosslinkable 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) acrylate, methoxypolypropylene glycol (meth) acrylate , And vinyl alkyl ethers. Other monomers are not limited to these examples.

The non-fluorine polymer (1) may contain a (meth) acrylate monomer having a cyclic hydrocarbon group, but preferably does not contain it.
In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylamide” means acrylamide or methacrylamide.

  Each of the monomers is preferably an acrylate ester because the water and oil repellency becomes high.

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

The amount of monomer (a) is 40% by weight or more, preferably 50 parts by weight or more based on the polymer. The amount of the monomer (a) may be 95 parts by weight or less, for example 80 parts by weight or less, or 75 parts by weight or less, or 70 parts by weight or less based on the polymer.
In the polymer, with respect to 100 parts by weight of the monomer (a),
The amount of the repeating unit (b) is 0 to 150 parts by weight, preferably 1 to 30 parts by weight,
The amount of the repeating unit (c) is 0 to 50 parts by weight, preferably 1 to 10 parts by weight,
The amount of the repeating unit (d) is 0 to 100 parts by weight, preferably 1 to 30 parts by weight,
The amount of the repeating unit (e) may be 0 to 100 parts by weight, preferably 1 to 30 parts by weight.

The number average molecular weight (Mn) of the polymer may generally be 1000 to 1000000, for example 5000 to 500000, in particular 3000 to 200000. The number average molecular weight (Mn) of the polymer is generally measured by GPC (gel permeation chromatography).
The polymer may be one kind of polymer or a combination of two or more kinds of polymers.

  In the present invention, a monomer is polymerized to obtain a treating agent composition in which the polymer is dispersed or dissolved in a medium.

The monomer used in the present invention may be as follows.
Monomer (a),
Monomer (a) + (b),
Monomer (a) + (c),
Monomer (a) + (b) + (c),
Monomer (a) + (d),
Monomer (a) + (b) + (d),
Monomer (a) + (c) + (d), or Monomer (a) + (b) + (c) + (d).
In addition to the above, the monomer (e) may be used.

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

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

(2-1) Examples of nonionic surfactants nonionic surfactants, ethers, esters, ester ethers, alkanol amine de Contact and amine oxides.
Examples of the ether are compounds having an oxyalkylene group (preferably a polyoxyethylene group).
Examples of esters are alcohol and fatty acid esters. Examples of the alcohol are 1 to 6 (especially 2 to 5) carbon atoms having 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, in particular 5 to 30 carbon atoms.
An example of the ester ether is a compound obtained by adding an alkylene oxide (particularly, ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of the alcohol are 1 to 6 (especially 2 to 5) carbon atoms having 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, in particular 5 to 30 carbon atoms.
Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or dialkanolamino. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, in particular 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms having 1 to 3 amino groups and 1 to 5 hydroxyl groups .
A Min'okishido may be an amine (secondary amine or preferably a tertiary amine) oxide (e.g. 5 to 50 carbon atoms).

The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The alkylene group in the oxyalkylene group preferably has 2 to 10 carbon atoms. In general, the number of oxyalkylene groups in the molecule of the nonionic surfactant is preferably 2 to 100.
Nonionic surface active agents are ethers, esters, ester ethers are selected from the group consisting of alkanol amine de Contact and amine oxide, is preferably a nonionic surfactant having an oxyalkylene group.
Nonionic surfactants are alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, linear and / or branched fatty acids (saturated and / or unsaturated). Polyalkylene glycol ester, polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), alkylene oxide adduct of acetylene glycol, and the like. Among these, the structures of the alkylene oxide addition moiety and the polyalkylene glycol moiety are polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (random copolymer or block copolymer) Is preferred).
The nonionic surfactant preferably has a structure that does not contain an aromatic group because of environmental problems (biodegradability, environmental hormones, etc.).

Nonionic surfactants have the 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, an alkenyl group having 2 to 22 carbon atoms, or an acyl group,
Each of R ² is independently the same or different and is an alkylene group having 3 or more carbon atoms (for example, 3 to 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,
q is 0 or a number of 1 or more. ]
It may be a compound shown by these.
R ¹ preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. Preferable specific 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 a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, — (R ² O) _q — may form a polyoxyalkylene chain.
The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly, a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, among which an oxypropylene chain is preferable.
Preferred nonionic surfactants have the formula:
R ¹ O— (CH ₂ CH ₂ O) _p —H
[Wherein, R ¹ and p are as defined above. ]
Is a surfactant.

Specific examples of nonionic surfactants are:
C ₁₀ H ₂₁ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₂ H ₂₅ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₆ H ₃₁ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₈ H ₃₅ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₈ H ₃₇ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₂ H ₂₅ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -C ₁₂ H ₂₅
C ₁₆ H ₃₁ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -C ₁₆ H ₃₁
C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -C ₁₂ H ₂₅
iso-C ₁₃ H ₂₇ O- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₀ H ₂₁ COO- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -H
C ₁₆ H ₃₃ COO- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q -C ₁₂ H ₂₅
[Wherein, p and q are as defined above. ]
Etc.

Specific examples of the nonionic surfactant, ethylene oxide and hexyl phenol, isooctanoate butylphenol, hexadecanol, oleic acid, alkane _(C 12 _{-C 16)} thiol, sorbitan mono fatty acid _(C 7 _{-C 19)} or alkyl Condensation products with (C ₁₂ -C ₁₈ ) amine and the like are included.

The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, in particular 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 300 to 5,000, for example, 500 to 3,000.
Nonionic surfactants can be used alone or in combination of two or more.
The nonionic surfactant is preferably a combination of two or more. In a combination of two or more, at least one nonionic surfactant is R ¹ O— (CH ₂ CH) in which the R ¹ group (and / or R ³ group) is a branched alkyl group (eg, an isotridecyl group). ^{_{2 O) p - (R 2}} O) q -R 3 [ _{^{especially, R 1 O- (CH 2 CH}} 2 O) p -H] may be a compound represented by. The amount of the nonionic surfactant in which R ¹ group is a branched alkyl group is 5 to 100 parts by weight, for example, 8 to 50 parts by weight, particularly 10 parts per 100 parts by weight of the nonionic surfactant (B2). It may be up to 40 parts by weight. In a combination of two or more, the remaining nonionic surfactant is an R ¹ group (and / or R ³ group) (saturated and / or unsaturated) linear alkyl group (eg, lauryl group (n- lauryl _{^{group)) R 1 O- (CH 2}} CH 2 O) p - (R 2 O) q -R 3 [ _{^{especially, R 1 O- (CH 2 CH}} 2 O) p -H] a compound represented by It may be.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester , Polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkyl alkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, Examples thereof include polyethylene glycol polypropylene glycol block copolymers.

  Since the dynamic surface tension of the water-based emulsion becomes low (that is, the aqueous emulsion easily penetrates into the substrate), the nonionic surfactant may be acetylene alcohol (particularly acetylene glycol) or acetylene alcohol (particularly acetylene). Glycol) oxyethylene adducts are preferred.

A preferred nonionic surfactant is an alcohol having an unsaturated triple bond or an alkylene oxide adduct of the alcohol (both the alcohol and the alkylene oxide adduct are referred to as “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 one or more triple bonds and one or more hydroxyl groups. The acetylene alcohol compound may be a compound containing a polyoxyalkylene moiety. Examples of the polyoxyalkylene moiety include polyoxyethylene, polyoxypropylene, a random addition structure of polyoxyethylene and polyoxypropylene, and a block addition structure of polyoxyethylene and polyoxypropylene.

The acetylene alcohol compound has the formula:
HO—CR ¹¹ R ¹² —C≡C—CR ¹³ R ¹⁴ —OH, or HO—CR ¹⁵ R ¹⁶ —C≡C—H
[Wherein, each of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ is independently the same or different and is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ]
It may be a compound shown by these. The acetylene alcohol compound may be an alkylene oxide adduct of the compound represented by this chemical formula. The alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and particularly preferably a linear or branched alkyl group having 6 to 12 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group. Moreover, as alkylene oxide, C1-C20 (especially 2-5) alkylene oxides, such as ethylene oxide and a propylene oxide, are preferable, and the addition number of alkylene oxide is preferable 1-50.

  Specific examples of the acetylene alcohol compound include acetylene diol, propargyl alcohol, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4 , 7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1- Examples include pentyne-3-ol, 3-hexyne-2,5-diol, 2-butyne-1,4-diol, and the like. Polyethoxylates and ethylene oxide adducts of these specific examples are also included.

  The nonionic surfactant may not have a triple bond, or may have a triple bond. The nonionic surfactant may be only one of a nonionic surfactant having no triple bond or a nonionic surfactant having a triple bond, but a nonionic surfactant having no triple bond and a nonionic surfactant having a triple bond It may be a combination of active agents. A combination of a nonionic surfactant having no triple bond and a nonionic surfactant having a triple bond has a triple bond with a nonionic surfactant having no triple bond (eg, a nonionic surfactant having an oxyalkylene group). The weight ratio of the nonionic surfactant (for example, acetylene alcohol compound) may be 10:90 to 90:10, such as 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, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, Quaternary ammonium salt type surfactants such as alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like can be mentioned.

Examples of cationic surfactants are:
^{R 21 -N + (-R 22)} (- R 23) (- R 24) X -
[In the formula, 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. ]
It is a compound of this. The hydrocarbon group may have an oxygen atom, and may be, for example, an oxyalkylene such as a polyoxyalkylene group (the alkylene has 2 to 5 carbon atoms, for example). 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 araliphatic hydrocarbon).
Specific examples of R ²¹ , R ²² , R ²³ and R ²⁴ include an alkyl group (for example, methyl group, butyl group, stearyl group, palmityl group), aryl group (for example, phenyl group), aralkyl group (for example, benzyl group) (Phenylmethyl group), phenethyl group (phenylethyl group)).
Specific examples of X are halogen (for example, chlorine), acid (for example, inorganic acid such as hydrochloric acid, organic acid such as acetic acid (particularly fatty acid)).
The cationic surfactant is particularly preferably 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:
R ³¹ _p -N ⁺ R ³² _q X ⁻
Wherein each R ³¹ is independently the same or different and is a C12 or higher (eg C ₁₂ -C ₅₀ ) linear and / or branched aliphatic (saturated and / or unsaturated) group. Yes,
Each of R ³² is independently the same or different, and is an H or C 1-4 alkyl group, benzyl group, polyoxyethylene group (number of oxyethylene groups, for example, 1 (particularly 2, particularly 3) to 50). (CH ₃ and C ₂ H ₅ are particularly preferred),
X is a halogen atom (eg, chlorine and bromine), a C ₁ -C ₄ fatty acid base,
p is 1 or 2, q is 2 or 3, and p + q = 4. ]
It may be an ammonium salt represented by R ³¹ may have 12 to 50 carbon atoms, for example 12 to 30 carbon atoms.

  Specific examples of the cationic surfactant include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl Di (hydropolyoxyethylene) ammonium chloride and benzyldodecyl di (hydropolyoxyethylene) ammonium chloride are included.

  Examples of amphoteric surfactants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Examples include aminoacetic acid betaine and fatty acid amidopropyldimethylaminoacetic acid betaine.

Each of the nonionic surfactant, the cationic surfactant, and the amphoteric surfactant may be one kind or a 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 25% or more, in particular 30% or more, especially 35% or more. The upper limit of the amount of cationic surfactant can be, for example, 60% by weight, in particular 50% by weight, in particular 45% by weight. The weight ratio of the nonionic surfactant to the cationic surfactant is preferably 85:15 to 20:80, more preferably 80:20 to 40:60. The amount of the surfactant other than the nonionic surfactant and the cationic surfactant may be 50% by weight or less, for example, 20% by weight or less based on the total amount of the surfactant. It may be 1% by weight or more.
The amount of the cationic surfactant may be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight with respect to 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 with respect to 100 parts by weight of the polymer.

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

  The water / oil repellent composition of the present invention may contain only the non-fluorine polymer as a polymer (active ingredient), but contains a fluorine-containing polymer in addition to the non-fluorine polymer. Also good. In general, in a water / oil repellent composition (particularly, an aqueous emulsion), particles formed of a non-fluorine polymer and particles formed of a fluoropolymer exist separately. That is, it is preferable to mix the non-fluorine polymer and the fluoropolymer after separately producing the non-fluoropolymer and the fluoropolymer. Generally, a non-fluoropolymer emulsion (especially an aqueous emulsion) and a fluoropolymer emulsion (especially an aqueous emulsion) are prepared separately, and then the non-fluoropolymer emulsion and the fluoropolymer emulsion are mixed. It is preferable.

The fluorine-containing polymer is a polymer having a repeating unit derived from a fluorine-containing monomer. The fluorine-containing monomer has the general formula:
CH ₂ = C (−X) −C (= O) −Y−Z−Rf (I)
[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 (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl group 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 — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms) or
-CH ₂ CH (OZ ¹ ) CH ₂ -group (where 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 (where m is 1 to 10, n is 0 to 10, is there),
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. ]
An acrylate ester or acrylamide represented by
The number of carbon atoms in the Rf group is preferably 1-6, particularly 4-6.

The fluorine-containing polymer is a repeating polymer derived from at least one non-fluorine monomer selected from the group consisting of halogenated olefin monomers, non-fluorine non-crosslinkable monomers and non-fluorine crosslinkable monomers. You may have a unit.
The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. Specific examples of halogenated olefin monomers are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide.

Preferred non-fluorine non-crosslinkable monomers have the formula:
CH ₂ = CA-T
[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom);
T is a hydrogen atom, a linear or cyclic hydrocarbon group having 1 to 20 carbon atoms, or a linear or cyclic organic group having 1 to 20 carbon atoms having an ester bond. ]
It is a compound shown by these. Specific examples of non-fluorine non-crosslinkable monomers 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 are included.

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

The weight ratio of the non-fluoropolymer to the fluoropolymer in the water / oil repellent composition is 100: 0 to 10:90, for example, 90:10 to 20:80, preferably 80:20 to 30:70. Good.
Each of the non-fluorine polymer and the fluorine-containing polymer may be a single polymer, or may be a combination of two or more polymers.
When using a combination of a non-fluorinated polymer and a fluorinated polymer, performance (particularly, water / oil repellency) equivalent to or better than when only a fluorinated polymer is used is obtained.

The polymer (non-fluorine polymer and fluoropolymer) in the present invention can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization. Emulsion polymerization is preferred.
If the processing agent of this invention is a water-system emulsion, the manufacturing method of a polymer will not be limited. For example, a water-based emulsion can be obtained by producing a polymer by solution polymerization and then removing the solvent and adding a surfactant and water.

  In solution polymerization, a method in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, is heated and stirred in the range of 30 to 120 ° C. for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. Can be mentioned. The polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

  The organic solvent is inactive to the monomer and dissolves them. For example, an ester (for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate or butyl acetate), a ketone (for example, carbon It may be a ketone having 2 to 30 (specifically, methyl ethyl ketone, diisobutyl ketone) or 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, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, Examples include diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in the range of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total amount of monomers.

  Emulsion polymerization employs a method in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after substitution with nitrogen, the mixture is stirred and polymerized in the range of 50 to 80 ° C. for 1 to 10 hours. Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azo Water-soluble materials such as bisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide Oil-soluble ones such as t-butyl peroxypivalate and diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

  In order to obtain a polymer aqueous dispersion with excellent storage stability, the monomer is polymerized by submerging the monomer into water using an emulsifier that can impart strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. It is desirable. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and the emulsifier is used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. Preference is given to using anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not completely compatible with each other, it is preferable to add a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer that is sufficiently compatible with these monomers. By adding a compatibilizing agent, it is possible to improve emulsifying properties and copolymerization properties.

  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 and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water. For example, you may use in the range of 10-40 weight part. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers, For example, you may use in the range of 10-40 weight part.

  In the polymerization, a chain transfer agent may be used. Depending on the amount of chain transfer agent used, the molecular weight of the polymer can be varied. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (for example, having 1 to 30 carbon atoms)), inorganic salts such as sodium hypophosphite and sodium bisulfite. Etc. You may use the usage-amount of a chain transfer agent in 0.01-10 weight part with respect to 100 weight part of total amounts of a monomer, for example, 0.1-5 weight part.

The treatment agent 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 agent composition comprises a polymer (active component of the surface treating 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, particularly 10 to 80% by weight, based on the treatment agent composition.
In the treating agent composition, the concentration of the polymer may be 0.01 to 95% by weight, for example 5 to 50% by weight.

  The treatment agent composition of the present invention can be applied to an object to be treated by a conventionally known method. Usually, the treatment agent composition is dispersed in an organic solvent or water, diluted, and attached to the surface of an object to be treated by a known method such as dip coating, spray coating, foam coating, etc., and then dried. Taken. If necessary, curing may be carried out by applying together with a suitable crosslinking agent (for example, blocked isocyanate). Furthermore, an insect repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent and the like can be added to the treatment agent composition of the present invention. The concentration of the polymer in the treatment liquid brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example 0.05 to 10% by weight.

  Examples of the object to be treated with the treating agent composition (for example, water and oil repellent) of the present invention include textile products, stone materials, filters (for example, electrostatic filters), dust masks, fuel cell components (for example, gas). Diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, plasters and the like. Various examples can be given as textile products. For example, natural animal and vegetable fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, and carbon fibers , Inorganic fibers such as asbestos fibers, or mixed fibers thereof.

The fiber product may be in the form of a fiber, cloth or the like.
The treatment agent composition of the present invention can also be used as an internal release agent or an external release agent.

  The polymer can be applied to a fibrous substrate (eg, a textile product, etc.) by any of the methods known for treating textile products with liquids. When the textile product is a fabric, the fabric may be immersed in the solution, or the solution may be attached or sprayed onto the fabric. The treated textile product is dried and preferably heated at, for example, 100 ° C. to 200 ° C. in order to develop oil repellency.

  Alternatively, the polymer may be applied to the textile by a cleaning method, such as a laundry application or a dry cleaning method.

  The textile products to be treated are typically fabrics, which include woven, knitted and non-woven fabrics, fabrics and carpets in clothing form, but fibers or yarns or intermediate fiber products (eg sliver or It may be a roving yarn). The textile product material may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or rheocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers), or May be a mixture of fibers, such as a mixture of natural and synthetic fibers. The production polymer of the present invention is particularly effective in making cellulosic fibers (such as cotton or rayon) oleophobic and oleophobic. The method of the present invention also generally makes the textile product hydrophobic and water repellent.

Alternatively, the fibrous base material may be leather. In order to make the production polymer hydrophobic and oleophobic, aqueous solutions or aqueous emulsifications at various stages of leather processing, for example during the wet processing of leather or during the finishing of leather You may apply it to leather from things.
Alternatively, the fibrous substrate may be paper. The production polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example during the drying period of the paper.

  “Treatment” means that a treatment agent is applied to an object to be treated by dipping, spraying, coating, or the like. By the treatment, the polymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object.

The zeta potential of the aqueous emulsion treating agent is preferably +30 mV or more. The zeta potential is measured by a 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 is measured by the maximum bubble pressure method (BP-D5 manufactured by Kyowa Interface Science Co., Ltd.).

Next, the present invention will be specifically described with reference to examples and comparative examples. However, these explanations do not limit the present invention.
In the following, parts or% or ratio represents parts by weight or weight% or weight ratio unless otherwise specified.
The test procedure is as follows.

Shower water repellency A shower water repellency test was conducted according to JIS-L-1092. The shower water repellency test (as shown in the table below) is a water repellency no. Represented by.

  Use a glass funnel with a volume of at least 250 ml and a spray nozzle that can spray 250 ml of water for 20-30 seconds. The specimen frame is a metal frame having a diameter of 15 cm. Three test piece sheets having a size of about 20 cm × 20 cm are prepared, and the sheet is fixed to the test piece holder frame so that the sheet is not wrinkled. Center the spray on the center of the sheet. Room temperature water (250 mL) is placed in a glass funnel and sprayed onto the specimen sheet (over a time period of 25-30 seconds). Remove the holding frame from the base, grab one end of the holding frame, tap the front surface down and dab the opposite end with a hard substance. Rotate the holding frame 180 ° further and repeat the same procedure to drop excess water drops. Wet specimens are compared to wet reference standards to score 0, 50, 70, 80, 90 and 100 in order of poor water repellency. Results are obtained from the average of three measurements.

Water-repellent washing durability
JIS L-0217-103 washing is repeated 5 to 20 times, and the subsequent water and oil repellency is evaluated (HL5, 20).

Texture evaluation
The following five levels of sensory evaluation were carried out by five measurers, and the average was taken.
5: Very soft
4: Soft
3: Untreated cloth
2: Hard
1: Very hard

Mechanical stability test The mechanically stable aqueous dispersion was diluted to 1% with tap water, stirred with a homomixer at 3,000 rpm for 10 minutes, and the generated scum was filtered onto a black cotton cloth.
○: No scum △: Some scum ×: Many scum

Peel strength <br/> Peel strength of synthetic film
A treatment liquid was prepared by diluting an aqueous dispersion of the polymer with water so that the solid content concentration was 1% by weight. A nylon cloth is dipped in a treatment solution, squeezed with a mangle at 4 kg / cm ² and 4 m / min, heat treated at 170 ° C. for 1 minute, and then a urethane resin-based adhesive having a concentration of 50% using MEK and ethyl acetate as a solvent ( Crisbon 4010FT manufactured by DIC Corporation) was applied to one side of a nylon cloth in a dot shape, and a polyurethane synthetic film was pressure-bonded, followed by heat treatment at 120 ° C. for 2 minutes. The obtained nylon cloth was repeatedly washed 20 times with AATCC 88B (1) (III), and then the peeled state of the synthetic film was visually observed, and the state was evaluated as follows.
A: No peeling at all
○: There is very little peeling
×: Clear separation

Production Example 1
500mL autoclave with stearyl acrylate = 50g, pure water = 145g, tripropylene glycol = 15g, sorbitan monooleate = 1.5g, polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether = 2g, dioctadecyldimethyl Ammonium chloride = 1.5 g was added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added and reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Production Example 2
In a 500 mL autoclave, stearyl acrylate = 50 g, pure water = 145 g, tripropylene glycol = 15 g, acetylene glycol polyoxyethylene adduct = 1 g, polyoxyethylene (EO: 18) isotridecyl ether = 2 g, dioctadecyldimethylammonium chloride = 2 g was added and emulsified and dispersed with ultrasound at 60 ° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added and reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Production Example 3
Stearyl acrylate = 50 g, pure water = 145 g, tripropylene glycol = 15 g, acetylene glycol polyoxyethylene adduct = 1 g, polyoxyethylene (EO: 18) lauryl ether = 2.9 g, octadecyltrimethylammonium chloride = 1.1 g in a 500 mL autoclave The mixture was emulsified and dispersed with ultrasound at 60 ° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added and reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Production Example 4
Behenyl acrylate = 47.5g, glycidyl methacrylate = 2.5g, pure water = 145g, tripropylene glycol = 15g, acetylene glycol polyoxyethylene adduct = 1g, polyoxyethylene (EO: 18) isotridecyl ether = 2g in a 500mL autoclave Then, dioctadecyldimethylammonium chloride = 2 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added and reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Production Example 5
Stearyl acrylate = 47.5 g, glycidyl methacrylate = 2.5 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan monooleate = 1.5 g, polyoxyethylene (EO: 18) secondary alkyl (C12-14) Ether = 2 g and dioctadecyldimethylammonium chloride = 1.5 g were added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added and reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Production Example 6
Stearyl acrylate = 20 g, behenyl acrylate = 15 g, behenyl methacrylate = 12.5 g, glycidyl methacrylate = 2.5 g, pure water = 145 g, tripropylene glycol = 15 g, acetylene glycol polyoxyethylene adduct = 1 g, polyoxyethylene (500 mL autoclave) EO: 18) Isotridecyl ether = 2g and dioctadecyldimethylammonium chloride = 2g were added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added and reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Production Example 7
Stearyl acrylate = 20 g, lauryl acrylate = 30 g, pure water = 145 g, tripropylene glycol = 15 g, acetylene glycol polyoxyethylene adduct = 1 g, polyoxyethylene (EO: 18) isotridecyl ether = 2 g, 500 mL autoclave Octadecyldimethylammonium chloride = 2 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added and reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Production Example 8
500 mL autoclave with behenyl acrylate = 20 g, lauryl acrylate = 27.5 g, hydroxyethyl methacrylate = 2.5 g, pure water = 145 g, tripropylene glycol = 15 g, acetylene glycol polyoxyethylene adduct = 1 g, polyoxyethylene (EO: 18) Isotridecyl ether = 2 g and dioctadecyldimethylammonium chloride = 2 g were added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added and reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Production Example 9
Stearyl acrylate = 10g, behenyl acrylate = 10g, cetyl acrylate = 27.5g, hydroxyethyl methacrylate = 2.5g, pure water = 145g, tripropylene glycol = 15g, acetylene glycol polyoxyethylene adduct = 1g, polyoxyethylene (EO: 18) Lauryl ether = 2.9 g and octadecyltrimethylammonium chloride = 1.1 g were added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added and reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Production Example 10
In a 500 mL autoclave, stearyl acrylate = 35 g, glycidyl methacrylate = 2.5 g, pure water = 145 g, tripropylene glycol = 15 g, acetylene glycol polyoxyethylene adduct = 1 g, polyoxyethylene (EO: 18) isotridecyl ether = 2 g, Dioctadecyldimethylammonium chloride = 2 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After replacing the inside of the autoclave with nitrogen, 12.5 g of vinyl chloride was charged by injection, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C. for 3 hours to disperse the polymer in water. A liquid was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Production Example 11
500mL autoclave with stearyl acrylate = 17.5g, behenyl acrylate = 17.5g, hydroxyethyl methacrylate = 5g, pure water = 145g, tripropylene glycol = 15g, sorbitan monooleate = 1.5g, polyoxyethylene (EO: 18) grade 2 Alkyl (C12-14) ether = 2 g and dioctadecyldimethylammonium chloride = 1.5 g were added, and the mixture was emulsified and dispersed with ultrasound at 60 ° C. for 15 minutes with stirring. After the inside of the autoclave was replaced with nitrogen, 10 g of vinyl chloride was charged by injection, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of polymer. Got. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Production Example 12
Stearyl acrylate = 30 g, lauryl acrylate = 10 g, glycidyl methacrylate = 2.5 g, pure water = 145 g, tripropylene glycol = 15 g, acetylene glycol polyoxyethylene adduct = 1 g, polyoxyethylene (EO: 18) lauryl ether in a 500 mL autoclave = 2.9 g and octadecyltrimethylammonium chloride = 1.1 g were added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After replacing the inside of the autoclave with nitrogen, 7.5 g of vinyl chloride was charged by injection, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C. for 3 hours to disperse the polymer in water. A liquid was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Production Example 13
In a 500 mL autoclave, stearyl acrylate = 35 g, glycidyl methacrylate = 2.5 g, pure water = 145 g, tripropylene glycol = 15 g, acetylene glycol polyoxyethylene adduct = 1 g, polyoxyethylene (EO: 18) isotridecyl ether = 2 g, Dioctadecyldimethylammonium chloride = 2 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After replacing the inside of the autoclave with nitrogen, 12.5 g of vinylidene chloride was charged by injection, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C for 3 hours to disperse the polymer in water. A liquid was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Production Example 14
Stearyl acrylate = 20 g, lauryl acrylate = 17.5 g, glycidyl methacrylate = 2.5 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan monooleate = 1.5 g, polyoxyethylene (EO: 18) secondary alkyl in a 500 mL autoclave (C12-14) Ether = 2 g and dioctadecyldimethylammonium chloride = 1.5 g were added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the inside of the autoclave was replaced with nitrogen, 10 g of vinyl chloride was charged by injection, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of polymer. Got. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Production Example 15
Behenyl acrylate = 20 g, lauryl acrylate = 17.5 g, glycidyl methacrylate = 2.5 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan monooleate = 1.5 g, polyoxyethylene (EO: 18) secondary alkyl in a 500 mL autoclave (C12-14) Ether = 2 g and dioctadecyldimethylammonium chloride = 1.5 g were added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the inside of the autoclave was replaced with nitrogen, 10 g of vinyl chloride was charged by injection, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of polymer. Got. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Comparative production example 1
500mL autoclave, lauryl acrylate = 50g, pure water = 145g, tripropylene glycol = 15g, sorbitan monooleate = 1.5g, polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether = 2g, dioctadecyldimethyl Ammonium chloride = 1.5 g was added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added and reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Comparative production example 2
500 mL autoclave with cetyl acrylate = 50 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan monooleate = 1.5 g, polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether = 2 g, dioctadecyldimethyl Ammonium chloride = 1.5 g was added, and the mixture was emulsified and dispersed with ultrasound at 60 ° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added and reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Comparative production example 3
In a 500 mL autoclave, stearyl acrylate = 15 g, lauryl acrylate = 35 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan monooleate = 1.5 g, polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether = 2 g and dioctadecyldimethylammonium chloride = 1.5 g were added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added and reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Comparative production example 4
Stearyl acrylate = 50g, pure water = 145g, tripropylene glycol = 15g, sorbitan monooleate = 2g, polyoxyethylene (EO: 18) stearyl ether = 2g, dioctadecyldimethylammonium chloride = 1g in a 500mL autoclave and stirred The mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes. After the atmosphere in the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added and reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Comparative production example 5
Stearyl acrylate = 50g, pure water = 145g, tripropylene glycol = 15g, acetylene glycol polyoxyethylene adduct = 0.25g, polyoxyethylene (EO: 18) lauryl ether = 3g, octadecyltrimethylammonium chloride = 0.75g The mixture was emulsified and dispersed with ultrasound at 60 ° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added and reacted at 60 ° C. for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Comparative production example 6
500 mL autoclave with stearyl acrylate = 35 g, glycidyl methacrylate = 2.5 g, pure water = 145 g, tripropylene glycol = 15 g, sorbitan monooleate = 2 g, polyoxyethylene (EO: 18) stearyl ether = 2 g, dioctadecyldimethylammonium chloride = 1 g was added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C for 15 minutes with stirring. After replacing the inside of the autoclave with nitrogen, 12.5 g of vinyl chloride was charged by injection, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C. for 3 hours to disperse the polymer in water. A liquid was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

Comparative production example 7
Stearyl acrylate = 35g, glycidyl methacrylate = 2.5g, pure water = 145g, tripropylene glycol = 15g, acetylene glycol polyoxyethylene adduct = 0.25g, polyoxyethylene (EO: 18) lauryl ether = 3g, octadecyl Trimethylammonium chloride = 0.75 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After replacing the inside of the autoclave with nitrogen, 12.5 g of vinyl chloride was charged by injection, 2,2-azobis (2-amidinopropane) dihydrochloride = 0.5 g was added, and the mixture was reacted at 60 ° C. for 3 hours to disperse the polymer in water. A liquid was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the produced polymer almost coincided with the monomer charge composition.

  Table 1 shows the raw materials used in the production examples and comparative production examples.

Reference Example 1 (Production of fluorinated repellent)
In a 500 ml reaction flask, CF ₃ CF ₂ — (CF ₂ CF ₂ ) _n —CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ (n = 2.0) 14.9 g, stearyl acrylate 43,46 g, pure water 110 g, Dipropylene glycol monomethyl ether 18.62g, distearyldimethylammonium chloride 3.08g, stearyltrimethylammonium chloride 0.87g, polyoxyethylene lauryl ether (EO: 18, EO represents the number of ethylene oxide units) 2.1g, polyoxy 0.65 g of ethylene isotridecyl ether (EO: 3) was added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the atmosphere in 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. An aqueous dispersion (fluorine repellent) was obtained. The composition of the polymer almost coincided with the composition of the charged monomer.

Example 1
A test liquid (1000 g) was prepared by diluting 50 g of the aqueous liquid produced in Production Example 1 with tap water. A cloth (510 mm × 205 mm) was immersed in this test solution, passed through a mangle, and treated with a pin tenter at 160 ° C. for 2 minutes. As the cloth, PET taffeta cloth, nylon taffeta cloth, and cotton twill cloth were used. Each cloth was divided into unwashed and washed 5 times, and a shower water repellency test (washing durability test) was conducted. The hand test and the mechanical stability test were performed on unwashed cloth. The results are shown in Table 2.

Examples 2-9 and Comparative Examples 1-5
After the same treatment as in Example 1, a shower water repellency test (washing durability test), a texture test, and a mechanical stability test were performed. The results are shown in Table 2.

Examples 10-15 and Comparative Examples 6-7
A test liquid (1000 g) was prepared by diluting 50 g of the aqueous liquid produced in each production example and 10 g of MDI-based blocked isocyanate (solid content concentration 20%) with tap water. Thereafter, the same treatment as in Example 1 was performed, and a shower water repellency test (washing durability test), a mechanical stability test, and a peel strength test were performed. The results are shown in Table 2.

Example 16
25 g of the aqueous liquid produced in Production Example 1 and 25 g of the fluorinated repellent produced in Reference Example 1 were diluted with tap water to prepare a test solution (1000 g). Thereafter, the same treatment as in Example 1 was performed, and a shower water repellency test (washing durability test), a texture, and a mechanical stability test were performed. The results are shown in Table 1.

Example 17
25 g of the aqueous liquid produced in Production Example 10, 25 g of the fluorinated repellent produced in Reference Example 1 and 10 g of MDI-based blocked isocyanate (solid content 20%) are diluted with tap water, and the test solution (1000 g) is obtained. Prepared. Thereafter, the same treatment as in Example 1 was performed, and a shower water repellency test (washing durability test), a mechanical stability test, a peel strength test, and a washing durability test were performed. The results are shown in Table 1.

注）
乳化剤1：ソルビタンモノオレエート/ポリオキシエチレン(ＥＯ：１８)2級アルキル(C12-14)エーテル /ジオクタデシルジメチルアンモニウムクロライド=3/4/3（重量比）
乳化剤2：アセチレングリコールポリオキシエチレン付加物/ポリオキシエチレン(ＥＯ：１８)イソトリデシルエーテル/ジオクタデシルジメチルアンモニウムクロライド=2/4/4（重量比）
乳化剤3：アセチレングリコールポリオキシエチレン付加物/ポリオキシエチレン(ＥＯ：１８)ラウリルエーテル/オクタデシルトリメチルアンモニウムクロライド=2/5.8/2.2（重量比）
乳化剤4：ソルビタンモノオレエート/ポリオキシエチレン(ＥＯ：１８)ステアリルエーテル/ジオクタデシルジメチルアンモニウムクロライド=4/4/2（重量比）
乳化剤5：アセチレングリコールポリオキシエチレン付加物/ポリオキシエチレン(ＥＯ：１８)ラウリルエーテル/オクタデシルトリメチルアンモニウムクロライド=0.5/6/1.5（重量比）

note)
Emulsifier 1: Sorbitan monooleate / Polyoxyethylene (EO: 18) Secondary alkyl (C12-14) ether / Dioctadecyldimethylammonium chloride = 3/4/3 (weight ratio)
Emulsifier 2: Acetylene glycol polyoxyethylene adduct / polyoxyethylene (EO: 18) isotridecyl ether / dioctadecyldimethylammonium chloride = 2/4/4 (weight ratio)
Emulsifier 3: Acetylene glycol polyoxyethylene adduct / polyoxyethylene (EO: 18) lauryl ether / octadecyltrimethylammonium chloride = 2 / 5.8 / 2.2 (weight ratio)
Emulsifier 4: Sorbitan monooleate / polyoxyethylene (EO: 18) stearyl ether / dioctadecyldimethylammonium chloride = 4/4/2 (weight ratio)
Emulsifier 5: Acetylene glycol polyoxyethylene adduct / polyoxyethylene (EO: 18) lauryl ether / octadecyltrimethylammonium chloride = 0.5 / 6 / 1.5 (weight ratio)

  The treatment agent of the present invention can be suitably used for substrates such as textiles and masonry, and imparts excellent water and oil repellency to the substrate.

Another aspect of the present invention is as follows.
<1>
(1) (a) 40% by weight or more of the formula:
^{_{CH 2 = CA 11 -C (=}} O) -O-A 12
[In the formula, A ¹¹ represents a hydrogen atom or a methyl group;
A ¹² is a linear or branched aliphatic hydrocarbon group having 18 to 30 carbon atoms. ]
A polymer having a repeating unit derived from a long-chain (meth) acrylate ester monomer represented by:
(2) A surfactant containing a nonionic surfactant and a cationic surfactant, the amount of the cationic surfactant being 15% by weight or more, and (3) an aqueous emulsion treating agent containing a liquid medium containing water .
<2>
The polymer (1) further has the formula (b):
^{_{CH 2 = CA 21 -C (=}} O) -O-A 22
[In the formula, A ²¹ represents a hydrogen atom or a methyl group;
A ²² is a linear or branched aliphatic hydrocarbon group having less than 18 carbon atoms. ]
The aqueous emulsion treating agent according to <1>, having a repeating unit derived from a short-chain (meth) acrylate ester monomer represented by:

<3>
The aqueous emulsion treating agent according to <1> or <2>, wherein the polymer (1) further has (c) a repeating unit derived from a non-fluorine crosslinkable monomer.
<4>
The non-fluorine crosslinkable monomer (c) is a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond and at least one reactive group <3> The aqueous emulsion treating agent according to 3>.
<5>
The polymer (1) is
(D) The aqueous emulsion treating agent according to any one of <1> to <4>, having a repeating unit derived from a halogenated olefin monomer.
<6>
The polymer (1) is
(D) The aqueous emulsion treating agent according to any one of <1> to <4>, which does not have a repeating unit derived from a halogenated olefin monomer.

<7>
The aqueous emulsion treating agent according to <5> or <6>, wherein the halogenated olefin monomer (d) is at least one selected from the group consisting of vinyl chloride and vinylidene chloride.
<8>
The polymer (1) does not contain both a (meth) acrylate monomer having a glass transition point of 50 ° C. or higher and a (meth) acrylate monomer having a cyclic hydrocarbon group. The aqueous emulsion treating agent according to any one of 1> to <7>.
<9>
The aqueous emulsion treating agent according to any one of <1> to <8>, wherein the polymer (1) does not contain a fluorine atom.

<10>
In the polymer (1), with respect to 100 parts by weight of the repeating unit (a),
The amount of the repeating unit (b) is 0 to 150 parts by weight,
The amount of the repeating unit (c) is 0 to 50 parts by weight,
The aqueous emulsion treating agent according to any one of <1> to <9>, wherein the amount of the repeating unit (d) is 0 to 100 parts by weight.
<11>
Nonionic surfactant has the 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, an alkenyl group having 2 to 22 carbon atoms, or an acyl group, and each R ² is independently the same or different and has 3 or more carbon atoms (for example, 3 To 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 0 or a number of 1 or more. . ]
The aqueous emulsion treating agent according to any one of <1> to <10>, which is a compound represented by the formula:

<12>
The aqueous emulsion treatment agent according to any one of <1> to <10>, wherein the nonionic surfactant is an acetylene alcohol compound selected from the group consisting of acetylene alcohol and an oxyethylene adduct of acetylene alcohol.
<13>
The acetylene alcohol compound has the formula:
HO—CR ¹¹ R ¹² —C≡C—CR ¹³ R ¹⁴ —OH, or HO—CR ¹⁵ R ¹⁶ —C≡C—H
[Wherein, each of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ is independently the same or different and is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ]
The aqueous emulsion treating agent according to <12>, which is a compound represented by the formula:

<14>
The cationic surfactant has the formula:
^{R 21 -N + (-R 22)} (- R 23) (- R 24) X -
[In the formula, 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. ]
The aqueous emulsion treating agent according to any one of <1> to <13>, which is a compound represented by:
<15>
The aqueous emulsion treatment agent according to any one of <1> to <14>, wherein the fiber treatment agent further contains a fluoropolymer.
<16>
The 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> 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 aqueous emulsion treating agent according to any one of <1> to <18>, which is a water / oil repellent or an antifouling agent.
<20>
A method for treating a textile product, comprising treating the textile product with the aqueous emulsion treating agent according to any one of <1> to <19>.
<21>
The textiles processed with the water-system emulsion processing agent in any one of <1>-<19>.

Claims (9)

(1) (a) Formula:
^{_{CH 2 = CA 11 -C (=}} O) -O-A 12
[In the formula, A ¹¹ represents a hydrogen atom or a methyl group;
A ¹² is a linear or branched aliphatic hydrocarbon group having 18 to 30 carbon atoms. ]
A non-fluorine polymer having a repeating unit derived from a long-chain (meth) acrylate ester monomer represented by:
(2) Including both a nonionic surfactant and a cationic surfactant, the amount of the cationic surfactant is 22 to 60% by weight with respect to the total amount of the nonionic surfactant and the cationic surfactant. A surface-treating agent that is an aqueous emulsion containing a surfactant and (3) a liquid medium containing water,
A surface treatment agent in which the surface treatment agent does not contain a fluoropolymer.   The surface treating agent according to claim 1, wherein the non-fluorine polymer (1) does not contain a (meth) acrylate monomer having a cyclic hydrocarbon group. Wherein the nonionic surfactant is an ether, ester, ester ether, at least one selected from the group consisting of alkanol amine de Contact and amine oxides,
The surface treatment agent according to claim 1 or 2, wherein the cationic surfactant is at least one selected from the group consisting of amines, amine salts, quaternary ammonium salts, imidazolines and imidazolinium salts. In addition to ether, which is a nonionic surfactant, a compound having an oxyalkylene group,
i) alcohol and fatty acid esters,
ii) the ester of the alcohol and a fatty acid, ester ether is a compound obtained by adding an alkylene-oxy-de
iii) alkanolamide, you and
The surface treating agent according to any one of claims 1 to 3, comprising at least one compound selected from the group consisting of iv ) amine oxides. In addition to ether, which is a nonionic surfactant, a compound having a polyoxyethylene group,
i) The surface treating agent according to any one of claims 1 to 4, comprising an ester of an alcohol and a fatty acid. The surface treatment agent according to any one of claims 1 to 5, wherein the amount of the cationic surfactant is 25 to 60% by weight .   The surface treatment agent according to any one of claims 1 to 6, which is a water / oil repellent or an antifouling agent.   A method for treating a textile product, comprising treating the textile product with the surface treatment agent according to claim 1.   The manufacturing method of the processed textiles including applying the surface treating agent in any one of Claims 1-7 to textiles.