JP6657730B2 - Surface treatment agent - Google Patents

Description

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

Conventionally, a fluorine-containing water- and oil-repellent containing a fluorine compound has been known. This water / oil repellent exhibits good water / oil repellency when applied to a substrate such as a fiber product.
Long chain 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, are becoming apparent. On April 14, 2003, the US Environmental Protection Agency (EPA) will strengthen scientific research on PFOA. Announced.
Meanwhile, 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) and EPA OPPT FACT SHEET April 14, 2003 (http: // www. epa.gov/opptintr/pfoa/pfoafacts.pdf) states that telomers can decompose or metabolize to form PFOA (telomers mean long-chain fluoroalkyl groups). He also announced that telomers are used in many products such as foams, water- and oil-repellent, antifouling foam, care products, cleaning products, carpets, textiles, paper and leather. I have. There is a concern that the fluorine-containing compound will accumulate in the environment.
Further, in order to exhibit water- and oil-repellency, the fluorine-containing water- and oil-repellent must be subjected to a heat treatment at a high temperature (for example, 100 ° C. or higher) after being attached to a substrate such as a textile product. High temperature heat treatment requires high energy.

JP-A-2006-328624 discloses a water repellent comprising a non-fluorinated polymer containing a (meth) acrylic ester having 12 or more carbon atoms in the ester portion as a monomer unit, comprising a (meth) acrylic ester Discloses a water repellent in which the composition ratio is 80 to 100% by mass based on the total amount of the monomer units constituting the non-fluorinated polymer.
However, this water repellent is inferior in water repellency and oil repellency.

JP 2006-328624 A

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

The present invention
(1) Equation (a):
^{_{CH 2 = CA 11 -C (=}} O) -O-A 12
[In the formula, A ¹¹ represents a halogen, a linear or branched alkyl group having 2 to 21 carbon atoms, a CFX ¹ X ² group (where X ¹ and X ² represent 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,
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 α-substituted acrylate ester monomer represented by the formula: (2) a surfactant containing a nonionic surfactant, and (3) a liquid medium containing water And a surface treatment agent which is an aqueous emulsion. It is preferable that the polymer (1) does not contain a fluorine atom.

Since the treating agent of the present invention does not use an alkylalkyl group-containing monomer, there is no concern about accumulation of the fluorine-containing compound in the environment. The treating agent of the present invention gives the substrate excellent water and oil repellency. Furthermore, it is not necessary to perform heat treatment at a high temperature, and water and oil repellency is exhibited by a low temperature treatment.
The processing agent of the present invention has good stability (emulsion stability). The treating agent of the present invention is excellent in durability of water and oil repellency (particularly, water repellency) (particularly, washing durability). Furthermore, the feeling of the substrate is good.

The polymer of the present invention is a polymer having no fluoroalkyl group. The polymer of the present invention is preferably a non-fluorine polymer having no fluorine atom.
In the present invention, the polymer is
(A) having a repeating unit derived from a long-chain α-substituted acrylate ester monomer;
The polymer was further derived from (b) a polymerizable monomer other than the long chain α-substituted acrylate ester monomer (a), preferably a non-fluorine polymerizable monomer other than the monomer (a). It may have a derived repeating unit.

The polymerizable monomer other than the monomer (a) may be a non-fluorine non-crosslinkable monomer or a non-fluorine crosslinkable monomer.
The non-fluorine non-crosslinkable monomer has the formula:
CH ₂ = CA-T
Wherein A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (eg, a chlorine atom, a bromine atom and an iodine atom);
T represents a hydrogen atom, a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom), a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or cyclic group having an ester bond. It is an organic group having 1 to 30 carbon atoms. ]
May be a compound represented by

  Examples of the chain or cyclic hydrocarbon group having 1 to 30 carbon atoms include a linear or branched saturated or unsaturated (eg, ethylenically unsaturated) aliphatic hydrocarbon group having 1 to 30 carbon atoms, A saturated or unsaturated (e.g., ethylenically unsaturated) cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an araliphatic hydrocarbon group having 7 to 30 carbon atoms.

  Examples of the chain or cyclic organic group having an ester bond and having 1 to 30 carbon atoms are -C (= O) -OQ and -OC (= O) -Q (where Q is 1 to 20 carbon atoms). A linear or branched saturated or unsaturated (eg, ethylenically unsaturated) aliphatic hydrocarbon group; a C 4-20 saturated or unsaturated (eg, ethylenically unsaturated) cyclic aliphatic group; An aromatic hydrocarbon group having 6 to 20 carbon atoms and an araliphatic hydrocarbon group having 7 to 20 carbon atoms).

  The non-fluorine crosslinkable monomer is as described later.

Examples of the polymerizable monomer other than the monomer (a) are as follows.
(B) an acrylate ester monomer other than the long-chain α-substituted acrylate ester monomer,
(C) a non-fluorine-crosslinkable monomer, and (d) a halogenated olefin.
The polymer may have a fluorine atom, but preferably has no fluorine atom. That is, the polymer is preferably a non-fluorine polymer, and all the monomers are preferably non-fluorine monomers.

(A) Preferred examples of long chain α-substituted acrylate ester monomer long chain α-substituted acrylate ester monomer has the formula:
^{_{CH 2 = CA 11 -C (=}} O) -O-A 12
[In the formula, A ¹¹ represents a halogen, a linear or branched alkyl group having 2 to 21 carbon atoms, a CFX ¹ X ² group (where X ¹ and X ² represent 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,
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 α-substituted acrylate ester monomer does not have a fluoroalkyl group. The long-chain α-substituted acrylate ester monomer may contain a fluorine atom, but preferably does not contain a fluorine atom.
Examples of A ¹¹ are, Cl, Br, I, F , CN, is CF _3. A ¹¹ is preferably a chlorine atom.
A ¹² is a linear or branched hydrocarbon group. The straight-chain or branched hydrocarbon group may in particular be a straight-chain 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 carbon atoms, and is generally preferably a saturated aliphatic hydrocarbon group, particularly preferably an alkyl group.

Particularly preferred specific examples of the long-chain α-substituted acrylate ester monomer are stearyl α-chloroacrylate, behenyl α-chloroacrylate, stearyl α-fluoroacrylate, and behenyl α-fluoroacrylate.
The presence of the long-chain α-substituted acrylate ester monomer increases the water repellency and oil repellency provided by the polymer.

(B) other acrylate ester monomer polymer may have the repeating units derived from other acrylate ester monomer.
Examples of other acrylate ester monomers are as follows.
(B1) a long-chain unsubstituted acrylate ester monomer,
(B2) a short-chain acrylate ester monomer, and (b3) an acrylate ester monomer having a cyclic hydrocarbon group. The polymer includes a monomer (b1), a monomer (b2), and a monomer (b3). May have a repeating unit derived from at least one monomer selected from the group consisting of

(B1) a long chain unsubstituted acrylate ester monomer polymer may have the repeating units derived from long chain unsubstituted acrylate ester monomers. The long chain unsubstituted acrylate ester monomer is a (meth) acrylate ester (ie, acrylate or methacrylate).
Preferred examples of long chain unsubstituted acrylate ester monomers have the formula:
^{_{CH 2 = CA 11 '-C (}} = O) -O-A 12'
[Wherein, A ^{11 ′} is a hydrogen atom or a methyl group,
A ^{12 ′} is a linear or branched aliphatic hydrocarbon group having 18 to 30 carbon atoms. ]
It is a compound shown by these.

Long chain unsubstituted acrylate ester monomers do not have fluoroalkyl groups. The long-chain unsubstituted acrylate ester monomer may contain a fluorine atom, but preferably does not contain a fluorine atom.
A ^{12 ′} is a linear or branched hydrocarbon group. The straight-chain or branched hydrocarbon group may in particular be a straight-chain 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 carbon atoms, and is generally preferably a saturated aliphatic hydrocarbon group, particularly preferably an alkyl group.
Particularly preferred specific examples of the long-chain unsubstituted acrylate ester monomer are stearyl acrylate, behenyl acrylate, stearyl methacrylate, and behenyl methacrylate.
The presence of the long-chain unsubstituted acrylate ester monomer increases the water and oil repellency provided by the polymer.

(B2) a short chain acrylate ester monomer polymer may have the repeating units derived from short-chain acrylate ester monomer.
The short-chain acrylate ester monomer has the formula:
^{_{CH 2 = CA 21 -C (=}} O) -O-A 22
[Wherein, A ²¹ is a hydrogen atom, a monovalent organic group, or a halogen atom;
A ²² is a linear or branched aliphatic hydrocarbon group having less than 18 carbon atoms. ]
May be indicated by
The short-chain acrylate ester monomer has the formula:
^{_{CH 2 = CA 21 -C (=}} O) -O-A 22
[Wherein, A ²¹ is a hydrogen atom, a methyl group, a halogen, a linear or branched alkyl group having 2 to 21 carbon atoms, a CFX ¹ X ² group (where X ¹ and X ² are 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,
A ²² is a linear or branched aliphatic hydrocarbon group having less than 18 carbon atoms. ]
It is preferable that the compound is represented by

Short-chain acrylate ester monomers have no fluoroalkyl groups. The short-chain acrylate ester monomer may contain a fluorine atom, but preferably does not contain a fluorine atom.
Examples of A ²¹ are a hydrogen atom, a methyl group, Cl, Br, I, F, CN, CF ₃ . A ³¹ is preferably a methyl group or a chlorine atom.
A ²² is a linear or branched hydrocarbon group. The straight-chain or branched hydrocarbon group may in particular be a straight-chain 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.

Particularly preferred specific examples of the short-chain acrylate ester monomer are lauryl (meth) acrylate, lauryl α-chloroacrylate, lauryl α-fluoroacrylate, cetyl (meth) acrylate, cetyl α-chloroacrylate, and cetyl α-fluoroacrylate.
The presence of the short-chain acrylate ester monomer improves the water repellency and hand of the polymer.

(B3) cyclic acrylate ester monomer polymer having a hydrocarbon group may have a repeating unit derived from a cyclic hydrocarbon group containing acrylate ester monomer.
Cyclic hydrocarbon group-containing acrylate ester monomer,
formula:
^{_{CH 2 = CA 31 -C (=}} O) -O-A 32
[Wherein, A ³¹ is a hydrogen atom, a methyl group, a halogen, a linear or branched alkyl group having 2 to 21 carbon atoms, a CFX ¹ X ² group (where X ¹ and X ² are 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,
A ³² is a cyclic hydrocarbon containing group having 4 to 30 carbon atoms. ]
It is preferable that the compound is represented by
The cyclic hydrocarbon group-containing acrylate ester monomer is preferably a homopolymer having a high glass transition point (for example, 50 ° C. or higher, particularly 80 ° C. or higher).

  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 does not contain a fluorine atom.

Examples of A ³¹ are a hydrogen atom, a methyl group, Cl, Br, I, F, CN, CF ₃ . A ³¹ is preferably a chlorine atom.
A ³² is a cyclic hydrocarbon group which may have a chain group (for example, a linear or branched hydrocarbon group). Examples of the cyclic hydrocarbon group include a saturated or unsaturated monocyclic group, polycyclic group, bridged ring group, and the like. The cyclic hydrocarbon group is preferably saturated. The cyclic hydrocarbon group has 4 to 30 carbon atoms, and preferably 6 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an araliphatic group having 7 to 20 carbon atoms. The number of carbon atoms 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, and a dicyclopentenyl group.

As specific examples of the cyclic hydrocarbon group-containing acrylate ester monomer,
Cyclohexyl acrylate, t-butyl cyclohexyl acrylate, benzyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate; and cyclohexyl methacrylate, t-butyl cyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, dicyclopentanyl Methacrylate, dicyclopentenyl methacrylate;
And the like.
The presence of the cyclic hydrocarbon group-containing acrylate ester monomer increases the water repellency and oil repellency provided by the polymer.

(C) a non-fluorinated crosslinking monomer polymer may have the repeating units derived from fluorine-free crosslinkable monomer.
The non-fluorine crosslinkable monomer is a monomer containing no fluorine atom. The non-fluorine crosslinkable monomer may be a compound having at least two reactive groups and / or an olefinic carbon-carbon double bond (preferably, a (meth) acrylate group) 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 olefinic carbon-carbon double bond. It may be a compound having a reactive group. Examples of reactive groups are hydroxyl, epoxy, chloromethyl, blocked isocyanate, amino, carboxyl, and the like.

  The non-fluorine crosslinkable monomer may be a 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 the non-fluorine crosslinkable monomer include diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and 2,3-dihydroxypropyl (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth) acrylate, 1,4-butanediol Examples include, but are not limited to, di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like. Not something.

  The presence of the non-fluorinated crosslinkable monomer increases the washing durability provided by the polymer.

(D) The halogenated olefin monomer copolymer may have a repeating unit derived from a halogenated olefin monomer.
It is preferable that the halogenated olefin monomer does not have a fluorine atom.
The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms substituted by 1 to 10 chlorine, bromine or iodine atoms. The halogenated olefin monomer 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 specific examples of the halogenated olefin monomer are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, and vinylidene halide such as vinylidene chloride, vinylidene bromide and vinylidene iodide. Vinyl chloride and vinylidene chloride are preferred because the water and oil repellency (particularly the durability of the water and oil repellency) increases.
The presence of the halogenated olefin increases the washing durability provided by the polymer.

(E) Other Monomers Other monomers (e) other than the 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.

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

  It is preferable that each of the (meth) acrylate monomers is an acrylate ester because the water / oil repellency is increased.

  Each of the monomers (a) to (e) may be used alone or as a mixture of two or more.

The amount of the monomer (a) may be at least 40% by weight, preferably at least 50 parts by weight, 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, based on 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 100 parts by weight, preferably 1 to 30 parts by weight,
The amount of the repeating unit (d) is 0 to 50 parts by weight, preferably 1 to 10 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.
In the polymer, the amount of each of the monomers (b1), (b2) and (b3) is preferably 0 to 150 parts by weight, preferably 100 parts by weight of the monomer (a). May be from 1 to 100 parts by weight, for example from 2 to 50, in particular from 3 to 30 parts by weight.

  The number average molecular weight (Mn) of the polymer may generally be between 1000 and 1,000,000, for example between 5000 and 500,000, especially between 3000 and 200,000. The number average molecular weight (Mn) of the polymer is generally measured by GPC (gel permeation chromatography).

In the present invention, the treating agent composition in which the monomer is polymerized and the polymer is dispersed or dissolved in the medium is obtained.
The monomers used in the present invention are as follows.
Monomer (a),
Monomer (a) + (b),
Monomers (a) + (b) + (c),
Monomer (a) + (b) + (d), or monomer (a) + (b) + (c) + (d).
In addition to the above, a monomer (e) may be used. The monomer (b) may be at least one of the monomer (b1), the monomer (b2) and the monomer (b3).

(2) Surfactant In the treatment agent of the present invention, the surfactant includes a nonionic surfactant. Further, the surfactant preferably includes at least one surfactant selected from a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. It is preferable to use a combination of a nonionic surfactant and a cationic surfactant. Preferably, the surfactant does not include an anionic surfactant.

(2-1) Nonionic surfactant Examples of the nonionic surfactant include ether, ester, ester ether, alkanolamide, polyhydric alcohol and amine oxide.
Examples of the ether are compounds 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 (particularly 2 to 5 valent) carbon atoms having 1 to 50 (particularly 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50, especially 5 to 30 carbon atoms.
Examples of ester ethers are compounds obtained by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols having 1 to 6 (particularly 2 to 5 valent) carbon atoms having 1 to 50 (particularly 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50, especially 5 to 30 carbon atoms.
Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamino. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50, especially 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50, especially 5 to 30 carbon atoms having 1 to 3 amino groups and 1 to 5 hydroxyl groups.
The polyhydric alcohol may be a divalent to pentavalent alcohol having 3 to 30 carbon atoms.
The amine oxide may be an oxide of an amine (secondary or preferably tertiary amine) (e.g. 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. Generally, the number of oxyalkylene groups in the molecule of the nonionic surfactant is preferably 2 to 100.
The nonionic surfactant is 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.
Nonionic surfactants include 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 structure of the alkylene oxide-added portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (even if it is a random copolymer or a block copolymer). May be preferable).
Further, the nonionic surfactant preferably has a structure containing no aromatic group due to environmental problems (biodegradability, environmental hormones, etc.).

The 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 or an alkenyl group or an acyl group having 2 to 22 carbon atoms,
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 greater than or equal to 2;
q is 0 or a number of 1 or more. ]
May be a compound represented by
R ¹ preferably has 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms. Preferred 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, - (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 them, 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 represented by

Specific examples of nonionic surfactants include:
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. ]
And so on.

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 _(C 12 _{-C 18)} condensation products such as the amines and the like.

The proportion of polyoxyethylene blocks can 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.
One type of nonionic surfactant may be used alone, or two or more types may be used in combination.
The nonionic surfactant is preferably a combination of two or more. In a combination of two or more, at least one nonionic surfactant includes an R ¹ O- (CH ₂ CH) in which the R ¹ group (and / or the R ³ group) is a branched alkyl group (eg, an isotridecyl group). ₂ O) _p- (R ² O) _q -R ³ [in particular, R ¹ O- (CH ₂ CH ₂ O) _p -H]. The amount of the nonionic surfactant in which the 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 to 100 parts by weight of the nonionic surfactant (B2). It may be up to 40 parts by weight. In the combination of two or more, the remaining nonionic surfactants are those in which the R ¹ group (and / or the R ³ group) is a linear (saturated and / or unsaturated) linear alkyl group (eg, a lauryl group (n- A compound represented by R ¹ O— (CH ₂ CH ₂ O) _p — (R ² O) _q —R ³ [particularly R ¹ O— (CH ₂ CH ₂ O) _p —H] which is a lauryl group)) It may be.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and 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, alkylalkanolamide, acetylene glycol, acetylene glycol oxyethylene adduct, Examples include polyethylene glycol polypropylene glycol block copolymer.

  Since the dynamic surface tension of the water-based emulsion is reduced (that is, the water-based emulsion easily penetrates the substrate), the nonionic surfactant may be acetylene alcohol (particularly, acetylene glycol) or acetylene alcohol (particularly, acetylene alcohol). Oxyethylene adduct of (glycol) is 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"). A particularly preferred nonionic surfactant is an alkylene oxide adduct of a monol or polyol having an unsaturated triple bond.
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 between polyoxyethylene and polyoxypropylene, and a block addition structure between 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, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ may be the same or different and are a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ]
May be a compound represented by The acetylene alcohol compound may be an alkylene oxide adduct of the compound represented by this chemical formula. The alkyl group is preferably a straight-chain or branched alkyl group having 1 to 12 carbon atoms, and particularly preferably a straight-chain or branched alkyl group having 6 to 12 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group and the like can be mentioned. As the alkylene oxide, an alkylene oxide having 1 to 20 (particularly 2 to 5) carbon atoms such as ethylene oxide and propylene oxide is preferable, and the number of addition 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-4-octyne-3,6-diol, and 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- Pentin-3-ol, 3-hexyne-2,5-diol, 2-butyne-1,4-diol and the like. Examples thereof include polyethoxylates and ethylene oxide adducts of these specific compounds.

  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 activators. In a combination of a nonionic surfactant having no triple bond and a nonionic surfactant having a triple bond, a nonionic surfactant having no triple bond (for example, a nonionic surfactant having an oxyalkylene group) has a triple bond The weight ratio of the nonionic surfactant (for example, acetylene alcohol compound) 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.

  The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene addition type ammonium salt. Specific examples of the cationic surfactant include, but are not particularly limited to, an alkylamine salt, an amino alcohol fatty acid derivative, a polyamine fatty acid derivative, an amine salt type surfactant such as imidazoline, an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, Examples include quaternary ammonium salt type surfactants such as alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride.

Preferred examples of the cationic surfactant include:
^{R 21 -N + (-R 22)} (- R 23) (- R 24) X -
Wherein R ²¹ , R ²² , R ²³ and R ²⁴ are a hydrocarbon group having 1 to 30 carbon atoms,
X is an anionic group. ]
Is a compound of
Specific examples of R ²¹ , R ²² , R ²³ and -R ²⁴ are an alkyl group (for example, a methyl group, a butyl group, a stearyl group, a palmityl group). Specific examples of X are a halogen (eg, chlorine) and an acid (eg, hydrochloric acid, acetic acid).
It is particularly preferred that the cationic surfactant is a monoalkyltrimethylammonium salt (alkyl having 4 to 30 carbon atoms).

Preferably, the cationic surfactant is an ammonium salt. The cationic surfactant has the formula:
R ¹ _p -N ⁺ R ² _q X ⁻
[In the formula, R ¹ represents linear and / or branched aliphatic C12 or higher (e.g., _C 12 _{-C 50)} (saturated and / or unsaturated) group,
R ² is H or a C 1-4 alkyl group, benzyl group, polyoxyethylene group (the number of oxyethylene groups, for example 1 (particularly 2, especially 3) to 50)
(CH ₃ and C ₂ H ₅ are particularly preferred),
X is a halogen atom (e.g.,), fatty bases C ₁ -C _4,
p is 1 or 2, q is 2 or 3, and p + q = 4. ]
May be the ammonium salt represented by The carbon number of R ¹ may be 12-50, for example 12-30.

  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, benzyldodecyldi (hydropolyoxyethylene) ammonium chloride, N- [2- (diethylamino) ethyl] oleamide hydrochloride are included.

  Examples of the amphoteric surfactant include alanines, imidazolinium betaines, amido betaines, betaine acetate and the like.Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethylhydroxyethyl imidazolinium betaine, lauryl dimethyl Betaine aminoacetate, betaine fatty acid amidopropyldimethylaminoacetate and the like.

Each of the nonionic surfactant, the cationic surfactant, and the amphoteric surfactant may be one kind or a combination of two or more kinds.
The amount of the cationic surfactant is at least 15% by weight, preferably at least 20% by weight, more preferably at least 25% by weight, based on the total amount of the surfactant. 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 cationic surfactant may be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight based on 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.

(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% by weight or more) based on the liquid medium. The liquid medium is preferably water alone.

  The water / oil repellent composition of the present invention may contain only the above-mentioned non-fluorinated polymer as a polymer (active ingredient), but contains a fluorinated polymer in addition to the above-mentioned non-fluorinated polymer. Is also good. Generally, in a water / oil repellent composition (particularly, an aqueous emulsion), particles formed by a non-fluorinated polymer and particles formed by a fluoropolymer are separately present. That is, it is preferable to mix the non-fluorinated polymer and the fluorinated polymer after separately producing the non-fluorinated polymer and the fluorinated polymer. Generally, an emulsion of a non-fluorinated polymer (especially, an aqueous emulsion) and an emulsion of a fluorinated polymer (especially, an aqueous emulsion) are separately prepared, and then the emulsion of the non-fluorinated polymer and the emulsion of the fluorinated polymer are mixed. Is preferred.

The fluorinated polymer is a polymer having a repeating unit derived from a fluorinated monomer. The fluorine-containing monomer has the general formula:
CH ₂ = C (−X) −C (= O) −Y−Z−Rf (I)
[In the formula, X is 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 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 or a cycloaliphatic group having 6 to 18 carbon atoms,
A —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 (. However, Z ¹ is a hydrogen atom or an acetyl group) or
_{- (CH 2) m -SO 2} - (CH 2) n - group or a _{- (CH 2) m -S- (} CH 2) n - group (where, m is 1 to 10, n is 0 to 10 in, is there),
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. ]
Is preferably an acrylate ester or acrylamide represented by
The number of carbon atoms of the Rf group is preferably 1 to 6, particularly 4 to 6, and particularly preferably 6.

The fluorine-containing polymer is a repeating unit 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. It may have a unit.
The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms substituted by 1 to 10 chlorine, bromine or iodine atoms. Specific examples of the halogenated olefin monomer are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, and vinylidene halide such as vinylidene chloride, vinylidene bromide, and vinylidene iodide.

Preferred non-fluorine non-crosslinkable monomers have the formula:
CH ₂ = CA-T
Wherein A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (eg, a chlorine atom, a bromine atom and an iodine atom);
T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 20 carbon atoms, or a chain or cyclic organic group having 1 to 20 carbon atoms having an ester bond. ]
It is a compound shown by these. Specific examples of the non-fluorine non-crosslinkable monomer include alkyl (meth) acrylate ester, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and methoxy polyethylene glycol (meth). Acrylates, methoxy polypropylene glycol (meth) acrylates, and vinyl alkyl ethers are included.

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

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

The polymer (a polymer having no fluoroalkyl group, particularly a non-fluorinated polymer, and a fluorine-containing polymer, particularly a copolymer having a fluoroalkyl group) in the present invention can be produced by any of ordinary polymerization methods. Reaction conditions 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 method for producing the polymer is not limited. For example, after producing a polymer by solution polymerization, removal of a solvent and addition of a surfactant and water can be performed to obtain an aqueous emulsion.

  In the solution polymerization, a method is used in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after stirring with nitrogen, the mixture is heated and stirred at 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, diisopropyl peroxydicarbonate, and the like. No. 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 monomer and dissolves them. For example, an ester (eg, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (eg, carbon It may be a ketone having 2 to 30 atoms, 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 thereof 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 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 of the monomers.

  In the emulsion polymerization, a method is employed in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen replacement, polymerization is performed by stirring at 50 to 80 ° C. for 1 to 10 hours. The polymerization initiator is benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine-dihydrochloride, azo Water-soluble substances such as bisisobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide , T-butyl peroxypivalate, diisopropyl peroxydicarbonate and the like are 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 polymer aqueous dispersion having excellent standing stability, a monomer is finely divided into water and polymerized using an emulsifying apparatus capable of imparting 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 are used in the range of 0.5 to 20 parts by weight based on 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 that makes the monomers sufficiently compatible with each other, for example, a water-soluble organic solvent or a low molecular weight monomer. By adding a compatibilizer, emulsifiability and copolymerizability can be improved.

  Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol, and 1 to 50 parts by weight with respect to 100 parts by weight of water. , For example, in the range of 10 to 40 parts by weight. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and the like. 1 to 50 parts by weight, based on 100 parts by weight of the total amount of the monomer, For example, it may be used in the range of 10 to 40 parts by weight.

  In the polymerization, a chain transfer agent may be used. The molecular weight of the polymer can be changed according to the amount of the chain transfer agent used. Examples of the chain transfer agent include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol and thioglycerol (particularly, alkyl mercaptans (for example, having 1 to 30 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium bisulfite. And so on. 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 polymer (the active ingredient of the surface treating agent) and a medium (particularly a liquid medium, for example, an organic solvent and / or water). The amount of medium can be, for example, from 5 to 99.9% by weight, in particular from 10 to 80% by weight, based on the treatment composition.
In the treatment composition, the concentration of the polymer may be 0.01 to 95% by weight, for example 5 to 50% by weight.

  The treating agent composition of the present invention can be applied to an object to be treated by a conventionally known method. Generally, a method of dispersing the treatment agent composition in an organic solvent or water, diluting the dispersion, applying the dispersion to a surface of the object to be treated by a known method such as dip coating, spray coating, foam coating, and the like, followed by drying. Taken. If necessary, the composition may be applied together with a suitable crosslinking agent (for example, a blocked isocyanate) and cured. 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 treating agent composition of the present invention. The concentration of the polymer in the treatment liquid to be brought into contact with the substrate may be from 0.01 to 10% by weight (particularly in the case of dip coating), for example from 0.05 to 10% by weight.

  Examples of the object to be treated with the treatment agent composition (eg, water / oil repellent) of the present invention include textiles, stone materials, filters (eg, electrostatic filters), dust masks, and fuel cell components (eg, gas). Diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, plasters and the like. Various examples can be given as fiber products. For example, animal and plant natural 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. And inorganic fibers such as asbestos fibers, or a mixed fiber thereof.

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

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

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

  The textile products to be treated are typically fabrics, including fabrics, knits and nonwovens, fabrics and carpets in the form of clothing, but with fibers or yarns or intermediate textiles (eg slivers or slivers). Roving, etc.). The textile material can be natural fibers (such as cotton or wool), synthetic fibers (such as viscose rayon or rheocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers), or , A mixture of fibers (eg, a mixture of natural and synthetic fibers, etc.). The produced polymers of the present invention are particularly effective in rendering cellulosic fibers (such as cotton or rayon) oleophobic and oleophobic. Also, the method of the present invention generally renders textiles hydrophobic and water repellent.

Alternatively, the fibrous substrate may be leather. The aqueous solution or aqueous emulsification at various stages of the leather processing, for example during the wet processing of the leather or during the finishing of the leather, in order to render the produced polymer hydrophobic and oleophobic in the leather It can be applied from object to leather.
Alternatively, the fibrous substrate may be paper. The production polymer may be applied to preformed paper or may be applied at various stages of the papermaking, for example, during the drying of the paper.

  “Treatment” means applying a treatment agent to an object to be treated by dipping, spraying, coating, or the like. By the treatment, the polymer which is an effective component of the treatment agent permeates into the inside of the article and / or adheres to the surface of the article.

It is preferable that the zeta potential of the surface treatment agent is +30 mV or more. The zeta potential is measured by a laser Doppler method (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.).
It is preferable that the dynamic surface tension of the surface treatment agent is 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.).

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.
In the following, parts or percentages or ratios are by weight unless otherwise specified.
The test procedure is as follows.

Spray water repellency test A test solution was prepared by diluting a polymer dispersion with tap water so that the solid content concentration was 1% by weight, and a polyester and nylon cloth was immersed in this test solution, passed through a mangle, and heated at 160 ° C. for 2 hours. The water repellency was evaluated with a test cloth that had been heat treated for a minute. Washing durability was determined by washing in a washing liquid at 40 ° C. 10 times, followed by tumbler drying according to JIS-L-0217-103 method, and then evaluating the water repellency. (HL10) The water repellency of the treated cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). As shown in Table 1 below, water repellency Nos. Represented by The higher the score, the better the water repellency. Depending on the state, an intermediate value (95, 85, 75) is given.

Bundesmann repellency an aqueous test polymer dispersion solids concentration to prepare a test solution diluted with tap water so as to be 1 wt%, passed through a mangle after immersing the polyester and nylon cloth to the test solution at 160 ° C. A test cloth heat-treated for 2 minutes was prepared. According to the Bundesmann test described in JIS-L-1092 (C) method, rainfall was performed under the conditions of a rainfall of 80 cc / min, a rainwater temperature of 20 ° C., and a rainfall time of 5 or 10 minutes, and the water repellency was evaluated. did. The evaluation method was the same as in the spray water repellency test, as shown in Table 1. Represented by

Example 1
Stearyl α-Cl acrylate = 100 g, pure water = 180 g, tripropylene glycol = 30 g, sorbitan monooleate = 3 g, sec-C _12-14 H _25-29 (C ₂ H ₄ O) ₂₀ H = 4 g in a 500 mL autoclave. And 3 g of dioctadecyldimethylammonium chloride, and the mixture was emulsified and dispersed by ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, 0.5 g of lauryl mercaptan was added, the inside of the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g was added, and the mixture was reacted at 60 ° C. for 3 hours to obtain an aqueous solution of the polymer. A dispersion was obtained. Further, the solid content concentration was adjusted to 30% with pure water, and the water repellency was evaluated.

Example 2
In a 500 mL autoclave, stearyl α-Cl acrylate = 80 g, stearyl acrylate = 20 g, pure water = 180 g, tripropylene glycol = 30 g, sorbitan monooleate = 3 g, sec-C _12-14 H _25-29 (C ₂ H ₄ O ₂₀ H = 4 g and dioctadecyldimethylammonium chloride = 3 g were added, and the mixture was emulsified and dispersed by ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, 0.5 g of lauryl mercaptan was added, the inside of the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g was added, and the mixture was reacted at 60 ° C. for 3 hours to obtain an aqueous solution of the polymer. A dispersion was obtained. Further, the solid content concentration was adjusted to 30% with pure water, and the water repellency was evaluated.

Example 3
In a 500 mL autoclave, stearyl α-Cl acrylate = 80 g, lauryl acrylate = 20 g, pure water = 180 g, tripropylene glycol = 30 g, sorbitan monooleate = 3 g, sec-C _12-14 H _25-29 (C ₂ H ₄ O ₂₀ H = 4 g and dioctadecyldimethylammonium chloride = 3 g were added, and the mixture was emulsified and dispersed by ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, 0.5 g of lauryl mercaptan was added, the inside of the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g was added, and the mixture was reacted at 60 ° C. for 3 hours to obtain an aqueous solution of the polymer. A dispersion was obtained. Further, the solid content concentration was adjusted to 30% with pure water, and the water repellency was evaluated.

Example 4
In a 500 mL autoclave, stearyl α-Cl acrylate = 80 g, isobornyl methacrylate = 20 g, pure water = 180 g, tripropylene glycol = 30 g, sorbitan monooleate = 3 g, sec-C _12-14 H _25-29 (C ₂ H _{4 O)} 20 H = 4g, placed dioctadecyl dimethyl ammonium chloride = 3 g, 15 minutes at 60 ° C. under stirring, were charged and emulsified by ultrasonic wave. After emulsification, 0.5 g of lauryl mercaptan was added, the inside of the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g was added, and the mixture was reacted at 60 ° C. for 3 hours to obtain an aqueous solution of the polymer. A dispersion was obtained. Further, the solid content concentration was adjusted to 30% with pure water, and the water repellency was evaluated.

Example 5
In a 500 mL autoclave, stearyl α-Cl acrylate = 95 g, 2,3-dihydroxypropyl methacrylate = 5 g, pure water = 180 g, tripropylene glycol = 30 g, sorbitan monooleate = 3 g, sec-C _12-14 H _25-29 ( (C ₂ H ₄ O) ₂₀ H = 4 g and dioctadecyldimethylammonium chloride = 3 g were added, and the mixture was emulsified and dispersed by ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, 0.5 g of lauryl mercaptan was added, the inside of the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g was added, and the mixture was reacted at 60 ° C. for 3 hours to obtain an aqueous solution of the polymer. A dispersion was obtained. Further, the solid content concentration was adjusted to 30% with pure water, and the water repellency was evaluated.

Example 6
Stearyl α-Cl acrylate = 80 g, pure water = 180 g, tripropylene glycol = 30 g, sorbitan monooleate = 3 g, sec-C _12-14 H _25-29 (C ₂ H ₄ O) ₂₀ H = 4 g in a 500 mL autoclave. And 3 g of dioctadecyldimethylammonium chloride, and the mixture was emulsified and dispersed by ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, 0.5 g of lauryl mercaptan was added, and the inside of the autoclave was replaced with nitrogen. Then, 20 g of vinyl chloride was press-filled, and 1 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added. The reaction was carried out for 3 hours to obtain an aqueous dispersion of the polymer. Further, the solid content concentration was adjusted to 30% with pure water, and the water repellency was evaluated.

Example 7
In a 500 mL autoclave, stearyl α-Cl acrylate = 70 g, isobornyl methacrylate = 10 g, 2,3-dihydroxypropyl methacrylate = 5 g, pure water = 180 g, tripropylene glycol = 30 g, sorbitan monooleate = 3 g, sec-C _{12 -14 H 25-29 (C 2 H 4} O) 20 H = 4g, placed dioctadecyl dimethyl ammonium chloride = 3 g, 15 minutes at 60 ° C. under stirring, were charged and emulsified by ultrasonic wave. After emulsification, 0.5 g of lauryl mercaptan was added, and the inside of the autoclave was replaced with nitrogen. Then, 15 g of vinyl chloride was press-filled, and 1 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added. The reaction was carried out for 3 hours to obtain an aqueous dispersion of the polymer. Further, the solid content concentration was adjusted to 30% with pure water, and the water repellency was evaluated.

Comparative Example 1
Stearyl acrylate = 100 g, pure water = 180 g, tripropylene glycol = 30 g, sorbitan monooleate = 3 g, sec-C _12-14 H _25-29 (C ₂ H ₄ O) ₂₀ H = 4 g, dioctadecyl in a 500 mL autoclave Dimethylammonium chloride = 3 g was added, and the mixture was emulsified and dispersed by ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, 0.5 g of lauryl mercaptan was added, the inside of the autoclave was replaced with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g was added, and the mixture was reacted at 60 ° C. for 3 hours to obtain an aqueous solution of the polymer. A dispersion was obtained. Further, the solid content concentration was adjusted to 30% with pure water, and the water repellency was evaluated.

Comparative Example 2
In a 500 mL autoclave, stearyl acrylate = 80 g, pure water = 180 g, tripropylene glycol = 30 g, sorbitan monooleate = 3 g, sec-C _12-14 H _25-29 (C ₂ H ₄ O) ₂₀ H = 4 g, dioctadecyl Dimethylammonium chloride = 3 g was added, and the mixture was emulsified and dispersed by ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, 0.5 g of lauryl mercaptan was added, and the inside of the autoclave was replaced with nitrogen. Then, 20 g of vinyl chloride was press-filled, and 1 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added. The reaction was carried out for 3 hours to obtain an aqueous dispersion of the polymer. Further, the solid content concentration was adjusted to 30% with pure water, and the water repellency was evaluated.

  Table 2 shows the shower and Bundesmann water repellency of each example.

  The treating agent of the present invention can be used as a water / oil repellent or an antifouling agent. The treating 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.

Claims (10)

(1) Equation (a):
^{_{CH 2 = CA 11 -C (=}} O) -O-A 12
Wherein A ¹¹ is Cl, Br, I 2 or a cyano group ;
A ¹² is a linear or branched aliphatic hydrocarbon group having 18 to 30 carbon atoms. ]
A non-fluorinated polymer having a repeating unit derived from a long-chain α-substituted acrylate ester monomer represented by the formula: and (2) a surfactant containing a nonionic surfactant, and (3) water. A surface treatment agent that is a water-based emulsion containing a liquid medium,
A surface treating agent which does not contain a fluoropolymer. The non-fluorinated polymer (1) further has a repeating unit derived from a polymerizable monomer other than the monomer (a),
A polymerizable monomer other than the monomer (a) has the formula:
CH ₂ = CA-T
Wherein, A represents a hydrogen atom, a methyl group, or a halogen atom other than fluorine atom,
T represents a hydrogen atom, a halogen atom other than a fluorine atom, a linear or cyclic hydrocarbon group or a chain or cyclic organic group having 1 to 30 carbon atoms having an ester bond, having from 1 to 30 carbon atoms. ]
The surface treatment agent according to claim 1, which is a compound represented by the formula: A polymerizable monomer other than the monomer (a),
(B) an acrylate ester monomer other than the long-chain α-substituted acrylate ester monomer,
The surface treatment agent according to claim 2, wherein the surface treatment agent is at least one selected from the group consisting of (c) a non-fluorine crosslinkable monomer and (d) a halogenated olefin. Another acrylate ester monomer (b) is
(B1) a long-chain unsubstituted acrylate ester monomer,
The surface treatment agent according to claim 3, wherein the surface treatment agent is at least one selected from the group consisting of (b2) a short-chain acrylate ester monomer, and (b3) an acrylate ester monomer having a cyclic hydrocarbon group.   The non-fluorinated crosslinkable monomer (c) is a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond and at least one reactive group. Item 4. The surface treatment agent according to item 3.   The surface treatment agent according to claim 3, wherein the halogenated olefin monomer (d) is at least one selected from the group consisting of vinyl chloride and vinylidene chloride.   The surface treating agent according to any one of claims 1 to 6, wherein a chain transfer agent is used in the polymerization.   The surface treating agent according to any one of claims 1 to 7, which is a water / oil repellent or an antifouling agent.   A method for treating textile products, comprising treating textile products with the surface treatment agent according to any one of claims 1 to 8.   A textile product treated with the surface treatment agent according to claim 1.