JP2017066325A - Surface preparation agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface preparation agent without using a fluorine-containing monomer, especially a fluoroalkyl group-containing monomer.SOLUTION: There is provided the surface preparation agent containing: a polymer (1) having a repeating unit derived from a long chain α substituted acrylate ester monomer represented by (a) formula: CH=CA-C(=O)-O-A[Ais halogen, a linear or branched alkyl group having 2 to 21 carbon atoms, a CFXXgroup (Xand Xare 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 and Ais a linear or branched aliphatic hydrocarbon having 18 to 30 carbon atom]; a surfactant (2) containing a nonionic surfactant; and a liquid medium (3) including water.SELECTED DRAWING: None

Description

  The present invention relates to a surface treatment agent, particularly a water / oil repellent or 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 and oil repellent agent must be heat treated at a high temperature (for example, 100 ° C. or higher) after being attached to a substrate such as a textile product in order to exhibit water and oil repellency. High energy is required for heat treatment at high temperature.

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 does not use a fluoroalkyl group-containing monomer, preferably a fluorine-containing monomer.

The present invention
(1) (a) Formula:
^{_{CH 2 = CA 11 -C (=}} O) -O-A 12
[Wherein A ¹¹ is halogen, a linear or branched alkyl group having 2 to 21 carbon atoms, or 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 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, and (2) a surfactant containing a nonionic surfactant, and (3) a liquid medium containing water A surface treatment agent that is a water-based emulsion is provided. It is preferable that a polymer (1) does not contain a fluorine atom.

Since the treatment agent of the present invention does not use an alloalkyl 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 stability of the treating agent of the present invention (emulsion stability) is good. 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.

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.
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 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 ring having an ester bond It is a C1-C30 organic group. ]
It may be a compound shown by these.

  Examples of the linear or cyclic hydrocarbon group having 1 to 30 carbon atoms include a linear or branched saturated or unsaturated (for example, ethylenically unsaturated) aliphatic hydrocarbon group having 1 to 30 carbon atoms, carbon number They are a 4-30 saturated or unsaturated (for example, ethylenically unsaturated) cyclic aliphatic group, a C6-C30 aromatic hydrocarbon group, and a C7-C30 araliphatic hydrocarbon group.

  Examples of the linear or cyclic organic group having 1 to 30 carbon atoms having an ester bond 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 saturated or unsaturated (eg ethylenically unsaturated) cyclic aliphatic group having 4 to 20 carbon atoms, carbon An aromatic hydrocarbon group having 6 to 20 carbon atoms, an araliphatic hydrocarbon group having 7 to 20 carbon atoms).

  The non-fluorine crosslinkable monomer is as described later.

Examples of polymerizable monomers other than the monomer (a) are as follows.
(B) other acrylate ester monomers 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 does not have a 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
[Wherein A ¹¹ is halogen, a linear or branched alkyl group having 2 to 21 carbon atoms, or 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 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, CF ₃ . A ¹¹ is preferably a chlorine atom.
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.

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 is monomer (b1), monomer (b2) and monomer (b3). It 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).
A preferred example of a long chain unsubstituted acrylate ester monomer has the formula:
^{_{CH 2 = CA 11 '-C (}} = O) -O-A 12'
[Wherein 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.

Long chain unsubstituted acrylate ester monomers do not have a fluoroalkyl group. 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 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.
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 repellency 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
[In the formula, A ²¹ represents 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.
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, or a CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, Fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, 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 it is a compound shown by these.

The short chain acrylate ester monomer does not have a fluoroalkyl group. 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, and CF ₃ . A ³¹ is preferably a methyl group or a chlorine atom.
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.

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 texture imparted by 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, Fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl Group,
A ³² is a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms. ]
It is preferable that it is a compound shown by these.
The cyclic hydrocarbon group-containing acrylate ester monomer is preferably a monomer whose homopolymer has 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, and 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 saturated or unsaturated monocyclic groups, polycyclic groups, and bridged cyclic groups. The cyclic hydrocarbon group is preferably saturated. Carbon number of a cyclic hydrocarbon group is 4-30, and it is preferable that it is 6-20. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an 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 are a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, and a dicyclopentenyl group.

As a specific example 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;
Etc.
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.
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.
Non-fluorine crosslinkable monomers include, for example, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 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 a thing.

  The presence of the non-fluorine crosslinkable monomer increases the washing durability imparted by the polymer.

(D) The halogenated olefin monomer copolymer may have a repeating unit derived from a halogenated olefin monomer.
The halogenated olefin monomer preferably does not have a fluorine atom.
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. 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, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide. Vinyl chloride and vinylidene chloride are preferred because of high water and oil repellency (especially durability of water and oil repellency).
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.

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

  Since the water and oil repellency is enhanced, each of the (meth) acrylate monomers is preferably an acrylate ester.

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

The amount of monomer (a) may be 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 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 monomer (b1), the monomer (b2) and the monomer (b3) is 0 to 150 parts by weight, preferably 100 parts by weight of the monomer (a). May be 1 to 100 parts by weight, for example 2 to 50, in particular 3 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).

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 monomers used in the present invention are as follows.
Monomer (a),
Monomer (a) + (b),
Monomer (a) + (b) + (c),
Monomer (a) + (b) + (d), or Monomer (a) + (b) + (c) + (d).
In addition to the above, the 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 contains a nonionic surfactant. Furthermore, the surfactant preferably contains one or more surfactants 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. It is preferable that the surfactant does not contain an anionic surfactant.

(2-1) Nonionic surfactant Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, 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.
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 amine or preferably tertiary amine) (for example having 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.
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 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
[In formula, R < ¹¹ >, R < ¹² >, R < ¹³ >, R < ¹⁴ >, R < ¹⁵ >, R < ¹⁶ > may be the same or different, and is a hydrogen atom or a C1-C30 alkyl group. ]
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.

  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 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.

Preferred examples of the cationic surfactant are:
^{R 21 -N + (-R 22)} (- R 23) (- R 24) X -
[Wherein R ²¹ , R ²² , R ²³ and R ²⁴ represent a hydrocarbon group having 1 to 30 carbon atoms,
X is an anionic group. ]
It is a compound of this.
Specific examples of R ²¹ , R ²² , R ²³ and —R ²⁴ are alkyl groups (eg, methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogen (for example, chlorine) and acid (for example, hydrochloric acid, acetic 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. The cationic surfactant has the formula:
R ¹ _p -N ⁺ R ² _q X ⁻
[Wherein R ¹ is a linear and / or branched aliphatic (saturated and / or unsaturated) group of C12 or more (for example, C _{12 to} C ₅₀ ),
R ² is H or an alkyl group of C1-4, benzyl group, polyoxyethylene group (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. ]
It may be an ammonium salt represented by R ¹ 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, benzyldodecyl di (hydropolyoxyethylene) ammonium chloride, N- [2- (diethylamino) ethyl] oleamide hydrochloride 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 15% by weight or more, preferably 20% by weight or more, more preferably 25% by weight or more 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 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% by weight 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, in particular 4-6, especially 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 in the present invention (a polymer having no fluoroalkyl group, particularly a non-fluorine polymer, and a fluorine-containing polymer, particularly a copolymer having a fluoroalkyl group) can be produced by any ordinary polymerization method. The reaction conditions can also 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 surface treatment 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 surface 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.).

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.
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.

A test solution is prepared by diluting the spray water repellency test polymer dispersion with tap water so that the solid concentration is 1% by weight, and the polyester and nylon cloths are immersed in this test solution and then passed through a mangle and heated at 160 ° C. for 2 The water repellency was evaluated with a test cloth heat-treated for a minute. According to the JIS-L-0217-103 method, the washing durability was determined by performing tumbler drying after washing 10 times with a washing liquid at 40 ° C. and evaluating the subsequent water repellency. (HL10) The water repellency of the treated fabric was evaluated according to the spray method of JIS-L-1092 (AATCC-22). As shown in Table 1 below, the water repellency No. Is represented by The larger the score, the better the water repellency, and an intermediate value (95, 85, 75) is given depending on the state.

A test solution is prepared by diluting the Bundesmann water repellency test polymer dispersion with tap water so that the solid content concentration is 1% by weight, and the polyester and nylon cloth are immersed in this test solution and then passed through a mangle at 160 ° C. A heat-treated test cloth was prepared for 2 minutes. In accordance with the Bundesmann test described in JIS-L-1092 (C) method, the water repellency is evaluated by raining at a rainfall rate of 80 cc / min, a rainwater temperature of 20 ° C. and a rainfall time of 5 minutes or 10 minutes did. The evaluation method was the same as in the spray water repellency test, as shown in Table 1. Is represented by

Example 1
In a 500 mL autoclave, 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 Dioctadecyldimethylammonium chloride = 3 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, 0.5 g of lauryl mercaptan is added, the inside of the autoclave is purged with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g is added, and the mixture is reacted for 3 hours at 60 ° C. A dispersion was obtained. Further, the solid content concentration was adjusted to 30% with pure water, and 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 emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, 0.5 g of lauryl mercaptan is added, the inside of the autoclave is purged with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g is added, and the mixture is reacted for 3 hours at 60 ° C. A dispersion was obtained. Further, the solid content concentration was adjusted to 30% with pure water, and 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 emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, 0.5 g of lauryl mercaptan is added, the inside of the autoclave is purged with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g is added, and the mixture is reacted for 3 hours at 60 ° C. A dispersion was obtained. Further, the solid content concentration was adjusted to 30% with pure water, and water repellency was evaluated.

Example 4
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 = 4 g and dioctadecyldimethylammonium chloride = 3 g were added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, 0.5 g of lauryl mercaptan is added, the inside of the autoclave is purged with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g is added, and the mixture is reacted for 3 hours at 60 ° C. A dispersion was obtained. Further, the solid content concentration was adjusted to 30% with pure water, and 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 with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, 0.5 g of lauryl mercaptan is added, the inside of the autoclave is purged with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g is added, and the mixture is reacted for 3 hours at 60 ° C. A dispersion was obtained. Further, the solid content concentration was adjusted to 30% with pure water, and water repellency was evaluated.

Example 6
In a 500 mL autoclave, 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 Dioctadecyldimethylammonium chloride = 3 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, lauryl mercaptan = 0.5 g is added, the inside of the autoclave is purged with nitrogen, vinyl chloride = 20 g is press-fitted, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g is added, and at 60 ° C. Reaction was performed for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water, and water repellency was evaluated.

Example 7
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 = 4 g and dioctadecyldimethylammonium chloride = 3 g were added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, lauryl mercaptan = 0.5 g was added, the inside of the autoclave was purged with nitrogen, vinyl chloride = 15 g was press-filled, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g was added, and at 60 ° C. Reaction was performed for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water, and water repellency was evaluated.

Comparative Example 1
In a 500 mL autoclave, 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 Dimethylammonium chloride = 3 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, 0.5 g of lauryl mercaptan is added, the inside of the autoclave is purged with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g is added, and the mixture is reacted for 3 hours at 60 ° C. A dispersion was obtained. Further, the solid content concentration was adjusted to 30% with pure water, and 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 emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, lauryl mercaptan = 0.5 g is added, the inside of the autoclave is purged with nitrogen, vinyl chloride = 20 g is press-fitted, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g is added, and at 60 ° C. Reaction was performed for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water, and water repellency was evaluated.

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

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

Claims (12)

(1) (a) Formula:
^{_{CH 2 = CA 11 -C (=}} O) -O-A 12
[Wherein A ¹¹ is halogen, a linear or branched alkyl group having 2 to 21 carbon atoms, or 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 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, and (2) a surfactant containing a nonionic surfactant, and (3) a liquid medium containing water A surface treatment agent that is an aqueous emulsion. The polymer (1) further has a repeating unit derived from a polymerizable monomer other than the monomer (a),
The polymerizable monomer other than the monomer (a) has 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 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 ring having an ester bond It is a C1-C30 organic group. ]
The surface treating agent according to claim 1, which is a compound represented by the formula: A polymerizable monomer other than the monomer (a) is
(B) other acrylate ester monomers other than the long chain α-substituted acrylate ester monomer,
The surface treating agent according to claim 2, which is at least one selected from the group consisting of (c) a non-fluorine crosslinkable monomer and (d) a halogenated olefin. The other acrylate ester monomer (b)
(B1) a long-chain unsubstituted acrylate ester monomer,
The surface treating agent according to claim 3, which 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-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. Item 4. The surface treating agent according to Item 3.   The surface treating 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 treatment agent according to any one of claims 1 to 7, wherein the surface treatment agent does not contain a fluoropolymer.   The surface treating agent according to any one of claims 1 to 7, wherein the surface treating agent further contains a fluoropolymer.   The surface treating agent according to claim 1, 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 textiles processed with the surface treating agent in any one of Claims 1-10.