JPWO2017145918A1 - Surface treatment agent - Google Patents

Abstract

Disclosed is a surface treatment agent having improved processing stability, particularly gum-up properties, for water and oil repellent processing of fibers and the like. (A) a water- and oil-repellent polymer having a repeating unit derived from one or both of a fluorine-containing monomer (A1) having a fluoroalkyl group and a long-chain (meth) acrylate ester monomer (A2); B) a polymer type surfactant, and (C) a surface treatment agent comprising a liquid medium. The polymer surfactant (B) is preferably a quaternary ammonium salt polymer.

Description

  The present invention relates to a surface treatment agent comprising a water / oil repellent polymer and a polymer surfactant. Specifically, the present invention can impart excellent water repellency, oil repellency and antifouling properties to textile products (for example, carpets), paper, non-woven fabrics, stones, electrostatic filters, dust masks, and fuel cell components. .

  Conventionally, various fluorine-containing compounds have been proposed. The fluorine-containing compound has an advantage of excellent properties such as heat resistance, oxidation resistance, and weather resistance. The fluorine-containing compound is used as, for example, a water / oil repellent and an antifouling agent by utilizing the characteristic that the free energy of the fluorine-containing compound is low, that is, it is difficult to adhere.

  Examples of the fluorine-containing compound that can be used as a water / oil repellent include a fluorine-containing polymer having a (meth) acrylate ester having a fluoroalkyl group as a constituent monomer. In practical treatment of fibers with surface treatment agents, various research results so far indicate that dynamic contact angles, particularly receding contact angles, are important as surface characteristics, not static contact angles. That is, the advancing contact angle of water does not depend on the carbon number of the side chain of the fluoroalkyl group, but the receding contact angle of water is significantly smaller at 7 or less than the carbon number of the side chain of 8 or more. . Correspondingly, X-ray analysis shows that side chain crystallization occurs when the side chain has 7 or more carbon atoms. It is known that practical water repellency correlates with the side chain crystallinity, and the mobility of surface treatment agent molecules is an important factor in the development of practical performance (for example, Takashi Maekawa , Fine Chemicals, Vol23, No.6, P12 (1994)). For the above reason, the (meth) acrylate polymer having a short fluoroalkyl group with a side chain having 7 or less carbon atoms (especially 6 or less) has a problem of not satisfying the practical performance as it is because the side chain has low crystallinity. .

  A fluorine-containing surface treatment agent having excellent product stability has been proposed.

  Japanese Patent Application Laid-Open No. 9-118877 discloses a water dispersion type repellent containing a polymer (a) containing polymer units of acrylate or methacrylate containing a polyfluoroalkyl group dispersed in an aqueous medium, and a surfactant (b). In the water / oil repellent composition, the surfactant (b) contains at least three of the following surfactant (c), the following surfactant (d), and the following surfactant (e). In addition, a water-dispersed water / oil repellent composition having excellent stability of impurities is disclosed.

Japanese Patent Application Laid-Open No. 9-125051 discloses a stability comprising an aqueous medium, a polymer (a) containing a polymer unit of acrylate or methacrylate containing a polyfluoroalkyl group dispersed in the aqueous medium, and a surfactant (b). A water-dispersed water / oil repellent composition that is excellent in water resistance is disclosed.
JP-A-2015-120984 discloses one or more antibacterial agents selected from metal oxides, pyridine compounds, and cationic polymers, water absorbing agents, nonionic softeners, and cationic softeners. Disclosed is a textile product provided with one or more selected compounds.

  Conventional fluorine-containing water and oil repellents have insufficient processing stability in water and oil repellent processing.

JP-A-9-118877 Japanese Patent Laid-Open No. 9-125051 JP-A-2015-120984

One object of the present invention is to provide a surface treatment agent having improved processing stability, particularly gum-up properties, for water and oil repellent processing of fibers and the like.
Another object of the present invention is to provide a surface treatment agent having excellent chemical stability (contaminant stability) and mechanical stability.

The present invention
(A) a water- and oil-repellent polymer having a repeating unit derived from one or both of a fluorine-containing monomer (A1) having a fluoroalkyl group and a long-chain (meth) acrylate ester monomer (A2),
A surface treatment agent comprising (B) a polymeric surfactant and (C) a liquid medium is provided.
The present invention further provides:
(I) In the presence of a liquid medium, a fluoroalkyl group-containing fluorine-containing monomer (A1) or a monomer containing a long-chain (meth) acrylate ester monomer (A2) is polymerized to produce a fluoro Obtaining an aqueous dispersion of a water- and oil-repellent polymer having a repeating unit derived from a fluorine-containing monomer having an alkyl group (A1) or a long-chain (meth) acrylate ester monomer (A2); and
(ii) Provided is a method for producing a surface treating agent comprising a step of adding a polymer surfactant to an aqueous dispersion of a water / oil repellent polymer.

The surface treatment agent of the present invention does not cause sedimentation of particles, and does not cause soiling of the fabric due to the polymer adhering to the roll.
According to the present invention, excellent durability such as excellent water repellency, oil repellency, antifouling property and dirt detachability, for example, water and oil repellency can be obtained.
The surface treating agent of the present invention can be used as a water / oil repellent, an antifouling agent and / or a soil release agent.

The surface treatment agent is generally an aqueous emulsion of a water / oil repellent polymer.
Surface treatment agent
(A) a water- and oil-repellent polymer having a repeating unit derived from one or both of a fluorine-containing monomer having a fluoroalkyl group (A1) or a long-chain (meth) acrylate ester monomer (A2),
(B) a polymeric surfactant and (C) a liquid medium.

The water / oil repellent polymer is a fluoropolymer having a fluoroalkyl group or a homopolymer having a repeating unit derived from a long chain (meth) acrylate ester monomer, and a fluorine-containing monomer having a fluoroalkyl group. And a copolymer having a repeating unit derived from two or more monomers selected from a monomer and a long chain (meth) acrylate ester monomer, or a fluorinated monomer or a long chain having a fluoroalkyl group ( A copolymer having a repeating unit derived from another polymerizable compound copolymerizable with a repeating unit derived from a (meth) acrylate ester monomer.
The water / oil repellent polymer is a fluorine-containing polymer or a non-fluorine polymer. The fluorine-containing polymer is a polymer having a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group, and the non-fluorine polymer is a repetition derived from a long-chain (meth) acrylate ester monomer A polymer having units.

In the present invention, the water / oil repellent polymer (A) is (A1) a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group and / or (A2) a long chain (meth) acrylate ester monomer. May consist only of repeating units derived from
In addition to the repeating units (A1) and / or (A2)
It is preferable to have one or both of (A3) a repeating unit derived from a non-fluorine crosslinkable monomer and (A4) a repeating unit derived from a non-fluorine crosslinkable monomer.

  The water / oil repellent polymer (A) has a repeating unit derived from one or both of (A1) a fluorine-containing monomer having a fluoroalkyl group and (A2) a long-chain (meth) acrylate ester monomer. . That is, the water / oil repellent polymer (A) was derived from (A1) a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group and (A2) a long-chain (meth) acrylate ester monomer. Has one or both of the repeating units.

(A1) Fluorinated monomer The fluorinated monomer is generally a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group, a methacrylic acid group, or an α-substituted acrylic acid group.

The fluorine-containing monomer has the formula:
CH ₂ = C (-X) -C (= O) -YZ-Rf
[Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-,
Z is a direct bond or a divalent organic group,
Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]
It is preferable that it is a compound shown by these.

Z is, for example, a linear or branched aliphatic group having 1 to 20 carbon atoms (particularly an alkylene group), for example, a formula — (CH ₂ ) _x — (wherein x is 1 to 10). Or a group represented by the formula —R ² (R ¹ ) N—SO ₂ — or a formula —R ² (R ¹ ) N—CO— (wherein R ¹ has 1 to 1 carbon atoms) 10 is an alkyl group, and R ² is a linear alkylene group having 1 to 10 carbon atoms or a branched alkylene group.) Or a formula —CH ₂ CH (OR ³ ) CH ₂ — (Ar—O). _P- (wherein R ³ is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (eg, formyl or acetyl), Ar is an arylene group optionally having a substituent, and p is 0 or 1) . group represented by representing) a or formula _{-CH 2 -Ar- (O) q -} ( wherein, Ar , An arylene group having necessary a substituent, group q is represented by a 0 or _{1), -. (CH 2} ) m -SO 2 - (CH 2) n - group or a - (CH _{2) m} -S It may be a — (CH ₂ ) _n — group, where m is 1 to 10 and n is 0 to 10.
Specific examples of X are H, CH ₃ , Cl, Br, I, F, CN, and CF ₃ . X is preferably a methyl group or a chlorine atom, and particularly preferably a chlorine atom.

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 a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group, a —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ Is an alkyl group having 1 to 4 carbon atoms.),
-CH ₂ CH (OZ ¹ ) CH _2- (Ph-O) _p -group (where Z ¹ is a hydrogen atom or an acetyl group, Ph is a phenylene group, p is 0 or 1),-(CH ₂ ) _n -Ph-O-group (where, Ph is a phenylene radical, n is _{0~10), -. (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 0-10),
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. ]
An acrylate ester or acrylamide represented by

In the fluorine-containing monomer, the Rf group is preferably a perfluoroalkyl group. The number of carbon atoms in the Rf group is preferably 1 to 12, for example 1 to 6, in particular 4 to 6, particularly 6. Examples of Rf _{groups, -CF 3, -CF 2 CF 3} , -CF 2 CF 2 CF 3, -CF (CF 3) 2, -CF 2 CF 2 CF 2 CF 3, -CF 2 CF (CF 3) ₂ , -C (CF ₃ ) ₃ ,-(CF ₂ ) ₄ CF ₃ ,-(CF ₂ ) ₂ CF (CF ₃ ) ₂ , -CF ₂ C (CF ₃ ) ₃ , -CF (CF ₃ ) CF ₂ CF ₂ CF ₃ , — (CF ₂ ) ₅ CF ₃ , — (CF ₂ ) ₃ CF (CF ₃ ) ₂ , — (CF ₂ ) ₄ CF (CF ₃ ) ₂ , —C ₈ F _{17 and the} like.

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),
-CH ₂ CH (OZ ¹ ) CH _2- (Ph-O) _p -group (where Z ¹ is a hydrogen atom or an acetyl group, Ph is a phenylene group, p is 0 or 1),-(CH ₂ ) _n -Ph-O-group (where, Ph is a phenylene radical, n is _{0~10), -. (CH 2} ) m -SO 2 - (CH 2) n - group or - (CH _{2) m} It is preferably a —S— (CH ₂ ) _n — group (where m is 1 to 10 and n is 0 to 10). The aliphatic group is preferably an alkylene group (particularly having 1 to 4, for example, 1 or 2 carbon atoms). The aromatic group or cycloaliphatic group may be substituted or unsubstituted. The S group or SO ₂ group may be directly bonded to the Rf group.

Specific examples of the fluorine-containing monomer include, for example, the following, but are not limited thereto.
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −Rf
CH ₂ = C (−H) −C (= O) −O−C ₆ H ₄ −Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₂ −Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ N (−CH ₃ ) SO ₂ −Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ N (−C ₂ H ₅ ) SO ₂ −Rf
CH ₂ = C (-H) -C (= O) -O-CH ₂ CH (-OH) CH ₂ -Rf

CH ₂ = C (-H) -C (= O) -O-CH ₂ CH (-OCOCH ₃ ) CH ₂ -Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-H) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-CH ₃ ) -C (= O) -NH- (CH ₂ ) ₂ -Rf

CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-F) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -S-Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -NH- (CH ₂ ) ₂ -Rf

CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-CF ₃ ) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-CF ₂ H) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-CN) -C (= O) -NH- (CH ₂ ) ₂ -Rf

CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-CF ₂ CF ₃ ) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-F) -C (= O) -NH- (CH ₂ ) ₃ -Rf

CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -S-Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf

CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
[In the above formula, Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]

(A2) a long chain (meth) acrylate ester monomer long chain (meth) acrylate ester monomer has the formula:
^{_{CH 2 = CA 11 -C (=}} O) -O-A 12
[In the formula, A ¹¹ represents a hydrogen atom or a methyl group;
A ¹² is a linear or branched hydrocarbon group having 18 to 30 carbon atoms. ]
It may be a compound shown by these.
The long chain (meth) acrylate ester monomer does not have a fluoroalkyl group. The long chain (meth) acrylate ester monomer may contain a fluorine atom, but preferably does not contain a fluorine atom.
A ¹¹ is particularly preferably a methyl group.
A ¹² is a linear or branched hydrocarbon group. The linear or branched hydrocarbon group may in particular be a linear hydrocarbon group. The linear or branched hydrocarbon group has 18 to 30 carbon atoms. The linear or branched hydrocarbon group preferably has 18 to 28 carbon atoms, particularly 18 or 22, and is generally a saturated aliphatic hydrocarbon group, particularly preferably an alkyl group.

Preferred specific examples of the long-chain (meth) acrylate ester monomer are stearyl (meth) acrylate and behenyl (meth) acrylate. Stearyl (meth) acrylate is particularly preferred.
The presence of the long-chain (meth) acrylate ester monomer increases the water repellency, oil repellency and texture imparted by the water / oil repellent polymer.

(A3) Non-fluorine non-crosslinkable monomer The non-fluorine non-crosslinkable monomer (A3) is a monomer other than the long-chain (meth) acrylate ester monomer (A2). The non-fluorine non-crosslinkable monomer (A3) is a monomer containing no fluorine atom. The non-fluorine non-crosslinkable monomer (A3) does not have a crosslinkable functional group. Unlike the crosslinkable monomer (A4), the non-fluorine noncrosslinkable monomer (A3) is noncrosslinkable. The non-fluorine non-crosslinkable monomer (A3) is preferably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine non-crosslinkable monomer (A3) is preferably a vinyl monomer containing no fluorine. The non-fluorine non-crosslinkable monomer (A3) is generally a compound having one carbon-carbon double bond.

A preferred non-fluorine non-crosslinkable monomer (A3) 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 linear or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a linear or cyclic organic group having 1 to 31 carbon atoms having an ester bond. ]
It is a compound shown by these.

  Examples of the linear or cyclic hydrocarbon group having 1 to 30 carbon atoms include linear or branched aliphatic hydrocarbon groups having 1 to 30 carbon atoms, cyclic aliphatic groups having 4 to 30 carbon atoms, and 6 to 6 carbon atoms. 30 aromatic hydrocarbon groups, and C 7-30 araliphatic hydrocarbon groups.

  Examples of the linear or cyclic organic group having 1 to 31 carbon atoms having an ester bond are -C (= O) -OQ and -OC (= O) -Q (where Q is 1-30 carbon atoms). A straight or branched aliphatic hydrocarbon group, a 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). .

  Preferred examples of the non-fluorine non-crosslinkable monomer (A3) include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, Methoxy polypropylene glycol (meth) acrylate and vinyl alkyl ether are included. The non-fluorine non-crosslinkable monomer (A3) is not limited to these examples.

The non-fluorine non-crosslinkable monomer (A3) may be a (meth) acrylate ester having an alkyl group. The number of carbon atoms in the alkyl group may be 1-17. For example, the non-fluorine non-crosslinkable monomer (A3) has the general formula:
CH ₂ = CA ¹ COOA ²
[Wherein, A ¹ 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),
A ² is an alkyl group represented by C _n H _{2n + 1} (n = 1 to 17). ]
An acrylate represented by
The fluorine-containing monomer may not have a repeating unit derived from a (meth) acrylate ester having an alkyl group having 1 to 17 carbon atoms.

  The non-fluorine non-crosslinkable monomer (A3) may be a (meth) acrylate monomer having a cyclic hydrocarbon group. The (meth) acrylate monomer having a cyclic hydrocarbon group is a compound having a (preferably monovalent) cyclic hydrocarbon group and a monovalent (meth) acrylate group. The monovalent cyclic hydrocarbon group and the monovalent (meth) acrylate group are directly bonded. 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. The cyclic hydrocarbon group preferably has 4 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an 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 10 or less. It is preferred that the carbon atom in the ring of the cyclic hydrocarbon group is directly bonded to the ester group in the (meth) acrylate group. 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, a dicyclopentenyl group, and an adamantyl group. The acrylate group is preferably an acrylate group or a methacrylate group, but a methacrylate group is particularly preferable. Specific examples of the monomer having a cyclic hydrocarbon group include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. , Dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl -2-Adamantyl (meth) acrylate and the like.

  The non-fluorine non-crosslinkable monomer (A3) may be a halogenated olefin. The halogenated olefin may be a halogenated olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atom, bromine atom or iodine atom. The halogenated olefin (b) 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 (b) are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide and vinylidene halides such as vinylidene chloride, vinylidene bromide and vinylidene iodide.

(A4) Non-fluorine crosslinkable monomer The water / oil repellent polymer may have a repeating unit derived from the non-fluorine crosslinkable monomer (A4). A non-fluorine crosslinkable monomer (A4) is a monomer which does not contain a fluorine atom. The non-fluorine crosslinkable monomer (A4) may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine. The non-fluorine crosslinkable monomer (A4) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, and the like.

  Examples of the non-fluorine crosslinkable monomer (A4) include diacetone acrylamide, (meth) acrylamide, N-methylol acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and 3-chloro-2-hydroxy. Propyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate These are exemplified, but not limited thereto.

  By copolymerizing the non-fluorine non-crosslinkable monomer (A3) and / or the non-fluorine crosslinkable monomer (A4), water and oil repellency and antifouling properties, and cleaning resistance and washing resistance of these performances Various properties such as solubility, solubility in solvents, hardness, and feel can be improved as necessary.

  The monomer may be polymerized in the presence of at least one compound selected from the group consisting of blocked isocyanate compounds and organopolysiloxane compounds. The amount of the blocked isocyanate compound (or organopolysiloxane compound) may be 0 to 100 parts by weight, for example 1 to 50 parts by weight with respect to 100 parts by weight of the monomer.

  A polymer having a blocked isocyanate group is obtained by polymerizing the monomer in the presence of the blocked isocyanate compound. A blocked isocyanate compound is an isocyanate that is blocked by at least one blocking agent. Examples of blocking agents include oximes, phenols, alcohols, mercaptans, amides, imides, imidazoles, ureas, amines, imines, pyrazoles, and active methylene compounds. Other examples of blocking agents include pyridinols, thiophenols, diketones and esters. The blocked isocyanate compound may be modified with a compound having a hydrophilic group.

A polymer having a siloxane group is obtained by polymerizing the monomer in the presence of an organopolysiloxane compound (for example, mercapto functional organopolysiloxane, vinyl functional organopolysiloxane). In one embodiment, the mercaptofunctional organopolysiloxane has siloxy units having the following average formula:
(R ₂ SiO) _a (RR ^N SiO) _b (RR ^S SiO) _c
[Wherein a is 0 to 4000, alternatively 0 to 1000, alternatively 0 to 400,
b is 1-1000, alternatively 1-100, alternatively 1-50,
c is 1-1000, alternatively 1-100, alternatively 1-50;
R is independently a monovalent organic group,
Alternatively, R is a hydrocarbon having 1 to 30 carbon atoms,
Alternatively, R is a monovalent alkyl group having 1 to 12 carbon atoms,
Alternatively, R is a methyl group;
^RN is a monovalent amino functional organic group as defined above;
R ^S is a monovalent mercapto functional organic group as defined above. ]

Respective amounts of the fluorine-containing monomer (A1) and the long-chain (meth) acrylate ester monomer (A2) (or the total of the monomer (A1) and the monomer (A2)) (however, the monomer The total of (A1) and monomer (A2) is 100% by weight or less.) Is 30 to 100% by weight, preferably 32 to 98% by weight, for example 35% to water / oil repellent polymer. It may be 95% by weight, in particular 40-90% by weight.
In the water / oil repellent polymer, the total amount of 100 parts by weight of the fluorine-containing monomer (A1) and the long-chain (meth) acrylate ester monomer (A2),
The amount of the non-fluorine non-crosslinkable monomer (A3) is 1000 parts by weight or less, such as 0.1 to 300 parts by weight, particularly 1 to 200 parts by weight,
The amount of the non-fluorine crosslinkable monomer (A4) may be 50 parts by weight or less, for example, 30 parts by weight or less, particularly 0.1 to 20 parts by weight.
The amount of the non-fluorine non-crosslinkable monomer (A3) is based on the water / oil repellent polymer (or the sum of the monomer (A1), the monomer (A2) and the monomer (A3)). It may be 2 to 68% by weight, for example 5 to 65% by weight, in particular 10 to 60% by weight.

  The number average molecular weight (Mn) of the water / oil repellent polymer may generally be 1000 to 1000000, for example 2000 to 500000, in particular 3000 to 200000. The number average molecular weight (Mn) of the water / oil repellent polymer is generally measured by GPC (gel permeation chromatography).

(2) Polymer Type Surfactant The polymer type surfactant may be a polymerization surfactant added before polymerization and / or a post-addition surfactant added after polymerization is completed. The polymer surfactant is preferably a post-addition surfactant.
The polymer surfactant is preferably a cationic polymer surfactant, particularly a quaternary ammonium salt polymer. In the polymer surfactant, the nitrogen atom preferably forms an imino group. In the polymer surfactant, the nitrogen atom preferably forms part of the main chain.

The polymeric surfactant has the formula:
_{^{- [(N + Y 4)}} ] r (X -) r -
[In the formula, X fatty bases halogen atoms or C ₁ -C _4,
Each Y is the same or different and is a direct bond or a hydrocarbon group having 1 to 10 carbon atoms which may have a monovalent or divalent oxygen atom;
At least two Y may form a ring together with the adjacent nitrogen atom,
r is 1 or 2; ]
It may have a repeating unit represented by

In X, specific examples of the halogen atom are a chlorine atom, a bromine atom and an iodine atom. The fatty acid base is a group obtained by removing a hydrogen atom from a fatty acid. The fatty acid is preferably a fatty acid having 2 to 20 carbon atoms. Specific examples of the fatty acid are acetic acid and butyric acid.
Y is preferably a linear and / or branched aliphatic group having 1 to 10 carbon atoms which may have a monovalent or divalent oxygen atom (for example, an alkyl group or an alkylene group). . Examples of the aliphatic group which may have an oxygen atom include a hydroxyalkyl group or a hydroxyalkylene group (for example, —CH ₂ CH (OH) CH ₂ —), an oxyalkyl group or an oxyalkylene group (—OCH _2). a) - CH _2.
When r is 2, the eight Y groups may be the same or different from each other.

A preferred polymeric surfactant is of the formula:
^{- [(- Y 1 - (} - Y 2 -N + (Z 1) (Z 2) -Y 3 -) r -Y 4 -) (X -) r] n -
[In the formula, X fatty bases halogen atoms or C ₁ -C _4,
Y ¹ , Y ² , Y ³ and Y ⁴ are a direct bond or a C 1-10 divalent aliphatic group which may have an oxygen atom,
Y ² and Y ³ may form a ring with the adjacent nitrogen atom,
Z ¹ and Z ² are linear and / or branched aliphatic groups having 1 to 10 carbon atoms,
r is 1 or 2,
n is a number of 2 or more. ]
It is a compound shown by these.

In X, specific examples of the halogen atom are a chlorine atom, a bromine atom and an iodine atom. The fatty acid base is a group obtained by removing a hydrogen atom from a fatty acid. The fatty acid is preferably a fatty acid having 2 to 20 carbon atoms. Specific examples of the fatty acid are acetic acid and butyric acid.
Y ¹ , Y ² , Y ³ and Y ⁴ are preferably a direct bond or an alkylene group having 1 to 10 carbon atoms. When Y ² and Y ³ form a ring together with the adjacent nitrogen atom, the ring formed is preferably a 5-membered ring or a 6-membered ring. Specific examples of the ring formed are an aziridine ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring. A pyrrolidine ring is preferred.
Specific examples of Z ¹ and Z ² are a methyl group and an ethyl group.
n may be a number from 5 to 10,000, for example 10 to 1000.
The polymer surfactant preferably does not have one of an oxyalkylene group or an OH group, and more preferably does not have both (both) an oxyalkylene group and an OH group.

Preferred specific examples of the polymeric surfactant are as follows.
Polydiallyldimethylammonium chloride,

Dimethylamine / epichlorohydrin copolymer

Poly [oxyethylene (dimethylimino) propylene (dimethylimino) ethylene dichloride],
Poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride].

The weight average molecular weight of the polymeric surfactant is preferably 3,000 to 100,000, particularly 5,000 to 50,000. The weight average molecular weight can be measured by gel permeation chromatography (GPC) using polyethylene glycol as a standard substance.
The amount of the polymeric surfactant is 0.01 to 10 parts by weight, for example, 0.02 to 5 parts by weight, particularly 0.03 to 2 parts by weight, based on 100 parts by weight of the water / oil repellent polymer. It may be.

(3) Liquid medium The liquid medium may be an aqueous medium, that is, water alone or a mixture of water and a (water-miscible) organic solvent. The amount of the organic solvent may be 30% by weight or less, for example, 10% by weight or less (preferably 0.1% or more) with respect to the liquid medium. The liquid medium is preferably water alone. The liquid medium may be only an organic solvent.
The amount of the liquid medium may be 30 to 99.1% by weight, particularly 50 to 99% by weight, based on the surface treatment agent.

(4) Surfactant for polymerization In the present invention, it is generally preferable to polymerize a monomer in the presence of a surfactant for polymerization.
In the present invention, the polymerization surfactant may be at least one selected from a nonionic surfactant, a cationic surfactant, an anionic surfactant and an amphoteric surfactant.

(4-1) Nonionic surfactant Examples of the nonionic surfactant 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 valent (particularly 2 to 5 valent) alcohols 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 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 valent (particularly 2 to 5 valent) alcohols 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 carbon atoms, in particular 5 to 30 carbon atoms.

  An example of an alkanolamide is a compound formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamide. 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 15 to 30 carbon atoms.
The amine oxide may be an oxide (for example, 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

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. In general, the number of oxyalkylene groups in the nonionic surfactant molecule 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 represents 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 greater than or equal to 2,
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 nonionic surfactants include ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C ₁₂ -C ₁₆ ) thiol, sorbitan monofatty 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.
The 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). It may be a compound represented by ₂ O) _p- (R ² O) _q -R ³ [particularly R ¹ O- (CH ₂ CH ₂ O) _p -H]. 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 to 40 parts by weight, based on 100 parts by weight of the nonionic surfactant. It may be part by weight. In a combination of two or more, the remaining nonionic surfactant is a group in which the R ¹ group (and / or R ³ group) is a (saturated and / or unsaturated) linear alkyl group (eg, lauryl group (n- 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.

  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.

(4-2) Cationic surfactant The cationic surfactant is preferably a compound having no amide group.

Examples of cationic surfactants include amines, amine salts, quaternary ammonium salts, imidazolines and imidazolinium salts.
The cationic surfactant is preferably an amine salt, a quaternary ammonium salt, or an oxyethylene addition type ammonium salt. Specific examples of the cationic surfactant include, but are not limited to, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, Quaternary ammonium salt type surfactants such as alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like can be mentioned.

Examples of cationic surfactants are:
^{R 21 -N + (-R 22)} (- R 23) (- R 24) X -
[In the formula, each of R ²¹ , R ²² , R ²³ and R ²⁴ is independently the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms;
X is an anionic group. ]
It is a compound of this. The hydrocarbon group may have an oxygen atom, and may be, for example, an oxyalkylene such as a polyoxyalkylene group (the alkylene has 2 to 5 carbon atoms, for example). R ²¹ , R ²² , R ²³ and R ²⁴ are preferably a hydrocarbon group having 1 to 30 carbon atoms (for example, an aliphatic hydrocarbon, an aromatic hydrocarbon or an araliphatic hydrocarbon).

Specific examples of R ²¹ , R ²² , R ²³ and R ²⁴ include an alkyl group (for example, methyl group, butyl group, stearyl group, palmityl group), aryl group (for example, phenyl group), aralkyl group (for example, benzyl group) (Phenylmethyl group), phenethyl group (phenylethyl group)).
Specific examples of X are halogen (for example, chlorine), acid (for example, inorganic acid such as hydrochloric acid, organic acid such as acetic acid (particularly fatty acid)).
The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 30 carbon atoms).

The cationic surfactant is preferably an ammonium salt, particularly a quaternary ammonium salt. The cationic surfactant has the formula:
R ³¹ _p -N ⁺ R ³² _q X ⁻
Wherein each R ³¹ is independently the same or different and is a C12 or higher (eg C ₁₂ -C ₅₀ ) linear and / or branched aliphatic (saturated and / or unsaturated) group,
Each of R ³² is independently the same or different, and is an H or C 1-4 alkyl group, benzyl group, polyoxyethylene group (number of oxyethylene groups, for example, 1 (particularly 2, particularly 3) to 50). (CH ₃ and C ₂ H ₅ are particularly preferred),
X is a halogen atom (e.g., chlorine and bromine), 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 ³¹ may have 12 to 50 carbon atoms, for example 12 to 30 carbon atoms.

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

(4-3) Anionic surfactant The anionic surfactant is preferably a salt of an organic acid (for example, a salt of an organic acid and an inorganic base or amine).
Specific examples of anionic surfactants include sodium lauryl sulfate, lauryl sulfate triethanolamine, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene nonylphenyl ether sodium sulfate, polyoxyethylene lauryl ether sulfate triethanolamine, cocoyl sarcosine. Sodium, sodium N-cocoyl methyl taurine, sodium polyoxyethylene coconut alkyl ether sulfate, sodium diether hexyl sulfosuccinate, sodium α-olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethylene lauryl ether phosphate, perfluoroalkyl carboxyl Acid salt (trade name Unidyne DS-101, 102 (manufactured by Daikin Industries, Ltd.)) and the like.

(4-4) Amphoteric surfactants Specific examples of amphoteric surfactants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, lauryl betaine, stearyl betaine, Examples include lauryl carboxymethylhydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

Each of the nonionic surfactant, the cationic surfactant, the anionic surfactant, and the amphoteric surfactant may be one or a combination of two or more.
The amount of the surfactant for polymerization may be 0.05 to 20 parts by weight, for example, 0.1 to 10 parts by weight with respect to 100 parts by weight of the water / oil repellent polymer.

(5) Other component The surface treating agent may contain at least one of a non-fluorine water repellent compound and an additive as a component other than the water / oil repellent polymer, the liquid medium and the surfactant.
(5-1) Non-fluorine water-repellent compound The surface treatment agent may contain a water-repellent compound not containing a fluorine atom (non-fluorine water-repellent compound).
The non-fluorine water repellent compound may be a non-fluorine acrylate polymer, a saturated or unsaturated hydrocarbon compound, or a silicone compound.

The non-fluorine acrylate polymer is a homopolymer composed of one type of non-fluorine acrylate monomer, a copolymer composed of at least two types of non-fluorine acrylate monomers, or at least one type of non-fluorine acrylate monomer. It is a copolymer composed of an acrylate monomer and at least one other non-fluorine monomer (ethylenically unsaturated compound such as ethylene or vinyl monomer).
The non-fluorine acrylate monomer constituting the non-fluorine acrylate polymer 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 linear or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a linear or cyclic organic group having 1 to 31 carbon atoms having an ester bond. ]
It is a compound shown by these.

  Examples of the linear or cyclic hydrocarbon group having 1 to 30 carbon atoms include linear or branched aliphatic hydrocarbon groups having 1 to 30 carbon atoms, cyclic aliphatic groups having 4 to 30 carbon atoms, and 6 to 6 carbon atoms. 30 aromatic hydrocarbon groups, and C 7-30 araliphatic hydrocarbon groups.

  Examples of the linear or cyclic organic group having 1 to 31 carbon atoms having an ester bond are -C (= O) -OQ and -OC (= O) -Q (where Q is 1-30 carbon atoms). A straight or branched aliphatic hydrocarbon group, a 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 non-fluorinated acrylate monomers include, for example, alkyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate It is.

The non-fluorine acrylate monomer is preferably an alkyl (meth) acrylate ester. The number of carbon atoms of the alkyl group may be 1 to 30, for example, 6 to 30 (for example, 10 to 30). Specific examples of non-fluorine acrylate monomers are lauryl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate.
The non-fluorine acrylate polymer can be produced by the same polymerization method as the water / oil repellent polymer.

The saturated or unsaturated hydrocarbon compound is preferably a saturated hydrocarbon. In the saturated or unsaturated hydrocarbon compound, the carbon number may be 15 or more, preferably 20 to 300, for example 25 to 100. Specific examples of the saturated or unsaturated hydrocarbon compound include paraffin.
Silicone compounds are generally used as water repellents. The silicone compound is not limited as long as it is a compound exhibiting water repellency.
The amount of the non-fluorine water-repellent compound may be 500 parts by weight or less, for example, 5 to 200 parts by weight, particularly 5 to 100 parts by weight with respect to 100 parts by weight of the water / oil repellent polymer.

(5-2) Additive The surface treatment agent may contain an additive.
Examples of additives are silicon-containing compounds, waxes, acrylic emulsions and the like. Other examples of additives include other fluoropolymers, drying rate modifiers, crosslinking agents, film-forming aids, compatibilizers, surfactants, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants Agents, pH adjusting agents, antifoaming agents, texture adjusting agents, slipperiness adjusting agents, antistatic agents, hydrophilizing agents, antibacterial agents, antiseptics, insecticides, fragrances, flame retardants and the like.

  The water / oil repellent polymer and non-fluorine polymer in the present invention can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

  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, diisopropyl peroxydicarbonate, and the like. 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 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 treatment agent comprises a water / oil repellent polymer (active component of the surface treatment agent) and a medium (particularly a liquid medium such as an organic solvent and / or water). The amount of the medium may be, for example, 5 to 99.9% by weight, in particular 10 to 80% by weight, based on the treatment agent.
In the treatment agent, the concentration of the water / oil repellent polymer may be 0.01 to 95% by weight, for example 5 to 50% by weight.

  The treatment agent of the present invention can be applied to an object to be treated by a conventionally known method. Usually, the treatment agent is dispersed in an organic solvent or water, diluted, 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. . If necessary, curing may be carried out by applying together with a suitable crosslinking agent (for example, blocked isocyanate). Furthermore, insecticides, softeners, antibacterial agents, flame retardants, antistatic agents, paint fixing agents, anti-wrinkle agents, and the like can be added to the treatment agent of the present invention. The concentration of the water / oil repellent 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 objects to be treated with the treatment agent (for example, water / 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 of the present invention can also be used as an internal release agent or an external release agent.

  The water / oil repellent polymer can be applied to a fibrous substrate (eg, a fiber product, etc.) by any of the known methods for treating a fiber product with a liquid. 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 water / oil repellent polymer may be applied to the textile by a cleaning method, and may be applied to the textile by, for example, 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 water / oil repellent polymer of the present invention is particularly effective in making cellulosic fibers (eg, cotton or rayon) oleophobic and oil repellent. The method of the present invention also generally makes the textile product hydrophobic and water repellent.

Alternatively, the fibrous base material may be leather. Water- and oil-repellent polymers can be used in various stages of leather processing to make the leather hydrophobic and oleophobic, for example, during wet processing of leather or during leather finishing. Or you may apply to leather from aqueous emulsion.
Alternatively, the fibrous substrate may be paper. The water and oil repellent 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.

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.

Water Repellency Test 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 depending on the state, intermediate values (95, 85, 75) and +-are superior or inferior.

Dilute the aqueous dispersion of the gum-up polymer with tap water so that the solids concentration is 1.8% by weight, place the treatment bath in a pad whose temperature can be adjusted to 40 ° C, and wear a cotton cloth around the mangle roll. Thus, continuous treatment was performed at a pressure of 5.5 kgf / cm ² . The state of adhesion of the polymer to the mangle after 1 hour is visually observed, and the gum-up property is determined according to the criteria in Table 2 described below.

Production Example 1
In a 500 mL autoclave, C ₆ F ₁₃ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (C6SFMA) = 80 g, stearyl acrylate = 20 g, pure water = 200 g, tripropylene glycol = 30 g, polyoxyethylene (POE) oleyl ether = 3 g and polyoxyethylene (POE) isotridecyl ether = 7 g were added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, the interior of the autoclave was purged 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 dispersion of polymer. Further, the solid content concentration was adjusted to 30% with pure water.

Production Example 2
In a 500 mL autoclave, C ₆ F ₁₃ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (C6SFMA) = 80 g, stearyl acrylate = 20 g, pure water = 200 g, tripropylene glycol = 30 g, polyoxyethylene (POE) oleyl ether = 3 g, polyoxyethylene (POE) isotridecyl ether = 4 g, and dioctadecyldimethylammonium chloride (DOdDMAC) = 3 g were added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, the interior of the autoclave was purged 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 dispersion of polymer. Further, the solid content concentration was adjusted to 30% with pure water.

Production Example 3
In a 500 mL autoclave, C ₆ F ₁₃ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (C6SFMA) = 60 g, stearyl acrylate = 10 g, isobornyl methacrylate = 10 g, pure water = 200 g, tripropylene glycol = 30 g, polyoxy Ethylene (POE) oleyl ether = 3 g and polyoxyethylene (POE) isotridecyl ether = 7 g were added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, the inside of the autoclave was purged with nitrogen, and then vinyl chloride (VCM) = 20 g was injected and charged, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g was added, and the reaction was carried out at 60 ° C. for 3 hours for heavy reaction. A combined aqueous dispersion was obtained. Further, the solid content concentration was adjusted to 30% with pure water.

Production Example 4
In a 500 mL autoclave, C ₆ F ₁₃ CH ₂ CH ₂ OCOC (Cl) = CH ₂ (C6SFCLA) = 80 g, stearyl acrylate = 20 g, pure water = 200 g, tripropylene glycol = 30 g, polyoxyethylene (POE) oleyl ether = 3 g Polyoxyethylene (POE) isotridecyl ether = 7 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, the interior of the autoclave was purged 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 dispersion of polymer. Further, the solid content concentration was adjusted to 30% with pure water.

Production Example 5
In a 500 mL autoclave, C ₆ F ₁₃ CH ₂ CH ₂ OCOC (Cl) = CH ₂ (C6SFCLA) = 60 g, lauryl acrylate = 20 g, isobornyl methacrylate = 20 g, pure water = 200 g, tripropylene glycol = 30 g, polyoxyethylene (POE) oleyl ether = 3 g and polyoxyethylene (POE) isotridecyl ether = 7 g were added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, the interior of the autoclave was purged 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 dispersion of polymer. Further, the solid content concentration was adjusted to 30% with pure water.

Production Example 6
In a 500 mL autoclave, C ₆ F ₁₃ CH ₂ CH ₂ OCOC (Cl) = CH ₂ (C6SFCLA) = 40 g, lauryl acrylate = 20 g, isobornyl methacrylate = 20 g, pure water = 200 g, tripropylene glycol = 30 g, polyoxyethylene (POE) oleyl ether = 3 g and polyoxyethylene (POE) isotridecyl ether = 7 g were added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, the inside of the autoclave was purged with nitrogen, and then vinyl chloride (VCM) = 20 g was injected and charged, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g was added, and the reaction was carried out at 60 ° C. for 3 hours for heavy reaction. A combined aqueous dispersion was obtained. Further, the solid content concentration was adjusted to 30% with pure water.

Production Example 7
Stearyl acrylate = 90 g, 2,3-dihydroxypropyl methacrylate = 10 g, pure water = 200 g, tripropylene glycol = 30 g, polyoxyethylene (POE) oleyl ether = 3 g, polyoxyethylene (POE) isotridecyl ether = 7 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes under stirring. After emulsification, the interior of the autoclave was purged 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 dispersion of polymer. Further, the solid content concentration was adjusted to 30% with pure water.

Production Example 8
In a 500 mL autoclave, stearyl acrylate = 70 g, 2,3-dihydroxypropyl methacrylate = 10 g, pure water = 200 g, tripropylene glycol = 30 g, polyoxyethylene (POE) oleyl ether = 3 g, polyoxyethylene (POE) isotridecyl ether = 7 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes under stirring. After emulsification, the inside of the autoclave was purged with nitrogen, 2,2-azobis (2-amidinopropane) dihydrochloride = 1 g was added, reacted at 60 ° C. for 1 hour, and then injected and charged with vinyl chloride = 20 g. The polymer was reacted for a time to obtain an aqueous dispersion of polymer. Further, the solid content concentration was adjusted to 30% with pure water.

The composition for each production example is summarized in Table 3.

Example 1
An aqueous dispersion in which 0.1 part of a 30% aqueous solution of polydiallyldimethylammonium chloride (molecular weight 9000) (PDADMAC-9000) was mixed with 100 parts of the polymerization dispersion (30%) produced in Production Example 1 was prepared. . Prepare a test solution by diluting this dispersion with tap water so that the solids concentration is 0.15 wt%, 0.30 wt%, 0.60 wt%, soak the polyester cloth in this test solution, The water repellency was evaluated with a test cloth heat treated at 160 ° C. for 2 minutes (low concentration water repellency). Further, the water repellency was similarly evaluated for a test solution diluted with tap water so that the solid content concentration of the dispersion was 0.60% by weight and the disperse dye was 0.006% by weight. Furthermore, the gum-up property was evaluated.

Example 2
An aqueous dispersion prepared by mixing 0.1 part of a 30% aqueous solution of polydiallyldimethylammonium chloride (molecular weight 30000) (PDADMAC-30000) with 100 parts of the polymerization dispersion (30%) produced in Production Example 1 was prepared. Evaluation was performed in the same manner as in Example 1.

Example 3
An aqueous dispersion was prepared by mixing 0.5 part of a 30% aqueous solution of polydiallyldimethylammonium chloride (molecular weight 30000) (PDADMAC-30000) with 100 parts of the polymerization dispersion (30%) produced in Production Example 1. Evaluation was performed in the same manner as in Example 1.

Example 4
An aqueous dispersion prepared by mixing 0.1 part of a 30% aqueous solution of dimethylamine epichlorohydrin condensate salt (molecular weight 9000) (PDMAECH-9000) with 100 parts of the polymerization dispersion (30%) produced in Production Example 1 was prepared. Then, the evaluation was performed in the same manner as in Example 1.

Examples 5-11
An aqueous dispersion obtained by mixing 0.1 part of a 30% aqueous solution of polydiallyldimethylammonium chloride (molecular weight 30000) (PDADMAC-30000) with 100 parts of the polymerization dispersion (30%) produced in Production Examples 2 to 8 Prepared and evaluated in the same manner as in Example 1.

Comparative Example 1
Nothing was added to the polymer dispersion (30%) produced in Production Example 1, and evaluation was performed in the same manner as in Example 1.

Comparative Example 2
An aqueous dispersion prepared by mixing 0.1 part of a 30% aqueous solution of polyoxyethylene beef tallow alkylbenzylammonium chloride (TBzPOEC) to 100 parts of the polymerization dispersion (30%) produced in Production Example 1 was prepared. Evaluation was performed in the same manner as in 1.

Comparative Example 3
An aqueous dispersion in which 0.1 part of a 30% aqueous solution of lauryldimethylamine oxide (LDMAO) was mixed with 100 parts of the polymerization dispersion (30%) produced in Production Example 1 was prepared in the same manner as in Example 1. Evaluation was performed.

Comparative Example 4
An aqueous dispersion was prepared by mixing 0.1 part of a 30% aqueous solution of dimethylaminopropylamide stearate (StDMAPAD) with 100 parts of the polymer dispersion (30%) produced in Production Example 1. Evaluation was performed in the same manner.

Comparative Examples 5-8
Instead of Production Example 8, Production Example 1 was prepared and evaluated in the same manner as Comparative Examples 1 to 4.

  The performance of each example is shown in Table 4 and Table 5.

  The surface treating agent of the present invention can be used as, for example, a water / oil repellent, an antifouling agent and a soil release agent.

Claims (14)

(A) a water- and oil-repellent polymer having a repeating unit derived from one or both of a fluorine-containing monomer (A1) having a fluoroalkyl group and a long-chain (meth) acrylate ester monomer (A2),
A surface treatment agent comprising (B) a polymeric surfactant and (C) a liquid medium. The fluorine-containing monomer (A1) has the formula:
CH ₂ = C (-X) -C (= O) -YZ-Rf
[Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-,
Z is a direct bond or a divalent organic group,
Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]
The surface treating agent according to claim 1, which is a compound represented by the formula:   The surface treating agent according to claim 2, wherein in the fluorine-containing monomer (A1), Rf has 1 to 6 carbon atoms. The long chain (meth) acrylate ester monomer (A2) has the formula:
^{_{CH 2 = CA 11 -C (=}} O) -O-A 12
[In the formula, A ¹¹ represents a hydrogen atom or a methyl group;
A ¹² is a linear or branched hydrocarbon group having 18 to 30 carbon atoms. ]
The surface treating agent according to any one of claims 1 to 3, which is a compound represented by the formula: Water / oil repellent polymer
5. The method according to claim 1, further comprising at least one of (A3) a repeating unit derived from a non-fluorine crosslinkable monomer and (A4) a repeating unit derived from a non-fluorine crosslinkable monomer. The surface treating agent as described in.   The surface treating agent according to any one of claims 1 to 5, wherein the polymer surfactant (B) is a quaternary ammonium salt polymer. The polymeric surfactant (B) has the formula:
_{^{- [(N + Y 4)}} ] r (X -) r -
[In the formula, X fatty bases halogen atoms or C ₁ -C _4,
Each Y is the same or different and is a direct bond or a hydrocarbon group having 1 to 10 carbon atoms which may have a monovalent or divalent oxygen atom;
At least two Y may form a ring together with the adjacent nitrogen atom,
r is 1 or 2; ]
The surface treating agent according to any one of claims 1 to 6, which has a repeating unit represented by: The polymeric surfactant (B) has the formula:
^{- [(- Y 1 - (} - Y 2 -N + (Z 1) (Z 2) -Y 3 -) r -Y 4 -) (X -) r] n -
[In the formula, X fatty bases halogen atoms or C ₁ -C _4,
Y ¹ , Y ² , Y ³ and Y ⁴ are each a direct bond or a C 1-10 divalent aliphatic group which may have an oxygen atom,
Y ² and Y ³ may form a ring with the adjacent nitrogen atom,
Z ¹ and Z ² are linear and / or branched aliphatic groups having 1 to 10 carbon atoms,
r is 1 or 2,
n is a number of 2 or more. ]
The surface treating agent according to any one of claims 1 to 7, which is a compound represented by the formula:   The surface treating agent according to any one of claims 1 to 8, wherein the polymer type surfactant (B) has a weight average molecular weight of 3,000 to 100,000, particularly 5,000 to 50,000. The amount of the polymeric surfactant (B) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the water / oil repellent polymer (A),
The amount of a liquid medium (C) is 30-99.1 weight% with respect to a surface treating agent, The surface treating agent in any one of Claims 1-9. The total of the fluorine-containing monomer (A1) and the long chain (meth) acrylate ester monomer (A2) is 32 to 98% by weight with respect to the water / oil repellent polymer,
The amount of the non-fluorine non-crosslinkable monomer (A3) is 2 to 68% by weight based on the water / oil repellent polymer,
The amount of the non-fluorine crosslinkable monomer (A4) is 50 parts by weight or less with respect to 100 parts by weight in total of the fluorine-containing monomer (A1) and the long-chain (meth) acrylate ester monomer (A2). The surface treating agent according to any one of claims 5 to 10.   The surface treatment agent according to any one of claims 1 to 11, wherein the surface treatment agent is a water / oil repellent agent, an antifouling agent or a soil release agent. (I) In the presence of a liquid medium, a monomer comprising one or both of a fluoromonomer-containing fluorine-containing monomer (A1) and a long-chain (meth) acrylate ester monomer (A2) is polymerized. And obtaining an aqueous dispersion of a water / oil repellent polymer having a repeating unit derived from one or both of the fluorine-containing monomer (A1) and the long-chain (meth) acrylate ester monomer (A2) ,and
(ii) A method for producing a surface treating agent according to any one of claims 1 to 12, which comprises a step of adding a polymeric surfactant to an aqueous dispersion of a water / oil repellent polymer.   The manufacturing method of the processed base material including applying the surface treating agent in any one of Claims 1-12 to a base material.