WO2012133622A1 - Composition containing fluorinated copolymer - Google Patents

Abstract

Disclosed is a composition which can impart excellent water-absorbing properties, oil-repellent properties, stain-proof properties and stain-releasing properties to woven fiber fabrics and the like, and which has the same excellent properties as those of conventional compositions in spite of a fact that the number of carbon atoms in an Rf group is less than 8 that is smaller than those in the conventional compositions. The composition comprises: (1) a fluorinated copolymer which comprises, as essential components, (a) a fluorinated monomer represented by general formula CH₂=C(-X)-C(=O)-Y-[-(CH₂)_m-Z-]_p-(CH₂)_n-Rf (I) [wherein X represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like; Z represents a direct bond, -S- or -SO₂-; Rf represents a fluoroalkyl group having 1-6 carbon atoms; m represents 1-10; n represents 0-10; and p represents 0 or 1] and (b) an alkoxy-group-containing monomer represented by general formula CH₂=C(X')-C(=O)-O-(RO)_q-H (II) [wherein X' represents a hydrogen atom or a methyl group; R represents an alkylene group having 2-4 carbon atoms in which each of some or all of hydrogen atoms may be substituted by a hydroxy group; and q represents an integer of 1-50], and which does not contain any amino-group-containing monomer; (2) a block isocyanate compound; and (3) a liquid medium.

Description

Composition containing fluorine-containing copolymer

The present invention relates to a composition comprising a fluorine-containing copolymer (in particular, an SR agent (antifouling agent or soil release agent)). The composition of the present invention has excellent water absorption and antifouling properties.

A (meth) acrylic acid ester having a fluoroalkyl group (hereinafter also referred to as a fluorine-containing compound) is used as an antifouling agent that imparts water and oil repellency to textile fabrics and makes it easy to remove dirt adhering to fibers by washing. And a hydrophilic group-containing compound are known (see JP-A-53-134786, JP-A-59-204980, JP-A-62-7782). These antifouling finishing agents have a feature that dirt is easily removed by washing, and have been used in, for example, work clothes and uniforms. In recent years, the application range of antifouling agents tends to be expanded, and for example, processing into polo shirts, T-shirts, and the like has been studied.
However, the major drawback of the conventional antifouling agent is that the water absorption is insufficient.For example, since the fibers do not absorb sweat even if sweat is applied, wearing in a sweating environment is not unpleasant, and this application The development of was limited.

In general, oil repellency and flip-flop are important for obtaining sufficient soil detachability. In the air, perfluoroalkyl groups (hereinafter abbreviated as Rf groups) are oriented on the surface, and have high repellency. Contrary to this, in water, the Rf group recedes and the hydrophilic group is oriented on the surface while exhibiting oiliness, and dirt is easily removed. Flip-flop is a property in which the surface molecular structure changes depending on the environment in air and water, and is proposed by Sherman et al. [P.Sherman, S.Smith, B, Johannessen, Textile Research Journal, 39,499 (1969)]
When the chain length of the Rf group is short, the oil repellency tends to decrease with the decrease in crystallinity of Rf, and the article to be treated is easily contaminated with oil stains. For this reason, an Rf group having substantially 8 or more carbon atoms has been used. (See JP-A-53-134786 and JP-A-2000-290640)

Further, for compounds containing an Rf group having 8 carbon atoms, which have recently been obtained by telomerization,
Federal Register (FR Vol.68, No.73 / April 16,2003 [FRL-7303-8]) (http://www.epa.gov/opptintr/pfoa/pfoafr.pdf)
EPA Environmental News FOR RELEASE: MONDAY APRIL 14, 2003
EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID
(Http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) or
EPA OPPT FACT SHEET April 14, 2003 (http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf) allows telomers to produce perfluorooctanoic acid (hereinafter abbreviated as “PFOA”) by decomposition or metabolism It is announced that there is a sex.
The EPA (United States Environmental Protection Agency) has announced that it will strengthen scientific research against PFOA. (See 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)).

WO 2003/095083 describes a fluorine-containing graft polymer using an isocyanate group-containing vinyl monomer. Although it is described that this fluorine-containing graft polymer imparts antifouling properties, the resulting antifouling properties and / or water absorption are not sufficient.

JP-A-53-134786 JP 59-204980 A See JP-A-62-7782. JP-A-53-134786 JP 2000-290640 A WO 2003/095083

An object of the present invention is to provide a composition that imparts excellent water absorption, oil repellency, antifouling properties, and dirt release properties to textile fabrics and the like, and the Rf group has less than 8 carbon atoms. An object of the present invention is to provide a composition having the same excellent properties even if it is shorter than conventional ones.

The simplest method for improving water absorption is to reduce the fluorine content in the soil release (SR) polymer and relatively increase the ratio of hydrophilic components. This certainly improves the water absorption to some extent, but conversely reduces the oil repellency and dirt release (SR property). It is important to improve water absorption without deteriorating oil repellency and SR property.

The present invention
(1) a fluorine-containing copolymer,
(A) General formula:
CH ₂ = C (-X) -C (= O) -Y-[-(CH ₂ ) _m -Z-] _p- (CH ₂ ) _n -Rf (I)
[Wherein X is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, a fluorine atom or a chlorine atom) ), A cyano group, a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group;
Y is —O— or —NH—;
Z is a direct bond, —S— or —SO ₂ —;
Rf is a fluoroalkyl group having 1 to 6 carbon atoms;
m is 1 to 10, n is 0 to 10, and p is 0 or 1. ]
And a fluorine-containing monomer represented by
(b) General formula:
CH ₂ = C (X ')-C (= O) -O- (RO) _q -H (II)
Wherein X ′ is a hydrogen atom or a methyl group;
R is an alkylene group having 2 to 4 carbon atoms in which some or all of the hydrogen atoms may be substituted with hydroxyl groups;
q is an integer of 1 to 50. ]
As an essential component, an alkoxy group-containing monomer represented by
A fluorine-containing copolymer not containing a monomer having an amino group,
(2) A composition (particularly, a soil release agent) comprising a blocked isocyanate compound and (3) a liquid medium is provided.

The composition of the present invention (particularly, the soil release agent) is excellent in water absorption, and is excellent in antifouling properties and soil release properties.

The composition of the present invention comprises:
(1) a fluorine-containing copolymer,
(2) A blocked isocyanate compound and (3) a liquid medium.
Generally, the composition of the present invention is produced by adding a blocked isocyanate compound to a fluorinated copolymer liquid comprising a fluorinated copolymer and a liquid medium.

[(1) Fluorine-containing copolymer]
The fluorine-containing copolymer in the present invention generally does not have a repeating unit composed of a monomer having an amino group.
Amino groups generally have the formula:
(R ¹¹ ) (R ¹² ) N-
[Wherein, R ¹¹ and R ¹² are the same or different and each represents a monovalent group (for example, a hydrogen atom). ]
It is group shown by these. A monomer having an amino group generally has at least one carbon-carbon double bond in addition to the amino group.

The fluorine-containing monomer (a) has the general formula:
CH ₂ = C (-X) -C (= O) -Y-[-(CH ₂ ) _m -Z-] _p- (CH ₂ ) _n -Rf (I)
[Wherein X is a hydrogen atom, a methyl group, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom,
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 group having 1 to 21 carbon atoms A fluoroalkyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group;
Y is —O— or —NH—;
Z is a direct bond, —S— or —SO ₂ —;
Rf is a fluoroalkyl group having 1 to 6 carbon atoms;
m is 1 to 10, n is 0 to 10, and p is 0 or 1. ]
It is shown by. In general formula (I), it is preferable that p is 0.

A preferred example of X is a hydrogen atom.

In the fluorine-containing monomer (a), the Rf group is generally a perfluoroalkyl group and / or a partially fluorinated fluoroalkyl group. The Rf group is preferably a perfluoroalkyl group. The Rf group has 1 to 6 carbon atoms. The carbon number of the Rf group may be 4, 5 or 6, in particular 6. Examples of Rf groups are -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 and the} like.

m is 1 to 10, for example, 2 to 5. n is 0 to 10, for example 1 to 6, in particular 2 to 5.
The fluorine-containing monomer (a) may be used alone or in combination of two or more.

Examples of the fluorine-containing monomer (a) include the following.
CH ₂ = C (-X) -C (= O) -O- (CH ₂ ) _m -S- (CH ₂ ) _n -Rf
CH ₂ = C (-X) -C (= O) -O- (CH ₂ ) _m -SO _2- (CH ₂ ) _n -Rf
CH ₂ = C (-X) -C (= O) -O- (CH ₂ ) _n -Rf
CH ₂ = C (-X) -C (= O) -NH- (CH ₂ ) _n -Rf
[In the above formula, X is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, a fluorine atom or a chlorine atom) A cyano group, a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group;
Rf is a 1-6 fluoroalkyl group;
m is 1 to 10, and n is 0 to 10. ]

Specific examples of the fluorine-containing monomer (a) include, but are not limited to, for example, the following.
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) -O- (CH ₂ ) ₂ -Rf
CH ₂ = C (-H) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (-H) -C (= O) -OCH ₂ CH ₂ N (C ₂ H ₅ ) SO ₂ -Rf
CH ₂ = C (-H) -C (= O) -OCH ₂ CH ₂ N (CH ₃ ) SO ₂ -Rf
CH ₂ = C (-H) -C (= O) -OCH ₂ CH (OCOCH ₃ ) CH 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) -O- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -OCH ₂ CH ₂ N (C ₂ H ₅ ) SO ₂ -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -OCH ₂ CH ₂ N (CH ₃ ) SO ₂ -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -OCH ₂ CH (OCOCH ₃ ) CH 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) -O- (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) -O- (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) -O- (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) -O- (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) -O- (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) -O- (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) -O- (CH ₂ ) ₃ -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 1-6 fluoroalkyl group. ]

The alkoxy group-containing monomer (b) is a non-fluorine monomer and has the general formula:
(b) General formula:
CH ₂ = C (X ')-C (= O) -O- (RO) _q -H (II)
Wherein X ′ is a hydrogen atom or a methyl group;
R is an alkylene group having 2 to 4 carbon atoms in which some or all of the hydrogen atoms may be substituted with hydroxyl groups;
q is an integer of 1 to 50. ]
It is a compound (alkylene glycol (meth) acrylate) shown by these.
In the alkoxy group-containing monomer (b), q is preferably 1 to 30, for example 2 to 10, particularly 2 to 5.

In the general formula (II), R is preferably ethylene or propylene, particularly ethylene. R in the general formula (II) may be a combination of two or more types of alkylene. In that case, at least one of R is preferably ethylene. Examples of the combination of R include an ethylene group / propylene group combination and an ethylene group / butylene group combination.
The alkoxy group-containing monomer (b) may be a mixture of two or more types.

Specific examples of the alkoxy group-containing monomer (b) include, for example, the following, but are not limited thereto.
CH ₂ = CHCOO- (CH ₂ CH ₂ O) ₃ -H
CH ₂ = CHCOO- (CH ₂ CH ₂ O) ₅ -H
CH ₂ = CHCOO- (CH ₂ CH ₂ O) ₉ -H
CH ₂ = C (CH ₃ ) COO- (CH ₂ CH ₂ O) ₃ -H
CH ₂ = C (CH ₃ ) COO- (CH ₂ CH ₂ O) ₅ -H
CH ₂ = C (CH ₃ ) COO- (CH ₂ CH ₂ O) ₉ -H
CH ₂ = C (CH ₃ ) COO- (CH ₂ CH ₂ O) ₂₃ -H
CH ₂ = C (CH ₃ ) COO- (CH ₂ CH ₂ O) ₅₀ -H
CH ₂ = CHCOO- (CH ₂ CH (CH ₃ ) O) ₃ -H
CH ₂ = CHCOO- (CH ₂ CH (CH ₃ ) O) ₉ -H
CH ₂ = C (CH ₃ ) COO- (CH ₂ CH (CH ₃ ) O) ₄ -H
CH ₂ = C (CH ₃ ) COO- (CH ₂ CH (CH ₃ ) O) ₉ -H
CH ₂ = C (CH ₃ ) COO- (CH ₂ CH ₂ O) _2- (CH ₂ CH (CH ₃ ) O) ₂ -H
CH ₂ = C (CH ₃ ) COO- (CH ₂ CH ₂ O) _5- (CH ₂ CH (CH ₃ ) O) ₂ -H
_{CH 2 = C (CH 3)} COO- (CH 2 CH 2 O) 8 - (CH 2 CH (CH 3) O) 6 -H

The fluorine-containing copolymer may contain (c) a crosslinkable monomer. The crosslinkable monomer (c) may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine. The crosslinkable monomer (c) 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 isocyanates, carboxyl groups, and the like. In the present invention, a monomer having an amino group is not used.

The crosslinkable monomer (c) is preferably a non-fluorine crosslinkable monomer, and particularly preferably di (meth) acrylate.
The crosslinkable monomer (c) has the general formula:
CH ₂ = C (X ")-C (= O) -O- (R" O) _q -C (= O) -C (X ") = CH ₂ (III)
[Wherein each X ″ is a hydrogen atom or a methyl group;
R ″ is an alkylene group having 2 to 10 carbon atoms in which some or all of the hydrogen atoms may be substituted with hydroxyl groups;
q is an integer of 1 to 50. ]
It is preferable that it is a compound (alkylene glycol di (meth) acrylate) shown by these. R ″ has 2 to 10, for example, 2 to 6, particularly 2 to 4. R ″ is preferably an ethylene group. In the formula (III), q is preferably 1 to 30, for example 2 to 10.
Specific examples of the alkylene glycol di (meth) acrylate represented by the formula (III) are as follows.

CH ₂ = C (CH ₃ ) COO- (CH ₂ CH ₂ O) ₅ -COC (CH ₃ ) = CH ₂
CH ₂ = CHCOO- (CH ₂ CH ₂ O) ₉ -COCH = CH ₂
CH ₂ = C (CH ₃ ) COO- (CH ₂ CH (CH ₃ ) O) ₁₂ -COCH = CH ₂
CH ₂ = CHCOO- (CH ₂ CH ₂ O) _5- (CH ₂ CH (CH ₃ ) O) ₃ -COCH = CH ₂
CH ₂ = C (CH ₃ ) COO- (CH ₂ CH ₂ O) ₂₃ -OOC (CH ₃ ) C = CH _{2
CH 2 = C (CH 3)} COO- (CH 2 CH 2 O) 20 - (CH 2 CH (CH 3) O) 5 -COCH = CH 2

Other examples of the crosslinkable monomer (c) include diacetone (meth) acrylamide, (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3- Examples include, but are not limited to, chloro-2-hydroxypropyl (meth) acrylate, butadiene, chloroprene, glycidyl (meth) acrylate, 1,6-hexanediol acrylate, neopentyl glycol diacrylate, and the like.

Still other examples of the crosslinkable monomer (c) include isocyanate group-containing (meth) acrylates such as glycerol (meth) acrylate, acetoacetoxyethyl (meth) acrylate, 2-isocyanatoethyl methacrylate, methyl ethyl ketoxime, etc. Those (meth) acrylates whose isocyanate groups are blocked with the blocking agent are exemplified.
The crosslinkable monomer (c) may be a mixture of two or more.

The fluorine-containing copolymer may contain (d) a non-crosslinkable monomer. The non-crosslinkable monomer (d) is a monomer other than the alkoxy group-containing monomer (b), generally a non-fluorine monomer. The non-crosslinkable monomer (d) preferably contains no fluorine and has a carbon-carbon double bond. The non-crosslinkable monomer (d) is preferably a vinyl monomer that does not contain fluorine. The non-crosslinkable monomer is generally a compound having one carbon-carbon double bond.

Non-crosslinkable monomers (d) include butadiene, chloroprene, maleic acid derivatives, vinyl halides such as vinyl chloride, vinylidene halides such as ethylene and vinylidene chloride, vinyl alkyl ethers, styrene, alkyl (meth) Examples include, but are not limited to, acrylate and vinyl pyrrolidone.

The non-crosslinkable monomer (d) may be a (meth) acrylic acid ester containing an alkyl group. The alkyl group may have 1 to 30 carbon atoms, for example 6 to 30, for example 10 to 30 carbon atoms. For example, the non-crosslinkable monomer has the general formula:
CH ₂ = CA ¹ COOA ²
[Wherein, A ¹ represents a hydrogen atom or a methyl group, and A ² represents a (chain or cyclic) C _1-30 alkyl group. ]
It may be an acrylate represented by

The fluorine-containing copolymer contains 100 parts by weight of the fluorine-containing monomer (a). For 100 parts by weight of the fluorine-containing monomer (a),
The amount of the alkoxy group-containing monomer (b) is 10 to 400 parts by weight, for example 25 to 150 parts by weight, particularly 43 to 100 parts by weight,
The amount of the crosslinkable monomer (c) is 30 parts by weight or less, for example, 0.1 to 20 parts by weight, particularly 0.5 to 10 parts by weight,
The amount of the non-crosslinkable monomer (d) is preferably 20 parts by weight or less, for example, 0.1 to 15 parts by weight, particularly 0.5 to 10 parts by weight.

The weight average molecular weight of the fluorinated copolymer in the present invention may be 1,000 to 1,000,000, preferably 5,000 to 500,000. The weight average molecular weight is a value obtained by gel permeation chromatography in terms of polystyrene.

The polymerization of the fluorine-containing copolymer is not particularly limited, and various polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization can be selected. For example, solution polymerization using an organic solvent or emulsion polymerization using water or an organic solvent and water in combination is generally selected. After the polymerization, the solution is prepared by diluting with water or adding an emulsifier and emulsifying in water.
In the present invention, it is preferable to disperse the polymer in water by adding water after removing the solvent after polymerization (for example, solution polymerization or emulsion polymerization).
Examples of organic solvents include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and methyl acetate, glycols such as propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and low molecular weight polyethylene glycol. Examples thereof include alcohols such as ethyl alcohol and isopropanol.
As the emulsifier when emulsifying in water by adding an emulsifier after emulsion polymerization or polymerization, various general anionic, cationic and nonionic emulsifiers can be used.

As the polymerization initiator, for example, a peroxide, an azo compound or a persulfuric acid compound can be used. The polymerization initiator is generally water-soluble and / or oil-soluble.
Specific examples of the oil-soluble polymerization initiator include 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2, 4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl4-methoxyvaleronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), dimethyl 2,2′-azobis (2 -Methylpropionate), 2,2'-azobis (2-isobutyronitrile), benzoyl peroxide, di-tertiary-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxy Pivalate, diisopropyl peroxydicarbonate, t-butyl perpivalate and the like are preferable.

Specific examples of the water-soluble polymerization initiator include 2,2′-azobisisobutylamidine dihydrochloride, 2,2′-azobis (2-methylpropionamidine) hydrochloride, 2,2′-azobis [ 2- (2-imidazolin-2-yl) propane] hydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] sulfate hydrate, 2,2′-azobis [2- Preferred examples include (5-methyl-2-imidazolin-2-yl) propane] hydrochloride, potassium persulfate, barium persulfate, ammonium persulfate, hydrogen peroxide, and the like.
The polymerization initiator is preferably an organic peroxide having a 10-hour half-life temperature of 40 ° C. or higher. It is particularly preferred that the polymerization initiator is t-butyl peroxypivalate.
The polymerization initiator is used in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the monomer.
For the purpose of adjusting the molecular weight, a chain transfer agent such as a mercapto group-containing compound may be used, and specific examples thereof include 2-mercaptoethanol, thiopropionic acid, alkyl mercaptan and the like. The mercapto group-containing compound is used in an amount of 10 parts by weight or less and 0.01 to 5 parts by weight based on 100 parts by weight of the monomer.

Specifically, the fluorine-containing copolymer can be produced as follows.
In solution polymerization, a method is adopted in which a monomer is dissolved in an organic solvent, after substitution with nitrogen, a polymerization initiator is added, and the mixture is heated and stirred, for example, in the range of 40 to 120 ° C. for 1 to 10 hours. The polymerization initiator may generally be an oil-soluble polymerization initiator.

Examples of the organic solvent are those which are inert to the monomer and dissolve them, such as 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, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichloro And trifluoroethane. The organic solvent is used in the range of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total monomer.

In emulsion polymerization, a method is adopted in which a monomer is emulsified in water in the presence of an emulsifier and the like, after substitution with nitrogen, a polymerization initiator is added, and the mixture is stirred and polymerized in the range of 40 to 80 ° C. for 1 to 10 hours. Is done. 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 finely divided into water using an emulsifier that can give strong crushing energy such as a high-pressure homogenizer or ultrasonic homogenizer, and is oil-soluble. It is desirable to polymerize using a polymerization initiator. 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, it may be used in the range of 10 to 40 parts by weight. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers. For example, it may be used in the range of 10 to 40 parts by weight.

[(2) Blocked isocyanate compound]
A blocked isocyanate compound is an isocyanate that is blocked by at least one blocking agent.

The blocked isocyanate compound is a compound that has a blocked isocyanate group, does not have a polymerizable unsaturated group, and has an isocyanate residue of an isocyanate blocked by a blocking agent. The blocked isocyanate compound may be modified with a compound having a hydrophilic group.

Examples of hydrophilic groups include nonionic hydrophilic groups (eg, hydroxyl groups, amino groups, and polyoxyalkylene groups (particularly polyoxyethylene groups)); and ionic (cationic or anionic) hydrophilic groups (eg, Carboxyl group, sulfate group, sulfone group, sulfonate group and sulfite group).

Examples of isocyanates include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), MDI oligomer, naphthalene-1,5-diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate (HDI), 4,4-dicyclohexylmethane diisocyanate, norbornane diisocyanate. , Isophorone diisocyanate (IPDI), adducts (eg TDI or HDI TMP (trimethylolpropane) adduct), allophanate modified products, biuret modified products (eg biuret made from HDI), isocyanurate modified products Products (for example, isocyanurates produced from TDI, isocyanurates produced from HDI, isocyanurates produced from IPDI) DOO, and isocyanurates) prepared from TDI and HDI, or a carbodiimide-modified product or a urethane prepolymer, the foregoing compounds.

Examples of blocking agents include (i) oximes, (ii) phenols, (iii) alcohols, (iv) mercaptans, (v) amides, (vi) imides, (vii) imidazoles, ( viii) ureas, (ix) amines, (x) imines, (xi) pyrazoles, and (xii) 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.

(i) Oxime Examples of oximes include formamide oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime and cyclohexanone oxime.

(ii) Phenols Examples of phenols include phenols optionally having at least one (preferably one or two) C _1-10 alkyl group. Specific examples of phenols include: phenol; monoalkylphenol (eg, cresol, ethylphenol, propylphenol, butylphenol, hexylphenol, 2-ethylhexylphenol and octylphenol); and dialkylphenol (eg, diethylphenol, dipropylphenol, Dipropylcresol, dibutylphenol, di-2-ethylhexylphenol, dioctylphenol and dinonylphenol).
Specific examples of phenols include styrenated phenols and hydroxybenzoate esters.

(iii) Alcohols Examples of alcohols include (preferably monovalent) alcohols (particularly alkanols) having a C ₁ -C ₃₀ alkyl group.
Specific examples of alcohols include methanol, ethanol, propanol, 1-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxy-1-propanol, and 3- And methyl-2-penten-4-in-1-ol.
(iv) Mercaptans Specific examples of mercaptans include butyl mercaptan and dodecyl mercaptan.

(v) Amides Specific examples of amides (preferably acidic amides) include acetanilide, acetic acid amide, β-propiolactam, γ-butyrolactam, δ-valerolactam, ε-caprolactam, laurolactam, stearolactam, N-methyl-ε-caprolactam and pyrrolidinone.
(vi) Imides Specific examples of imides include acid imides such as maleic imide and succinimide.

(vii) Imidazoles Specific examples of imidazoles include imidazole and 2-methylimidazole.
(viii) Ureas Specific examples of ureas include urea, thiourea and ethyleneurea.

(ix) Amines Specific examples of the amines include diphenylamine, aniline, carbazole, diethylamine, dipropylamine and propylethylamine.
(x) Imines Specific examples of imines include ethyleneimine and polyethyleneimine.

(xi) Pyrazoles As specific examples of pyrazoles,
2-methyl-pyrazole, 3-methyl-pyrazole, 4-methyl-pyrazole, 2,4-dimethyl-pyrazole, 2,5-dimethyl-pyrazole, 3,4-dimethyl-pyrazole, 3,5-dimethyl-pyrazole, Examples include 4-nitro-3,5-dimethyl-pyrazole and 4-bromo-3,5-dimethyl-pyrazole.
(xii) Active methylene compounds Examples of active methylene compounds include malonate esters (eg, C _1-30 -alkyl malonic acid esters), acetoacetate esters (eg, C _1-30 -alkyl acetoacetate esters) And acetylacetone.

The blocking agent for forming the blocked isocyanate compound is preferably a pyrazole compound or a malonate ester compound.

The pyrazole compound has the formula:

[In the formula, each R ¹¹ is the same or different and is an alkyl group, an alkenyl group, an aralkyl group, an N-substituted carbamyl group, a phenyl group, NO ₂ , a halogen atom, or a —C (═O) OR ¹² group (R ¹² is an alkyl group having 1 to 4 carbon atoms.)
n is 0, 1, 2 or 3. ]
It may be shown by.

Specific examples of pyrazole compounds include
2-methyl-pyrazole, 3-methyl-pyrazole, 4-methyl-pyrazole, 2,4-dimethyl-pyrazole, 2,5-dimethyl-pyrazole, 3,4-dimethyl-pyrazole, 3,5-dimethyl-pyrazole, Examples include 4-nitro-3,5-dimethyl-pyrazole and 4-bromo-3,5-dimethyl-pyrazole.

The malonate ester compound is a reaction product (monoester or diester (preferably diester)) of malonic acid and alcohol (for example, monohydric alcohol). In general, the alcohol has a hydrocarbon group having 1 to 30 carbon atoms bonded to a hydroxyl group. The hydrocarbon group is preferably an alkyl group, especially an alkyl group having 1 to 4 carbon atoms.

Specific examples of the malonate ester include dimethyl malonate, diethyl malonate, dipropyl malonate, dibutyl malonate, methyl malonate, ethyl malonate, propyl malonate and butyl malonate. Diesters are preferred. Preferred specific examples of malonate esters include dimethyl malonate, diethyl malonate, dipropyl malonate and dibutyl malonate.

The blocked isocyanate compound may be modified with a compound having a hydrophilic group. The compound having a hydrophilic group may be a compound having a nonionic hydrophilic group or a compound having an ionic hydrophilic group. Alternatively, a compound having a hydrophilic group is a reaction between a compound having a nonionic hydrophilic group or a compound having an ionic hydrophilic group and an isocyanate, usually active hydrogen (eg, —OH or —NH ₂ ) And an isocyanate group (—NCO).

Each of the compound having a nonionic hydrophilic group and the compound having an ionic hydrophilic group preferably has a number average molecular weight of 100 to 4000, particularly 200 to 2000. A compound having a nonionic hydrophilic group is particularly preferred. The compound having a nonionic hydrophilic group is preferably a compound having an active hydrogen and a polyethylene oxide chain at one end. A compound having a nonionic hydrophilic group can be produced by addition reaction of an alkylene oxide, particularly ethylene oxide, with a monoalcohol such as methanol (for example, having 1 to 30 carbon atoms). Here, the ethylene oxide content is preferably at least 50% by weight based on the alkylene oxide (the upper limit of the ethylene oxide content is 100% by weight, for example 90% by weight, based on the alkylene oxide). ). The compound having a nonionic hydrophilic group may contain propylene oxide units in an amount of 0 to 50% by weight, for example 0 to 20% by weight, in particular 1 to 10% by weight, based on the alkylene oxide. The compound having an ionic hydrophilic group is preferably an anionic compound (for example, hydroxycarboxylic acid, amino acid, aminosulfonic acid and hydroxysulfonic acid). A cationic compound such as a tertiary amino compound having a hydroxy group (for example, dimethylaminopropanol) can be used as the compound having an ionic hydrophilic group. A tertiary amino compound having a hydroxy group is reacted with an isocyanate and then neutralized with an acid or reacted with a quaternizing agent (eg, benzyl chloride) to give a quaternized salt.

Examples of compounds having a hydrophilic group include monovalent to tetravalent alcohols having aliphatic groups (eg C ₁ -C ₃₀ ) and monovalents having at least one oxyalkylene group (eg C ₃ -C ₂₀₀ ). Examples include alcohol. This can be prepared by adding (eg C ₂ -C ₅ ) alkylene oxide to (eg C ₁ -C ₃₀ ) monohydric alcohols. As a specific example of the compound having a hydrophilic group,
R— (O—CH ₂ CH ₂ ) _n —OH
[Wherein R is a C ₁ -C ₁₀ aliphatic (or alkyl) group (eg, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ ), and n is 2 to 50, preferably Is 5-25. ]
The compound shown by these is mentioned.

The blocked isocyanate compound is an isocyanate [isocyanate is A (NCO) _m (where A and m are the same as described below (for example, A is a group remaining after the isocyanate-reactive group is removed, and m is It may be indicated by an integer from 2 to 8.]]
The blocking agent is indicated by RH (wherein R is a hydrocarbon group which may be substituted by a heteroatom such as a nitrogen atom and an oxygen atom, and H is a hydrogen atom). Good. ]
Can be made to react.

The blocked isocyanate compound has the formula:
AY _m
[In the formula, A represents an m-valent aliphatic group, alicyclic group, heterocyclic group or aromatic group (where m is an integer of 2 to 8);
Y is the same or different,

(However, each R ¹¹ is the same or different and is an alkyl group, an alkenyl group, an aralkyl group, an N-substituted carbamyl group, a phenyl group, NO ₂ , a halogen atom or a —C (═O) OR ¹² group (R ¹² Is an alkyl group having 1 to 4 carbon atoms),
n is 0, 1, 2 or 3. )
Or
-NH-C (= O) -CH- (C (= O) -OR ²¹ ) ₂
(R ²¹ is a hydrocarbon group having 1 to 30 carbon atoms or a monovalent group having a hydrophilic group.)
-NHCOO- (R ³¹ -O) _k -R ³²
(R ³¹ is an alkylene group having 2 to 5 carbon atoms;
R ³² is an aliphatic group (or alkyl group) having 1 to 10 carbon atoms, such as CH ₃ , C ₂ H ₅ , C ₃ H ₇ and C ₄ H ₉ ,
k is 2 to 50, preferably 5 to 25. )
m is 1 to 10, in particular 2 to 5. ]
It is preferable that it is a compound shown by these.

In the isocyanate compound, Y is
(I)

Or
(ii)
-NH-C (= O) -CH- (C (= O) -OR ²¹ ) ₂
Or
(iii)
-NHCOO- (R ³¹ -O) _k -R ³²
Or (iv) a combination comprising at least two of the above (i), (ii) and (iii).

The amount of the blocked isocyanate compound may be 0.5 to 50 parts by weight, for example, 1 to 20 parts by weight with respect to 100 parts by weight of all the monomers or the fluorinated copolymer.

[(3) Liquid medium]
The liquid medium is a solvent composed of water and / or an organic solvent. The liquid medium may be a mixture of water and an organic solvent. The liquid medium is preferably a solvent used when a monomer is polymerized to produce a fluorinated copolymer. A solvent may be added after producing the fluoropolymer. The solvent added after the polymerization may be the same as or different from the solvent used during the polymerization.

The amount of the liquid medium may be such that the concentration of the fluorine-containing copolymer and the blocked isocyanate compound in the composition is 0.02 to 70% by weight, for example 1 to 50% by weight.

The composition of the present invention (that is, the treatment agent (particularly, the soil release agent)) is preferably in the form of a solution, an emulsion or an aerosol. The treating agent comprises a fluorine-containing copolymer and a medium (for example, a liquid medium such as an organic solvent and water). In the treating agent, the concentration of the fluorinated copolymer may be, for example, 0.01 to 50% by weight, particularly 0.1 to 40% by weight.

The fluorine-containing polymer (fluorine-containing copolymer) in the present invention can be prepared by any method depending on the type of article to be treated and the preparation form (emulsion, organic solvent solution, aerosol, etc.). Can be applied to the article to be treated. For example, in the case of an aqueous emulsion or an organic solvent solution, a method of adhering to a surface of an object to be processed and drying by a known method of coating processing such as dip coating or spray coating can be employed. At this time, if necessary, heat treatment such as curing may be performed.
If necessary, other blenders can be used together. For example, water / oil repellent, wrinkle preventive, anti-shrink agent, flame retardant, crosslinking agent, antistatic agent, softener, water-soluble polymer such as polyethylene glycol and polyvinyl alcohol, wax emulsion, antibacterial agent, pigment, paint, etc. is there. These blenders may be used by being added to the object to be treated and the treatment bath at the time of treatment, or in advance, if possible, mixed with the fluoropolymer in the present invention.

The article to be treated is not particularly limited, but besides textiles, stones, filters (for example, electrostatic filters), dust masks, glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, Mention may be made of ceramic products, plastics, painted surfaces and plasters. It is particularly useful for textile products. Various examples can be given as textile products. For example, animal and vegetable natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, and carbon fibers , Inorganic fibers such as asbestos fibers, or mixed fibers thereof. The fiber product may be in the form of fiber, yarn, cloth or the like.

In the present invention, the article to be treated is treated with a treatment agent (particularly, a soil release agent). “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 fluoropolymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object.

Next, an Example, a comparative example, and a test example are given and this invention is demonstrated concretely. However, these explanations do not limit the present invention.
In the following, parts or% represents parts by weight or% by weight unless otherwise specified.
The test methods used below are as follows.

<Water absorption test, droplet method>
Using a micropipette, gently place 10 μL of drinking water (20 ± 2 ° C.) on the test cloth. Measure the time (unit: seconds) from when a water drop is placed on the test cloth until the water drop soaks into the test cloth and disappears. Here, the disappearance of water droplets means a state where the specular reflection of water disappears and only moisture remains. Five locations are measured and the average water absorption time is taken as the measured value.

<Water absorption test Wicking method>
The test cloth is cut into strips having a length of 16 cm and a width of 2.5 cm.
This is set in a 200 ml beaker containing 200 g of pure water so that the tip of the test cloth is immersed in water by 5 to 10 mm. After 30 minutes, the height from the surface of the water rising from the cloth by capillary action is read.

<Oil repellency test (OR test)>
The oil repellency test was conducted according to AATCC-TM118-2000 using a textile product. That is, the test cloth is spread horizontally, a few drops of the test solution shown in Table 3 is dropped, and the infiltration state after 30 seconds is determined. When the oil repellency is low, oil stains enter the article to be treated in the air, making it difficult to remove them. This is an important evaluation index along with the soil detachability (SR property) test.

<Soil detachment test (SR test)>
The soil detachment test was conducted according to the AATCC Stain Release Management Performance Test Method in the United States. Corn oil (corn oil), mineral oil (mineral oil) or chili oil was used as the soil for the test.
Spread a 20 cm square test cloth on blotting paper laid horizontally, and drop 5 drops (about 0.2 cc) of corn oil (or mineral oil or chili oil) on the test cloth as dirt. Put glassine paper on top of it, place an additional 2268 g of weight, and leave it for 60 seconds. After 60 seconds, the weight and the glassing paper are removed and left at room temperature for 15 minutes. After 15 minutes, the ballast cloth is added to the test cloth to make 1.8 kg, and 100 g of detergent (AATCC standard WOB detergent) is used, and the bath volume is 64 liters in the AATCC standard washing machine (manufactured by Kenmore, USA). After washing and rinsing at 38 ° C. for 12 minutes, the test cloth is dried with an AATCC standard tumbler dryer (manufactured by Kenmore, USA). The state of residual stain on the dried test cloth is compared with a standard photographic plate for judgment, and the dirt removal performance is expressed by the corresponding judgment grade (see Table 4). The standard photographic plate for judgment was AATCC-TM130-2000 (American Association of Textile Chemists and Colorists-Test Method 130-2000).

<Water-absorbing, oil-repellent (OR), SR-type washing durability>
Washing by AATCC-135 method is repeated 10 or 20 times, and the subsequent water absorption, oil repellency (OR property) and SR property are evaluated (HL-10, HL-20).

[Synthesis Example 1]
Synthesis of fluorinated copolymer 1:
Fluorinated monomer CH ₂ = CHC (= O) O-CH ₂ CH ₂ C ₆ F ₁₃ (hereinafter referred to as C6SFA (a)) in a 100 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer 18.0 g, 2-hydroxyethyl acrylate (hereinafter referred to as HEA) 3 g, polyethylene glycol acrylate CH ₂ = CHC (= O) O- (CH ₂ CH ₂ O) n-H (BLEMMER AE200, JP Oil Co., Ltd., average value of n is 4.5) (hereinafter referred to as AE200) 7.5 g, polyethylene glycol diacrylate CH ₂ = CHC (= O) O- (CH ₂ CH ₂ O) n-C (= O) CH = CH ₂ (BLEMMER ADE300, manufactured by NOF Corporation, the average value of n is 7) (hereinafter referred to as ADE300) is 1.5 g, 2-mercaptoethanol is 0.45 g and methyl ethyl ketone (hereinafter, 45 g) was charged and nitrogen bubbling was performed for 30 minutes.
After raising the internal temperature to 50-65 ° C. under a nitrogen stream, 0.4 g of perbutyl PV (hereinafter referred to as PV) was added and reacted at 60 to 65 ° C. for 6 hours. After the MEK was distilled off at about 70 ° C. under reduced pressure conditions to obtain a pale yellow polymer residue, 122.4 g of water was added and the internal temperature was kept at about 80 ° C. for 1 hr or longer. Cooling to prepare an aqueous dispersion having a solid content concentration of about 20% by weight.

[Synthesis Example 2]
Synthesis of blocked isocyanate 1:
To the reaction vessel, 32 g of methylene diphenyl diisocyanate (16 g) and methyl isobutyl ketone were added and heated to 72-75 ° C. Methyl ethyl ketoxime (6.0 g) was slowly charged and reacted at 60 to 70 ° C. until the isocyanate content as confirmed by an infrared spectrophotometer was zero, to obtain a white solid. This composition was added with lauryl polyethylene glycol ether (average number of moles of ethylene oxide added 16.2 g) and dispersed in water by forced emulsification to prepare an aqueous dispersion having a solid concentration of about 40%.

[Synthesis Example 3]
Synthesis of blocked isocyanate 2:
To the reaction vessel was added 32 g of hexamethylene diisocyanate-based isocyanurate (16 g, isocyanurate type of hexamethylene diisocyanate, NCO functional group number 3, Sumidur N-3300, manufactured by Sumika Bayer Urethane Co., Ltd.), and methyl isobutyl ketone. Heated to 72-75 ° C. Next, 11 g of polyethylene glycol monomethyl ether (average number of moles of ethylene oxide added: 12) was slowly charged and allowed to react for 1 hour. Next, 3,5-dimethylpyrazole (6.0 g, 62.4 mmol) was slowly charged, and the reaction was carried out at 60 to 70 ° C. until the isocyanate content as confirmed by an infrared spectrophotometer was zero. A liquid composition was obtained. This colorless and transparent liquid composition was dispersed in water to prepare an aqueous dispersion having a solid content of about 40%.

[Comparative Synthesis Example 1]
Synthesis of fluorinated copolymer C1:
In a 100 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, 18.0 g of C6SFA (a), 3 g of HEA, 7.5 g of AE200, dimethylaminoethyl methacrylate CH ₂ = C (CH ₃ ) 1.5 g of C (= O) O—CH ₂ CH ₂ N (CH ₃ ) ₂ (light ester DM, manufactured by Kyoeisha Chemical Co., Ltd.) (hereinafter referred to as DM), 0.3 g of 2-mercaptoethanol And 45 g of MEK were charged and nitrogen bubbling was performed for 30 minutes.
After raising the internal temperature to 50-65 ° C. under a nitrogen stream, 0.4 g of perbutyl PV (hereinafter referred to as PV) was added and reacted at 60 to 65 ° C. for 6 hours.
The conversion of C6SFA (a) was 99.2%.
MEK was distilled off from the resulting solution at about 70 ° C. under reduced pressure to obtain a pale yellow polymer residue. Then, 121.2 g of water and 0.6 g of acetic acid were added, and the internal temperature was about 80 ° C. After maintaining for 1 hour or more, the mixture was cooled to prepare an aqueous dispersion having a solid concentration of about 20% by weight.

[Comparative Synthesis Example 2]
Synthesis of fluorinated copolymer C2:
In Comparative Synthesis Example 1, AE200 was changed to methoxypolyethylene glycol # 400 methacrylate CH ₂ ═C (CH ₃ ) C (═O) O— (CH ₂ CH ₂ O) n—CH ₃
(NK ester M-90G, manufactured by Shin-Nakamura Chemical Co., Ltd., average value of n is 9) (hereinafter referred to as M-90G), the same polymerization reaction as in Comparative Synthesis Example 1 was performed, and the solid content concentration About 20% by weight of an aqueous dispersion was prepared.

[Example 1]
20 parts aqueous dispersion of fluorine-containing copolymer obtained in Synthesis Example 1 3.0 parts aqueous dispersion of blocked isocyanate obtained in Synthesis Example 2 0.25 parts Tap water 96.75 parts Synthesis at the above ratio The fluorine-containing copolymer dispersion obtained in Example 1 and the blocked isocyanate aqueous dispersion obtained in Synthesis Example 2 were diluted with water to prepare a processing solution. 100% cotton cloth and 100% PET cloth were immersed in the treatment solution thus obtained and squeezed with a roll so that the wet pickup (WPU) was 60 mass%. Next, the soil release agent treatment was completed by drying and heat-treating the fabric at 160 ° C. for 3 minutes. These fabrics were measured for water absorption (water droplet method, wicking method), soil release (SR) and oil repellency (OR).
The results are shown in Table 3.

[Example 2]
Except for changing the amount of the 20% aqueous dispersion of the fluorine-containing copolymer obtained in Synthesis Example 1 to 6.0 parts, a treatment solution was prepared and cloth-treated in the same manner as in Example 1 to remove soil. And oil repellency were measured.
The results are shown in Table 3.

[Example 3]
20 parts aqueous dispersion of fluorine-containing copolymer obtained in Synthesis Example 1 3.0 parts aqueous dispersion obtained in Synthesis Example 3 1.0 part tap water 96.75 parts The obtained fluorine-containing copolymer dispersion and the blocked isocyanate aqueous dispersion obtained in Synthesis Example 3 were diluted with water to prepare a processing solution. 100% cotton cloth and 100% PET cloth were immersed in the treatment solution thus obtained and squeezed with a roll so that the wet pickup (WPU) was 60 mass%. Next, the soil release agent treatment was completed by drying and heat-treating the fabric at 160 ° C. for 3 minutes. These fabrics were measured for water absorption (water droplet method, wicking method), soil detachment property and oil repellency.
The results are shown in Table 3.

[Example 4]
Except for changing the amount of the 20% aqueous dispersion of the fluorinated copolymer obtained in Synthesis Example 1 to 6.0 parts, a treatment solution was prepared and cloth-treated in the same manner as in Example 3 to remove dirt. And oil repellency were measured. The results are shown in Table 3.

[Example 5]
20% aqueous dispersion of fluorine-containing copolymer obtained in Synthesis Example 1 3.0 parts aqueous dispersion of blocked isocyanate obtained in Synthesis Example 2 0.25 parts Becamine NS-19 (Glyoxal Resin, Dainippon Ink Chemistry) 8.0 parts Becamine X-80 (Glyoxal Resin Catalyst, Dainippon Ink & Chemicals) 2.4 parts tap water 78.35 parts Fluorine-containing copolymer dispersion obtained in Synthesis Example 1 in the above proportion The blocked isocyanate aqueous dispersion obtained in Synthesis Example 2 was diluted with water to prepare a processing solution. 100% cotton cloth, 65% / 35% = PET / cotton cloth (T / C) was immersed in the treatment liquid thus obtained, and squeezed with a roll so that the wet pickup (WPU) was 60 mass%. . Next, the soil release agent treatment was completed by drying and heat-treating the fabric at 160 ° C. for 3 minutes. These fabrics were measured for water absorption (water droplet method, wicking method), soil detachment property and oil repellency.
The results are shown in Table 4.

[Example 6]
Except for changing the amount of the 20% aqueous dispersion of the fluorinated copolymer obtained in Synthesis Example 1 to 6.0 parts, a treatment solution was prepared and cloth-treated in the same manner as in Example 3 to remove dirt. And oil repellency were measured.
The results are shown in Table 4.

[Comparative Example 1]
20% aqueous dispersion of fluorine-containing copolymer obtained in Comparative Synthesis Example 1 3.0 parts tap water 97.0 parts In Comparative Synthesis Example 1, 20% aqueous dispersion of fluorine-containing copolymer was added in the above proportion. A 20% aqueous dispersion of the resulting fluorinated copolymer was diluted with water to prepare a processing solution. 100% cotton cloth, 65% / 35% = PET / cotton cloth (T / C) was immersed in the treatment liquid thus obtained, and squeezed with a roll so that the wet pickup (WPU) was 60 mass%. . Next, the soil release agent treatment was completed by drying and heat-treating the fabric at 160 ° C. for 3 minutes. These fabrics were measured for water absorption (water droplet method, wicking method), soil detachment property and oil repellency.
The results are shown in Table 5.

[Comparative Example 2]
A treatment liquid was prepared in the same procedure as in Example 1, except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Synthesis Example 1. After treatment, the soil release and oil repellency were measured.
The results are shown in Table 5.

[Comparative Example 3]
A treatment liquid was prepared in the same procedure as in Example 2, except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Synthesis Example 1. After treatment, the soil release and oil repellency were measured.
The results are shown in Table 5.

[Comparative Example 4]
A treatment liquid was prepared in the same procedure as in Example 5 except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Synthesis Example 1. After treatment, the soil release and oil repellency were measured.
The results are shown in Table 6.

[Comparative Example 5]
A treatment liquid was prepared in the same procedure as in Example 6 except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Synthesis Example 1. After treatment, the soil release and oil repellency were measured.
The results are shown in Table 6.

[Comparative Example 6]
A treatment liquid was prepared in the same procedure as in Example 1, except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Synthesis Example 2. After treatment, the soil release and oil repellency were measured.
The results are shown in Table 5.

[Comparative Example 7]
A treatment liquid was prepared in the same procedure as in Example 2, except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Synthesis Example 2. After treatment, the soil release and oil repellency were measured.
The results are shown in Table 5.

[Comparative Example 8]
A treatment liquid was prepared in the same procedure as in Example 5, except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Synthesis Example 2. After treatment, the soil release and oil repellency were measured.
The results are shown in Table 6.

[Comparative Example 9]
A treatment liquid was prepared in the same procedure as in Example 6, except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Synthesis Example 2. After treatment, the soil release and oil repellency were measured.
The results are shown in Table 6.

The composition of the present invention can be used as a soil release agent having excellent water absorption, antifouling properties and soil release properties.

Claims (17)

1. (1) (a) General formula:
   CH ₂ = C (-X) -C (= O) -Y-[-(CH ₂ ) _m -Z-] _p- (CH ₂ ) _n -Rf (I)
   [Wherein X is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, a fluorine atom or a chlorine atom) ), A cyano group, a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group;
   Y is —O— or —NH—;
   Z is a direct bond, —S— or —SO ₂ —;
   Rf is a fluoroalkyl group having 1 to 6 carbon atoms;
   m is 1 to 10, n is 0 to 10, and p is 0 or 1. ]
   And a fluorine-containing monomer represented by
   (b) General formula:
   CH ₂ = C (X ')-C (= O) -O- (RO) _q -H (II)
   Wherein X ′ is a hydrogen atom or a methyl group;
   R is an alkylene group having 2 to 4 carbon atoms in which some or all of the hydrogen atoms may be substituted with hydroxyl groups;
   q is an integer of 1 to 50. ]
   As an essential component, an alkoxy group-containing monomer represented by
   A fluorine-containing copolymer not containing a monomer having an amino group,
   (2) A composition comprising a blocked isocyanate compound and (3) a liquid medium.
2. The composition according to claim 1, wherein p is an integer of 0 in the fluorine-containing monomer (a).
3. The composition according to claim 1 or 2, wherein in the fluorine-containing monomer (a), X is a hydrogen atom.
4. The composition according to claim 1, wherein in the fluorine-containing monomer (a), Rf is a C 6 perfluoroalkyl group.
5. The composition according to any one of claims 1 to 4, wherein in the alkoxy group-containing monomer (b), q is an integer of 1 to 30.
6. 6. The composition according to claim 1, further comprising (c) a crosslinkable monomer.
7. The composition according to claim 6, wherein the crosslinkable monomer (c) is a non-fluorine crosslinkable monomer and is di (meth) acrylate.
8. The crosslinkable monomer (c) has the general formula:
   General formula:
   CH ₂ = C (X ")-C (= O) -O- (R" O) _q -C (= O) -C (X ") = CH ₂ (III)
   [Wherein each X ″ is a hydrogen atom or a methyl group;
   R ″ is an alkylene group having 2 to 10 carbon atoms in which some or all of the hydrogen atoms may be substituted with hydroxyl groups;
   q is an integer of 1 to 50. ]
   The composition of Claim 7 which is di (meth) acrylate shown by these.
9. 7. The fluorine-containing copolymer, wherein the non-fluorine non-crosslinking monomer (b) is 10 to 400 parts by weight with respect to 100 parts by weight of the fluorine-containing monomer (a). A composition according to 1.
10. The amount of the crosslinkable monomer (c) is 0.1 to 30 parts by weight based on 100 parts by weight of the total of the fluorine-containing monomer (a) and the alkoxy group-containing monomer (b). The composition according to any one of 1 to 9.
11. In the blocked isocyanate, the blocking agent is selected from the group consisting of oximes, phenols, alcohols, mercaptans, amides, imides, imidazoles, ureas, amines, imines, pyrazoles, and active methylene compounds. The composition according to any one of claims 1 to 10, which is selected.
12. The composition according to any one of claims 1 to 10, wherein in the blocked isocyanate, the blocking agent is a pyrazole.
13. The composition according to any one of claims 1 to 12, which is in the form of a solution, an emulsion or an aerosol.
14. A method for treating a substrate, comprising treating with the composition according to any one of claims 1 to 13.
15. A textile product treated with the composition according to any one of claims 1 to 13.
16. The composition according to any one of claims 1 to 13, wherein the composition is a soil release agent.
17. Use of the composition according to any one of claims 1 to 13 as a soil release agent.