TW201247717A - Soil releasing agent containing fluorine-containing copolymer - Google Patents

Abstract

The present invention provides a composition giving excellent water absorption ability, oil-repellent ability, soil resistance and soil releasing ability to fiber fabric and the like, and further, even the carbon atoms of the Rf group compared to prior arts being shorter, which is less than 8, still having same excellent properties. The said composition comprises: (1) a fluorine-containing copolymer having (a) and (b) as essential ingredient, and not containing any monomer having amino group: (a) a fluorine-containing monomer represented by the following formula (I), (b) an alkoxyl-containing monomer represented by the following formula (II); CH2=C(-X)-C(=O)-Y-[-(CH2)m-Z-]p-(CH2)n-Rf (I) [wherein, X is hydrogen atom, methyl group, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.; Z is a direct bond, -S- or -SO2-; Rf is a fluoroalkyl group having 1 to 6 carbon atoms; m is 1 to 10, n is 0 to 10, p is 0 or 1] CH2=C(X')-C(=O)-O-(RO)q-H (II) [wherein, X' is hydrogen atom or methyl group; R is an alkylene group having 2 to 4 carbon atoms, wherein a part or all of the hydrogen atoms may be optionally substituted by hydroxyl group; q is an integer of 1 to 50.] (2) a blocked isocyanate compound, and (3) liquid medium.

Description

201247717 VI. Description of the Invention: - [Technical Field to Be Invented by the Invention] The present invention relates to a composition comprising a fluorine-containing copolymer (particularly 'an SR agent (antifouling agent or soil release agent)). The composition of the present invention is excellent in water absorbability and excellent in antifouling property. [Prior Art] An antifouling agent which imparts water repellency and oil repellency to a fiber iron or the like, and which is easily removed by washing by adhesion to dirt such as fibers. A copolymer having a fluoroalkyl group (meth) acrylate (hereinafter referred to as a fluorine-containing compound) and a compound containing a hydrophilic group is known (refer to Japanese Patent Laid-Open No. Sho 53-134786, Japanese Patent Application Laid-Open No. 59-204980 Bulletin, Japanese Patent Laid-Open No. 62-7782). These antifouling agents have the advantage of being easy to remove dirt by washing, and can be used, for example, in work clothes and uniforms. In recent years, the application range of antifouling processing agents has been expanding. For example, it has been discussed for Polo shirts, T-shirts, etc. However, a major disadvantage of conventional antifouling processing agents is insufficient water absorption, for example, even sweating fibers. It does not absorb sweat, so it will be uncomfortable to wear in a sweaty environment. 'The development of this use is limited. Generally, it is necessary to obtain sufficient soil release property, and oil-repellent property and Flip-flop property are important. In the air, a perfluoroalkyl group (hereinafter abbreviated as Rf group) is aligned to the surface to exhibit high oil repellency, and at the same time In water, on the contrary, the Rf group recedes and the hydrophilic group is aligned to the surface, so that the dirt is easily peeled off. Transmutation refers to the nature of surface molecular structure changes in the air and in water, depending on the environment, as suggested by Sherman. [p.Sherman, S. Smith, 324129 5 201247717 B, Johannessen, Textile Research Journal, 39, 499 (1969)] If the Rf base chain length is short, the crystallinity of Rf is lowered, and the oil repellency is also lowered. 'Oil dirt is easy to contaminate the items being treated. Therefore, the carbon number of the Rf group is substantially 8 or more (refer to Japanese Laid-Open Patent Publication No. SHO-53-134786, JP-A-2000-290640). Further, 'a compound having an Rf group having a carbon number of 8 recently 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) and EPA OPPT FACT SHEET April 14, 2003 (http://www.epa·gov/opptintr/pfoa/pfoafacts.pdf) have been published to generate short-chain polymers by decomposition or metabolism. Perfluorooctanoic acid (hereinafter referred to as "PF0A").

The EPA (US Environmental Protection Agency) also published a scientific study to strengthen the PFOA. (Refer to 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 A fluorine-containing graft polymer of an ethylene monomer containing an isocyanate group. Although it is described that the fluorine-containing graft polymer imparts antifouling properties to 324129 6 201247717, the obtained antifouling property and/or water absorbability are insufficient. Japanese Patent Laid-Open No. Sho 59-134786 Patent Document 3: Japanese Laid-Open Patent Publication No. Hei 59-204980 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. For the fiber fabric, etc., it has excellent water absorption, oil repellency, antifouling property, and dirt detachment, and the composition of the composition is 'even if the carbon number of the Rf base is less than 8 and is shorter than before. The same excellent properties of lifting the water-absorbent simplest approach is to reduce the fluorine content soil release (SR) polymer, the relative ratio of the hydrophilic component of the lift. Indeed whereby

Increases some degree of water absorption, but the opposite oil repellency and soil detachment (SR ^ raw) will decrease. It is not important to improve oil absorption without reducing oiliness and SR properties. (Means for Solving the Problem) The present invention provides a composition (particularly a soil release agent) comprising: (1) a gas-containing copolymer which has (a) and (6) as essential components and does not contain a monomer having an amine group. Fluorinated copolymer, 〃 324129 7 201247717 (a) Fluorinated monomer CH2:c(_x)_c(=0)_y, b in the formula (i), argon atom, a == Wide ((^{(1), moth atom, CFXY group 111 atom, chlorine atom, desert atom or gas atom.), cyano group, carbon, χ2 is a hydrogen atom, a fluorogenic fluoroalkyl group, a substitution or a linear or sub-substituted phenyl group of 20; 'substituted benzyl, substituted or not Y is -0- or -NH-; Z is a direct bond, -S- or -S〇2 ~; is a fluoroalkyl group having 1 to 6 carbon atoms;

2 is 1 to 10, n is 0 to 10, P is 〇 or U (b) The alkoxy group-containing monomer represented by the formula (II) is CH2=C(X, )~C(=〇)-〇 -(r〇)(i_h (u) [wherein 'X' is a hydrogen atom or a fluorenyl group; R is a part or all of a hydrogen atom which may be substituted with a hydroxy group and has a carbon number of 2 to 4; q is 1 to (2) an integer of (2) a blocked isocyanate compound, and (3) a liquid medium. (Effect of the invention) The composition of the present invention (particularly a soil release agent) is excellent in water absorbability and antifouling property It is excellent in soil release property. f Embodiments The composition of the present invention contains 324129 201247717 (1) a fluorine-containing copolymer, (2) a blocked isocyanate compound, and (3) a liquid medium. The composition of the present invention is produced by adding a isocyanuric (tetra) compound to a fluorine-containing copolymer liquid containing a fluorine-containing copolymer and a liquid medium. [(1) Fluorinated copolymer] The present invention_ The fluorine-containing copolymer generally does not have a repeating unit composed of a monomer having an amine group. The amine group is generally a group represented by the following formula: (Rn)(R12)N- [wherein, R11 and R12 are the same or Different, one a group (for example, a nitrogen atom).] The monomer having an amine group generally has at least one carbon-carbon double bond in addition to the amine group. The oxygen-containing monomer (a) is represented by the formula (1). C(-x)-C(,冬卜(CH2Vz_]

(10) 2VZ-]P-(CH〇n-Rf (I) cyano group, carbon number 1 to 21

Linear or divergent to 21, iodine atom, CFXT group (but, bromine atom or iodine atom), linear or branched fluoroalkyl group, substituted or not 9 Z is a direct bond, -S_ or ~S〇2~~ · Rf is a fluoroalkyl group having 1 to 6 carbon atoms; 324129

C 9 201247717 111 is 1 to 10, 11 is 〇 to 1 〇, 1) is 〇 or 1. In the formula (I), P is preferably ruthenium. X is preferably, for example, a hydrogen atom. The 'Rf group' in the gas-containing monomer (a) is generally a perfluoroalkyl group and/or a partially deficient fluoroalkyl group. The Rf group is preferably a perfluoroalkyl group. The carbon number of the Rf group is from 丨 to 6. The number of Rf groups can be 4, 5 or 6, and particularly preferably 6. Examples of the Rf group include, for example, -CF3, -CF2CF3, -CF2CF2CF3, -CF(CF3)2, -CF2CF2CF2CF3, -CF2CF(CF3)2, -C(CF3)3, -(CF2)4CF3, -(CF2). 2CF(CF3)2, -CF2C(CF3)3, -CF(CF3)CF2CF2CF3, -(CF2)5CF3, etc. m is from 1 to 10, for example from 2 to 5. n is from 0 to 10, for example, preferably from 1 to 6' is particularly preferably from 2 to 5. The fluorine-containing monomer (a) may of course be used singly or in combination of two or more. The fluorine-containing monomer (a) is exemplified below. CH2=C(-X)-C(=0)-〇-(CH2)mS-(CH2)n-Rf CH2=C(-X)-C(=0)-〇-(CH2)ffl-S〇 2-(CH2)n-Rf CH2=C(-X)-C(=0)-〇-(CH2)n-Rf CH2=C(-X)-C(=0)-NH-(CH2)n -Rf [In the above formula, X is a hydrogen atom, a sulfhydryl group, a l atom, a gas atom, a ruthenium atom, or a CFXT group (but XjX2 is a hydrogen atom, a fluorine atom or a chlorine atom, and the carbon number is 1 to 2G). a chain or bifurcated fluoroalkyl group, a substituted benzyl group, a substituted or unsubstituted phenyl group;

Rf is a fluoroalkyl group of 1 to 6; m is 1 to 1 Torr, and η is 0 to 1 Å. 324129 10 201247717 Specific examples of the fluorine-containing monomer (a) include, for example, the following, but are not limited thereto. CH2=C(-H)-C(=0)-0-(CH2)2-S-Rf CH2=C(-H)-C(=0)-0-(CH2)2-S-(CH2) 2-Rf CH2=C(-H)-C(=0)-0-(CH2)3-S〇2-Rf CH2=C(-H)-C(=0)-〇-(CH2)2- S〇2-(CH2)2-Rf CH2=C(-Η)-C(=0)-〇-(CH2)2-Rf CH2=C(-H)-C(=0)-NH-(CH2 ) 2-Rf CH2=C(-H)-C(=0)-0CH2CH2N(C2H5)S02-Rf CH2=C(-H)-C(=0)^)CH2CH2N(CH3)S0 Wide Rf CH2=C (-H)-C(=0)-0CH2CH(0C0CH3)CH2-Rf CH2=C(-CH3)-C(=0)-0-(CH2)2-S-Rf CH2=C(-CH3)- C(=0)-0-(CH2)2-S-(CH2)2-Rf CH2=C(-CH3)-C(=0)-〇-(CH2)3-S〇2-Rf CH2=C (-CH3)-C(=0)-〇-(CH2)2-S〇2-(CH2)2-Rf CH2=C(-CH3)-C(=0)-0-(CH2)2-Rf CH2=C(-CH3)-C(=0)-NH-(CH2)2-Rf CH2=C(-CH3)-C(=0)-0CH2CH2N(C2H5)S02-Rf CH2=C(-CH3) -C(=0)-0CH2CH2N(CH3)S02-Rf CH2=C(-CH3)-C〇0)-0CH2CH(0C0CH3)CH2-Rf CH2=C(-F)-C(=0)-0- (CH2)2-S-Rf CH2=C(-F)-C(=0)-0-(CH2)2-S-(CH2)2-Rf CH2=C(-F)-C(=0) -0-(CH2)2-S02-Rf CH2=C(-F)-C(=0)-0-(CH2)2-S〇2-(CH2)2-Rf 324129 11 201247717 CH2=C(- F)-C(=0)-0-(CH2)2-Rf CH2=C(-F)-C(=0)-NH-(CH2)2-Rf CH2:C(-Cl)-C(= 0)-0-(CH2)2-S-Rf CH2=C(-Cl)-C(=0)-0-(CH2)2-S-(CH2)2-Rf CH2=C(-Cl)- C(=0)-0-(CH2)2-S02-Rf CH2=C(-Cl)-C(=0)-0-(CH2)2-S〇2 -(CH2)2-Rf CH2=C(-Cl)-C(=0)-0-(CH2)2-Rf CH2=C(-Cl)-C(=0)-NH-(CH2)2- Rf CH2=C(-CF3)-C(=0)-0-(CH2)2-S-Rf CH2=C(-CF3)-C〇0)-0-(CH2)2-S-(CH2) 2-Rf CH2=C(-CF3)-C(=0)-0-(CH2)2-S〇2-Rf CH2=C(-CF3)-C(=0)-0-(CH2)2- S02-(CH〇2-Rf CH2=C(-CF3)-C(=0)-0-(CH2)2-Rf CH2=C(-CF3)-C〇0)-NH-(CH2)2- Rf CH2=C(-CF2H)-C(=0)-0-(CH2)2-S-Rf CH2=C(-CF2H)-C(=0)-0-(CH2)2-S-(CH2 )2-Rf CH2=C(-CF2H)-C(=0)-〇-(CH2)2-S〇2-Rf CH2=C(-CF2H)-C(=0)-0-(CH2)2 -S〇2-(CH2)2-Rf CH2=C(-CF2H)-C(=0)-0-(CH2)2-Rf CH2=C(-CF2H)-C(=0)-NH-( CH2)2-Rf CH2=C(-CN)-C(=0)-0-(CH2)2-S-Rf CH2=C(-CN)-C(=0)-0-(CH2)2- S-(CH2)2-Rf CH2=C(-CN)-C(=0)-0-(CH2)2-S〇2-Rf CH2=C(-CN)-C(=0)-〇- (CH2)2-S〇2-(CH2)2-Rf 12 324129 201247717 CH2=C(-CN)-C(=0)-0-(CH2)2-Rf • CH2=C(-CN)-C (=0)-NH-(CH2)2-Rf CH2=C(-CF2CF3)-C(=0)-0-(CH〇2-S-Rf CH2=C(-CF2CF3)-C(=0) -0-(CH2)2-S-(CH2)2-Rf CH2=C(_CF2CF3)~*C (=0) _0_ (CH2)2-S〇2-Rf CH2=C(-CF2CF3)-C( =0)-0-(CH2)2-S〇2-(CH2)2-Rf CH2=C(-CF2CF3)-C(=0)-0-(CH2)2-Rf CH2=C(-CF2CF3) -C(=0)-NH-(CH2)2-Rf CH2=C(~F)-C(=0)-〇-(CH2)3-S-Rf CH 2FC(-F)-C(=0)-0-(CH2)3-S-(CH2)2-Rf CH2=C(-F)-C(=0)-〇-(CH2)3-S〇 2-Rf CH2=C(-F)-C(=0)-0-(CH2)3-S〇2-(CH2)2-Rf CH2=C(-F)-C(=0)-0- (CH2)3-Rf CH2=C(-F)-C(=0)-NH-(CH2)3-Rf CH2=C(-Cl)-C(=0)-0-(CH2)3-S -Rf CH2=C(-Cl)-C(=0)-0-(CH2)3-S-(CH2)2-Rf CH2=C(-Cl)-C(=0)-0-(CH2) 3-S〇2-Rf CH2=C(-Cl)-C(=0)-〇-(CH〇3-S〇2-(CH2)2-Rf CH2=C(-CF3)-C(=0 )-0-(CH2)3-S-Rf CH2=C(-CF3)-C(=0)-0-(CH2)3-S-(CH2)2-Rf CH2=C(-CF3)-C (=0)-0-(CH2)3-S〇2-Rf CH2=C〇CF3)-C(=0)-0-(CH2)3-S〇2-(CH〇2-Rf CH2=C (-CF2H)-C(=0)-0-(CH2)3-S-Rf CH2=C(-CF2H)-C(=0)-0-(CH2)3-S-(CH2)2-Rf 324129 13 201247717 CH2=C(-CF2H)-C(=〇)-〇-(CH2)3-S〇2-Rf CH2=C(-CF2H)-C(=0)-〇-(CH2)3- S〇2-(CH2)2-Rf CH2=C(-CN)-C(=〇)-〇-(CH2)3-S-Rf CH2-C(-CN)-C(=〇)-〇- (CH2)3-S-(CH2)2-Rf CH2=C(-CN)-C(=〇)-〇-(CH2)3-S〇2-Rf CH2=C(-CN)-C(= 〇)-〇-(CH2)3-S〇2-(CH2)2-Rf CH2=C(-CF2CF3)-C(=0)-〇-(CH2)3-S-Rf CH2=C(-CF2CF3 )-C(=0)-〇-(CH2)3-S-(CH2)2-Rf CH2=C(-CF2CF3)-C(=0)-〇-(CH2)3-S〇2-Rf CH2 =C(-CF2CF〇-C(=〇)-〇-(CH2)2-s〇2-(CH2)2-Rf [R in the above formula f is a fluoroalkyl group of 1 to 6. The alkoxy group-containing monomer (b) is a non-fluorine monomer and is a compound of the formula (π) (alkylglycol (meth) acrylate): (b) Formula: CHKXX,) -(:(=〇)-〇—(R0)q_H (II) [wherein, X' is a hydrogen atom or a methyl group; R is a part or all of a hydrogen atom which can be substituted by a hydroxyl group and has a carbon number of 2 to 4 q is an integer of 1 to 50.] In the alkoxy group-containing monomer (b), q is from 1 to 30, preferably from 2 to 10, particularly preferably from 2 to 5. In the formula (II) 'R is an exoethyl or a propyl group, and particularly preferably an exoethyl group. R in the formula (11) may be combined with two or more kinds of exudyl groups. In this case, preferably at least one of R is exfoliated. The combination of R and R may, for example, be a combination of an ethyl group and a propyl group, and a combination of an ethyl group and a butyl group. 14 324129 201247717 The alkoxy group-containing monomer (b) may be a mixture of two or more kinds. Specific examples of the alkoxy group-containing monomer (b) are as follows, but are not limited thereto.

CH2=CHC00-(CH2CH20)3-H

CH2=CHC00-(CH2CH20)5-H

CH2=CHCO〇-(CH2CH2〇)9-H

CH2=C(CH3)C00-(CH2CH20)3-H

CH2=C(CH3)COO-(CH2CH2〇)5-H

CH2=C(CH〇C00-(CH2CH20)9-H

CH2=C(CB〇C00-(CH2CH20)23-H

CH2=C(CH3)COO-(CH2CH2〇)50-H

CH2=CHC00-(CH2CH(CH3)0)3-H

CH2=CHC00-(CH2CH(CH3)0)9-H

CH2 II C(CH3)C00-(CH2CH(CH3)0)4-H

CH2=C(CH3)C0O-(CH2CH(CH3)O)9-H

CH2=C(CH3)C0〇-(CH2CH2〇)2-(CH2CH(CH3)O)2-H

CH2=C(CH3)C0〇-(CH2CH2〇)5-(CH2CH(CH3)O)2-H

CH2=C(CH3)C0〇-(CH2CH2〇)8-(CH2CH(CH3)O)6-H The fluorine-containing copolymer may contain (c) a crosslinkable monomer. The crosslinkable monomer (c) has at least two reactive groups and/or carbon-carbon double bonds, and may be a compound containing no 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 the reactive group are a hydroxyl group, an epoxy group, a chlorohydrazine group, a blocked isocyanate group, a carboxyl group and the like. A monomer having an amine group is not used in the present invention. 324129 15 201247717 The parent monomer (c) is preferably a non-fluorine crosslinkable monomer, particularly preferably a dibasic acrylate. The parent-linked stilbene monomer (c) is preferably a compound of the formula (?) (stretching ethylene glycol di(meth) acrylate). CH2=C(X-)-C(=〇)-〇-(r 〇)qC(=〇)-C(Xw)=ch2 (III) [wherein each X" is a hydrogen atom or a methyl group; R is a part or all of a hydrogen atom which may be substituted by a hydroxyl group to have a carbon number of 2 to 2; q is an integer of 1 to 5 Å.] R has a carbon number of 2 to 10, for example, preferably 2 to 6 Particularly preferred is 2 to 4. R" is preferably an ethyl group. In the formula (ΙΠ), q is J to 3 Å, for example, preferably 2 to 10. Specific examples of the alkylene glycol di(meth)acrylate represented by the formula (III) are as follows. CH2=C(CH3)COO-(CH2CH2〇)5-COC(CH3)=CH2 CH2=CHC00 -(CH2CH2〇)9-COCH=CH2 CH2=C(CH3)C00-(CH2CH(CH3)0)12- C0CH=CH2 cH2=CHCOO-(CH2CH2〇)5-(CH2CH(CH3)〇)3-COCH=CH2 cH2=C(CH3)C00-(CH2CH20)23-00C(CH3)C=CH2 CH2=C(CH3 Other examples of COO-(CH2CH2〇)2〇-(CH2CH(CH3)0)5-COCH=CH2 crosslinkable monomer (c) include, for example, diacetone (methyl) propyl sulfonamide, (methyl) ) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylate 3 ~ gas - 2 - propyl Ester 'butyl dilute' chloroprene, (A 324129 16 201247717 base) propylene acrylate, 1,6-hexanediol acrylate, neopentyl glycol dipropylene enoate, etc., but It is not limited to these. Other examples of the cross-linking monomer (c) include glyceryl (mercapto) acrylate, (mercapto) acetoacetoxyethyl acrylate, 2-isocyanate methacrylate, and the like, which contain isocyanate groups. (Mercapto) acrylate or the like which is blocked with an isocyanate S group by a blocking agent such as (meth) acrylate or methyl ketone. The crosslinkable monomer (c) may be a mixture of two or more kinds. The fluorine-containing copolymer may also contain (d) a non-crosslinkable monomer. The non-crosslinkable monomer (d) is a monomer other than the alkoxy group-containing monomer (b), and is generally a non-fluorine monomer. The non-crosslinkable monomer (d) does not contain fluorine, and is preferably a monomer having a carbon-carbon double bond. The non-crosslinkable monomer (d) is preferably an ethylenic monomer which does not contain fluorine. The non-crosslinkable monomer is generally a compound having one carbon-carbon double bond. The non-crosslinkable monomer (d) may, for example, be a butadiene, a chloroprene, a maleic acid derivative, a vinyl halide such as vinyl chloride, an ethyl group such as an ethylidene group or a dichloroethylene. Ethylene, vinyl alkyl ether, styrene, (meth)acrylic acid ester, ethylene D ratio, each of vinyl pyrrolidone, etc., but it is not limited to these. The non-crosslinkable monomer (d) may be a (fluorenyl) acrylate having an alkyl group. The alkyl group has a carbon number of from 1 to 30, for example from 6 to 30, and may be, for example, from 10 to 30. The non-crosslinkable monomer can be, for example, an acrylate represented by the following formula. ^^CA^OOA2 [wherein A1 is a hydrogen atom or a fluorenyl group, and A2 is a chain or a cyclic Wwq alkyl group.] The fluorinated copolymer contains 100 parts by weight of the fluorine-containing monomer (a). 324129 17 201247717 Fluoromonomer (a) ioo parts by weight, the amount of the alkoxy group-containing monomer (b) is up to 400 parts by weight, for example, preferably 25 to 15 parts by weight, particularly preferably 43 to 100 parts by weight. The amount of the crosslinkable monomer (4) is 30 parts by weight or less, for example, preferably from 1 to 20 parts by weight, particularly preferably from 5 parts by weight to parts by weight; and the amount of the non-crosslinkable monomer (4) is 2 parts by weight. In the following, for example, preferably 0.1 to 15 parts by weight, particularly preferably 0.5 to 10 parts by weight. The fluorine-containing copolymer of the present invention has a weight average molecular weight of from 1 Å to 1,000,000, preferably from __ The weight average molecular weight is a value obtained by conversion to styrene by a colloidal permeation chromatography. The polymerization of the fluorinated copolymer is not particularly limited, and a bulk polymerization, a solution polymerization, an emulsion polymerization, a radiation polymerization, or the like can be selected. Various polymerization methods, such as solution polymerization using organic solvents, or emulsion polymerization with water or organic solvents After the polymerization, it is diluted with water and emulsified by adding an emulsifier to the water to prepare a treatment liquid. In the present invention, it is preferred to remove the solvent after polymerization (for example, solution polymerization or emulsion polymerization), and then to add the water to disperse the polymer. Examples of the organic solvent include hydrazines such as propyl ketone and methyl ethyl ketone; esters such as ethyl acetate and methyl acetate; propylene glycol 'diene glycol monomethyl ether, dipropylene glycol, propylene glycol, and low molecular weight polyethylene glycol. Ethylene glycols, alcohols, alcohols, etc.. Emulsifiers after emulsification polymerization or emulsifier addition after polymerization and emulsification of water can make (iv) ionic, _ sub, _ sub-like I 324129 201247717 As the polymerization initiator, for example, a peroxide, an azo compound or a perrhenic acid-based compound can be used. The polymerization initiator is generally water-soluble and/or oil-soluble. Preferred examples of the oil-soluble polymerization initiator are exemplified. Such as 2, 2'-azobis(2-methylpropionitrile), 2,2,-azobis(2-methylbutyronitrile), 2'2'-azobis (2,4-dimethyl Valeronitrile, 2,2,-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 1,1,-even Nitrogen bis(cyclohexanecarbonitrile), dimethyl 2,2'-azobis(2-methyl propionate), 2,2,-azobis(2-isobutyronitrile), benzoyl peroxide Benzyl peroxide, bis(second butyl) peroxide, 1 aury 1 perox ide, cumene hydroperoxide, butyric acid isobutyrate Diisopropyl S-dicarbonate, tert-butyl perpivalate, etc. Further, preferred examples of the water-soluble polymerization initiator include, for example, 2, 2 '-azobisisobutylphosphonium 2 salt. Acid salt (2, 2'-Azobis (dihydrochloride), 2,2'-azobis(2-methylpropionamidine) hydrochloride, 2, 2,-azobis[2-(2-imidazoline-2) -yl)propane] hydrochloride, 2, 2'-azobis[2-(2-imidazolin-2-yl)propane]sulfate brine, 2, 2'-azobis[2-(5 -Methyl-2-imidazoline-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. A particularly preferred polymerization initiator is the second purpose of isobutyl peroxide. The polymerization initiator used is in the range of 〇 to 5 parts by weight based on 100 parts by weight of the monomer. Further, for the purpose of adjusting the molecular weight, a chain transfer agent 324129 19 201247717 transfer agent may be used, and for example, a compound containing a mercapto group may be used, and specific examples thereof include 2-mercaptoethanol, thiopropionic acid, Alkyl mercaptan and the like. The compound containing a mercapto group is 10 parts by weight or less based on 100 parts by weight of the monomer, and may be used in an amount of from 0.01 to 5 parts by weight. Specifically, the fluorinated copolymer can be produced in the following manner. The solution polymerization may be carried out by dissolving the monomer in an organic solvent and substituting with nitrogen, and adding a polymerization initiator, for example, at 40 to 120X: heating and mixing 1 to 1 Torr. The polymerization initiator can generally be an oil-soluble polymerization initiator. The organic solvent is one in which the monomer is inactively dissolved, and examples thereof include propylene glycol, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, cyclohexane, benzene, and hydrazine. , xylene, petroleum hydrazine, tetrahydrofuran, 1,4-dioxane, butanone, decyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2, 2-tetraethane, 1, bismuth, trichloroethane, trichloroethylene all-ethylene, tetra-difluoroethane, tri-gas trifluoroethane. The organic solvent is 50 to 2000 parts by weight, based on the total parts by weight of the monomers, and can be used, for example, in the range of 5 Å to 1000 parts by weight. ― Emulsification polymerization is a method in which a monomer is emulsified in water in the presence of an emulsified material, and after being substituted with nitrogen, a polymerization initiator is added, and the polymerization is carried out in the range of 40 to 80 Torr for 10 hours. The polymerization initiator can be made from benzoic acid peroxide: peroxidized Laurel I!, peroxybenzoic acid tert-butyl ester, dipyridylcyclohexyl hydroperoxide 3-methylpropionate peroxide, ethidium peroxide, and even Nitrogen diisobutyl hydrazine-dihydrochloride, azobisisobutyronitrile, sodium peroxide, persulfate, over, k money, etc.; or azobisisobutyronitrile, benzoyl peroxide , hydrogen peroxide (tert-butyl), peroxidized laurel, nitrous oxide, 324129 20 201247717 isobutyric acid, butyrate, diisopropyl peroxide, etc. 100 parts by weight of the monomer 'polymerization starting sword can be used in the range of 0.01 to 1 part by weight. In order to obtain a polymer aqueous dispersion which is excellent in stability, an emulsion device capable of imparting strong crushing energy such as a homogenizer or an ultrasonic homogenizer is used, and the monomer is granulated in water, and preferably oil is used. The soluble polymerization initiator is polymerized. Further, the emulsifier may be an anionic, cationic or nonionic emulsifier. The emulsifier may be used in an amount of from G 5 to 2 parts by weight based on 100 parts by weight of the monomer. Preferably, the (10) agent is anionic and/or nonionic and/or cationic. The monoterpenes are completely compatible. It is preferred to add a compatibilizing agent which sufficiently dissolves the monomers, for example, a single vessel. By adding a compatibilizing agent, diol ===_, propylene relative to water, 100, denditol, ethanol, etc., for example, 10 to liters of J: 7:1, and 1 to 5 parts by weight of the organic solvent can be used. A "return to acid A:: two: Bu: low molecular weight monomer enoic acid 2, 2, 2-: fluorine ... bisenoic acid % gram propylene, methyl propylene molecular weight monomer: Γ to 曰Λ, relative to single _^, low range. 1 to 5G rereading 'for example, using 1G to 40 parts by weight of [(2) blocked isocyanate compound] Isocyanate compound is blocked by at least one blocking agent 324129 21 201247717 The isocyanate compound is a compound having a blocked isocyanate group and having no polymerizable unsaturated group, and is an isocyanate residue having an isocyanate blocked by a blocking agent. The blocked isocyanate compound can be used. The compound is modified by a compound having a hydrophilic group. Examples of the hydrophilic group include, for example, a nonionic hydrophilic group (for example, a hydroxyl group, an amine group, and a polyoxyalkylene group (particularly a polyoxyethylene group); Ionic (cationic or anionic) hydrophilic group (eg carboxyl, sulfate, sulfhydryl, sulfonic acid) The isocyanate group can be, for example, toluene diisocyanate (TDI) 'diphenylmethane diisocyanate (MDI), MDI oligomer, naphthalene-1,5-diisocyanate, xylene diisocyanate , hexamethylene diisocyanate (HDI), 4, 4 - dicyclohexylmethane diisocyanate, norbornane diisocyanate, isophorone diisocyanate (IPDI), adduct (for example, TMP (trimethylolpropane) adduct of TDI or HDI), allophanate modified product, biuret modified product (for example, biuret made from HDI) a trimeric isocyanate modified product (for example, a trimeric isocyanate manufactured by TDI, a trimeric isocyanate manufactured by HDI, a trimeric isocyanate manufactured by IPDI, and a trimeric isocyanate produced from TDI and HDI), the aforementioned compound A carbodiimide modified product or an amino phthalate prepolymer. Examples of the blocking agent include, for example, (i) oxime type (ii) phenol, (iii) alcohol Class, (iv) mercaptans, (v) decylamines, (vi) quinone imines, (vi i) Imidazoles, (viii) ureas, (ix) amines, (x) imines, classes, and (xii) active methylene compounds. Other examples of blocking agents can be listed as 324129 22 201247717 Classes, thiophenols, diketones and esters. The blocked isocyanate compound can also be modified by a compound having a hydrophilic group. (i) Examples of fatty steroids include, for example, methotrexate and acetaldehyde.肟, acetone oxime, butanone oxime and cyclohexanone oxime. (ii) Examples of the phenols include at least one (preferably one or two) Ch depending on the case. Alkyl phenol. Specific examples of the phenols include, for example, phenols; monoalkanols (e.g., indophenol, ethylphenol, propanol, butanol, hexanol, 2-ethylhexidine, and octane); and two-burning (e.g., diethyl Hope, dipropyl expectation, dipropyl cresol, dibutyl phenol, di-2-ethylhexyl phenol, dioctyl phenol and diterpenoid. Specific examples of the phenols include styrenated phenols and hydroxybenzoic acid esters. (iii) Examples of the alcohols include, for example, C1-C3. A base (preferably a monohydric) alcohol (especially an alkanol). Specific examples of the alcohol include methanol, ethanol, propanol, 1-butanol, second butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-butoxyethanol, and 2 - alkoxy-1-propanol and 3-mercapto-2-en-4-yn-1-butanol. (iv) Mercaptans Specific examples of the mercaptans include, for example, butanol and dodecanethiol. (v) Specific examples of the guanamine amides (preferably acidic guanamines) include, for example, acetaminophen, guanamine acetate, cold-propiolactone, 7-butyrolactone, (5-valerolactone). , ε - 324129 23 201247717 Caprolactone, laurolactam, octadecyl lactone, N-methyl-ε-caprolactone and η pirone (vi) quinone imine Specific examples of the imines include, for example, bismuthimide maleate and ruthenium imide succinimide. (vii) Specific examples of the imidazole-based imidazoles include, for example, imidazole and 2-methyl group. (viii) Specific examples of the urea-based ureas include urea, sulfur urea, and ethylene urea. (ix) Specific examples of the amine amines include diphenylamine, aniline, sigma, and diethylamine. And dipropylamine and propylethylamine. Specific examples of the (X) imine imines include, for example, ethyl women's amines and polyethyleneimine. (xi) ° specific ratio of pyrimidines Examples thereof include 2-methyl-pyrazole, 3-methylpyrazole, 4-methyl-pyrazole, 2,4-dimethyl-pyrazole, 2,5-dimethyl-pyrazole, and 3 , 4-dimethyl-pyrazole, 3, 5-dimethyl-pyrazole, 4-nitro-3, 5-di基-〇 〇 、 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- ( ( ( ( ( ( xi xi xi xi xi xi xi xi xi xi xi xi xi xi xi xi xi xi xi xi xi xi xi xi xi -3 〇 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ It is preferred to sit 324129 24 201247717 or a malonate compound. ^ The pyrazole compound can be represented by the following formula: 'HN^^~(R11)n [wherein, each R11 is the same or different' An alkyl group, an alkenyl group, an arylalkyl group, a substituted amine indenyl group, a phenyl group, an N〇2 group, a halogen atom or a -C(=〇)〇R12 group (R12 is a carbon number of 1 to 4), n is 〇, 1, 2 or 3.] Specific examples of pyrazoles such as 2-methyl-pyrazole, 3-methyl-pyrazole, 4-methyl-carbazole, 2, dimethyl-σ ratio Jun, 2, 5~ dimethyl 1 嗤, 3, 4-dimethyl-pyrazole, 3, 5" dimethyl-pyrazole, guanidine nitro 2,5-dimethyl-anthracene, 4-Di-3, 5-didecyl 〇 〇 σ 坐. The malonate compound is a reaction product of malonic acid with an alcohol (for example, a monohydric alcohol) (monoester or The ester (comparatively diester)). Generally, the 'alcohol has a broken atomic hydrocarbon group bonded to the hydroxyl group of 1 to 30. The hydrocarbon group is preferably an alkyl group, particularly an alkyl group having 1 to 4 carbon atoms. Specific examples of the diester may, for example, be dimethyl malonate, diethyl malonate, dipropyl malonate, dibutyl malonate, decyl malonate, ethyl malonate or propyl acetate. The diacid propyl g is preferably butyl succinate, preferably di vinegar. Specific examples of preferred malonic esters include didecyl malonate, dipropyl malonate, and dipropyl malonate. And dibutyl malonate. The blocked isocyanate compound can be modified by 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, the compound having a hydrophilic group may be a reaction between a compound having a nonionic hydrophilic group or a compound having an ionic hydrophilic group of 324129 25 201247717 and an isocyanate, usually an active hydrogen (for example, -0H or -NIL·) Produced by reaction with an isocyanate group (-NCO). The compound having a nonionic hydrophilic group and the compound having an ionic hydrophilic group preferably have a number average molecular weight of up to 4,000, particularly 2 to 2000, respectively. Particularly preferred are compounds having a nonionic hydrophilic group. 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, particularly by addition reaction of an alkylene oxide, particularly ethylene oxide, in a monoalcohol such as methanol (for example, a carbon atom having from 丨 to 30) . 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 cerium to 5% by weight, for example 〇 to 20% by weight, based on the alkylene oxide, in particular! A propylene oxide unit in an amount of up to 1% by weight. The compound having an ionic hydrophilic group is preferably an anionic compound (e.g., a hydroxycarboxylic acid, an amino acid, an amine sulfonic acid, and a hydroxysulfonic acid). A cationic compound (e.g., dimethylaminopropanol) having a hydroxyl group-containing secondary amine compound can be used as the compound having an ionic hydrophilic group. The tertiary amine compound having a hydroxyl group is reacted with an isocyanate, followed by neutralization with an acid or reaction with a quaternizing agent such as gaseous toluene to obtain a quaternized salt. Examples of the compound having a hydrophilic group include, for example, an alcohol having a (e.g., C1-C3.) aliphatic group and a monohydric alcohol having at least an upper alkyl group (e.g., G-C2). These can be achieved by (for example, C2_Cs) ring 324129 26 201247717

Oxygen is added to (for example, Cl-C30)-alcohol to produce. Specific examples of the compound having a hydrophilic group include compounds represented by the following formula: R_(0_CH2CH2)n-0H

Wherein R is a Cl-ClD aliphatic (or in-house) group (e.g., CH3, C2H5, 〇3Η?, C4HO, η is 2 to 50, preferably 5 to 25.) The isocyanate is reacted with a blocking agent, Thereby, a blocked isocyanate compound can be produced [isocyanate can be represented by A(NCO)m (but Α and m are the same as described below (for example, A is a group remaining after removing an isocyanate-reactive group, and m is 2 to 8) Number 〇.] [The blocking agent can be represented by RH (but R is a hydrocarbon group which can be substituted by a hetero atom such as a nitrogen atom and an oxygen atom, and hydrazine is a hydrogen atom)] The blocked isocyanate compound is preferably the following formula Show compound: Α-Υ.

[wherein, Α is an m-valent aliphatic group, an alicyclic group, a heterocyclic group or an aromatic group (but m is an integer of 2 to 8), and Y is the same or different, and is the following

(R11) 〇 (However, each R11 is the same or different and is alkyl, alkenyl, aralkyl, N-substituted amine fluorenyl, phenyl, N〇2, halogen atom or -C(=0)0R12 a group (R12 is an alkyl group having 1 to 4 carbon atoms), n is 0, 1, 2 or 3); or -NH-C(=0)-CH-(C(=0)-0R21)2; or R21 is a hydrocarbon group having 1 to 30 carbon atoms or a group having a hydrophilic group. 324129 27 201247717 -NHC00-(R31-0)k~R32 (R is a carbon number of 2 to 5, and R32 is The aliphatic group (or alkyl group) having a number of 1 to 10 is, for example, CH3, (: also, (: and C4H9, k is 2 to 50' is preferably 5 to 25.) m is 1 to 10' Preferably 2 to 5.] In the isocyanate compound, γ is preferably

-NH-C(=0)-CH-(C(=〇)-〇r21)2; (iii) -NHC00-(R31-0)k~R32; or (iv) above (i) and (1)) (iii) A combination of at least two of them. The amount of the blocked isocyanate compound may be from 5 to 5 parts by weight, for example, from 1 to 2 parts by weight, based on 100 parts by weight of the total of the monomers or the fluorinated copolymer. [(3) Liquid medium] The liquid medium is a solvent formed by water and/or an organic solvent. The liquid medium can be a mixture of water and an organic solvent. The liquid medium is preferably a polymerizable monomer and is used as a solvent for producing a fluorine-containing copolymer. A solvent may be added after the fluoropolymer is produced. The solvent added after the polymerization may be the same as or different from the solvent used in the polymerization. The amount of the liquid medium may be such that the concentration of the fluorocopolymer and the capping 324129 28 201247717 isocyanate compound is from 0.02 to 70% by weight, for example from 1 to 50% by weight. Ir The composition of the present invention (i.e., the treating agent (particularly the soil release agent)) is preferably in the form of a solution, an emulsion or an aerosol. The treating agent contains a fluorinated copolymer and a medium (e.g., a liquid medium such as an organic solvent or water). 1至40重量百分比。 The concentration of the fluorinated copolymer may be, for example, from 0.01 to 50% by weight, in particular from 0.1 to 40% by weight. The fluoropolymer (fluorine-containing copolymer) of the present invention is applicable to a soil release agent by any method depending on the type of the article to be treated or the preparation form (emulsion, organic solvent solution, aerosol, etc.). For the item being processed. For example, in the case of an aqueous emulsion or an organic solvent solution, a method of adhering to a surface of a workpiece and drying it by a known method of coating processing such as immersion coating, spray coating or the like can be employed. At this time, heat treatment such as curing may be performed if necessary. In addition, other admixtures may be used in combination if necessary. For example, water-repellent and oil-repellent agents, anti-wrinkle agents, anti-shrinkage agents, flame retardants, cross-linking agents, antistatic agents, softeners such as polyethylene glycol or polyvinyl alcohol, water-soluble polymers, wax emulsions, antibacterial agents, pigments, Coatings, etc. These admixtures may be added to the treatment bath for use in the treatment of the object to be treated, and may be used in advance by mixing with the fluoropolymer of the present invention. The article to be treated is not particularly limited, but may be, for example, a stone material, a transition piece (for example, an electrostatic filter), a dust cover, glass, paper, wood, leather, fur, asbestos, brick, cement, metal, and the like. Oxide, kiln products, plastics, coated surfaces, and plaster. For fiber products, there are 324129 29 201247717. Various examples of the fiber product can be cited. For example, cotton, hemp, wool, and other animal and plant natural fibers; polyamine, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene and other synthetic fibers; sputum, acetic acid and other semi-synthetic fibers; glass Inorganic fibers such as fibers, carbon fibers, and asbestos fibers; or such mixed fibers. The fibrous product may be in any form such as fiber, silk or cloth. In the present invention, the object to be treated is treated with a treating agent (particularly a soil release agent). "Treatment" means that the treatment agent is used for the object to be treated by dipping, spraying, coating or the like. The fluoropolymer which is an active ingredient of the treating agent is impregnated into the inside of the object to be treated and/or adhered to the surface of the object to be treated. (Examples) Next, the present invention will be more specifically described by way of examples, comparative examples and test examples. However, the invention is not limited to the description. Hereinafter, parts or % represent parts by weight or % by weight unless otherwise specified. The test methods used below are as follows. <Water absorption test droplet method> Drink water (20 ± 2 ° C) 10 / / L was suspended on the test cloth using a micropipette. / Then, the time from the s-type test cloth containing water droplets, the water droplets seeping into the test cloth until the water droplets disappear (unit: second). Here, the disappearance of the water droplet means that the specular reflection of the water disappears, leaving only the wet state. Five points were measured and the average water absorption time was taken as the measured value. The water absorption test Wicking method was cut into a short piece having a length of 16 cm and a width of 2.5 cm. In a 200 ml beaker containing 2 g of pure water, the front end of the test cloth was set to 324129 30 201247717 5 to 10 mm in water. After 30 minutes, the height of the water rising from the water surface due to the capillary phenomenon was read. <Draining test (OR test)> The oil repellency test uses a fiber product and is ordered in accordance with AATCC_TM118_2〇〇〇. That is, the test cloth was horizontally spread, and a few drops of the test solution of Table 3 were dropped, and the state of impregnation after 3 seconds was determined. When the oil repellency is low, the oil dirt in the air enters the object to be treated and is difficult to remove. Therefore, the test for the detachability of the dirt (SR) is also an important evaluation index. Table 1 Determination of oil repellency, oil surface test solution surface tension (dyne/cm 25〇C) 8 η-hexanes 20. 0 7 η-octane 21. 8 6 η-decane 23. 5 5 η- Twelve burned 25. 0 4 η-tetradecoctene 26. 7 3 η-hexa burn 27. 2 2 hexadecane 35 / paraffin 65 mixture 29. 6 1 sarcophagus 31. 2 0 less than one one < Soil Detachment Test (SR Test)> The soil release test was carried out in accordance with the US AATCC Stain Release Management Performance Test Method. Test soil using corn oil or mineral oil or spicy oil 0 Spread 20cm square test cloth on horizontally spread absorbent paper, and test 5 drops on test cloth 324129 31 201247717 (about 〇· 2 Cc ) as a corn oil (or mineral oil or spicy oil). On it, cover the shy cellophane, which is filled with 2268g of crushed drink and placed for 6 seconds. The weight and cellophane were removed after 60 seconds and placed directly at room temperature for 15 minutes. After 15 minutes, a ballast cloth of 1.8 kg was applied to the test cloth, using 100 g of a lotion (AATCC standard WOB lotion), and an AATCC standard washing machine (manufactured by Kenmore, USA) with a water volume of 64 liters and a bath temperature. The mixture was washed for 12 minutes at 38 ° C. After washing, the test cloth was dried with an AATCC standard drum dryer (manufactured by Kenmore, USA). The state of the residual stain of the dried test cloth was compared with the standard picture plate for determination, and the soil release performance was judged by the determination level (refer to Table 4). AATCC-TM130-2000 (American Association of Textile Chemists and Colorists-Test Method 130-2000) was used for the determination of the standard picture plate. Table 2: Deterioration level of the degree of determination of the degree of soil release. 1. 0 Residual color spots 2.0 1 Residue There is a considerable degree of stains 3. 0 Residual color spots 4.0 Spots are not obvious 5.0 No residual spots <Water absorption, oil repellency (OR), SR-type sacrificial durability> By AATCC-135 method The washing was repeated 10 or 20 times, and then water absorption, oil repellency (OR), and SR property (HL-10, HL-20) were evaluated. [Synthesis Example 1] Synthesis of fluorinated copolymer 1 : 324129 32 201247717 A fluorine-containing monomer CH2=CHC(=〇)〇 was added to a 100 ml four-necked flask equipped with a reflux cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device.

(hereinafter referred to as C6SFA (a)) 18. g, 2-hydroxyethyl acrylate (hereinafter referred to as HEA) 3 g, polyethylene glycol acrylate CH2 = CHC (= 〇) 〇 _ (CH2CH2 〇) n H ( BLEMMER AE200, Nippon Oil Co., Ltd., the average value of n is 4. 5) (hereinafter referred to as AE200) 7. 5g, polyethylene glycol diacrylate CH2 = CHC (= O) 0 - (CH2CH2 〇) nc (=〇)CH=CH2 (BLEMMER ADE300, manufactured by Nippon Oil Co., Ltd., the average value of η is 7) (hereinafter referred to as ADE3〇〇) 1.5g, 2-mercaptoethanol 〇.45g and methyl ethyl ketone (hereinafter referred to as It was 45 g of MEK) and was bubbling for 3 minutes with nitrogen. After the internal temperature was raised to 5 Torr to 65 ° C under a nitrogen stream, PERBUTYL PV (hereinafter referred to as PV) 0.4 g was added, and the reaction was carried out at 60 to 65 t for 6 hours. After the obtained solution was distilled under reduced pressure, the MEK was distilled off at about 7 (rc), and after the pale yellow polymer residue was obtained, water (12. 4 g) was added and maintained at an internal temperature of about 8 ° C for 1 hour or more. The aqueous dispersion having a solid concentration of about 2% by weight was adjusted. [Synthesis Example 2] Synthesis of blocked isocyanate 1: Methylene diphenyl diisocyanate (16 g) and mercapto isobutyl ketone were added to a reaction vessel. 32g, heated to 72 to 75 ΐ. Slowly add methyl ethyl 肟 (6. 0g), confirm the reaction to zero isocyanate content to zero by infrared spectrophotometer from 60 to 702⁄4 and obtain a white solid β The composition was added with dodecyl polyethylene glycol ether (the average number of ethylene oxide addition moles was i6 2g), dispersed in water by forced emulsification, and the aqueous dispersion was adjusted to have a solid concentration of 324129 33 201247717 It is about 40%. [Synthesis Example 3] Synthesis of blocked isocyanate 2: To a reaction vessel, hexamethylene diisocyanate-based isocyanuric acid vinegar (16 g, hexamethylene diisocyanate, trimeric isocyanate type, NC〇官月& base 3, Sumijuir N-3300, Sumika Bayer Urethan e Co., Ltd.), and methyl isopropanone 32g, and heated to 72 to 75t:. Then, slowly add polyethylene glycol monomethyl ether (epoxy Ethylene addition molar average of 12) 1 lg 'Reaction for 1 hour. Then, slowly add 3,5-dimethyl alpha to saliva (6.0 g, 62.4 mmol), and react to the isocyanate content to zero at 6 to 70 Å with an infrared spectrophotometer. A colorless transparent liquid composition was obtained, and the colorless transparent thick liquid composition was dispersed in water, and the aqueous dispersion was adjusted to have a solid concentration of about 4% by weight. [Comparative Synthesis Example 1] Synthesis of fluorine-containing copolymer C1: In a 100 ml four-necked flask equipped with a reflux cooling tube, a nitrogen inlet tube, a thermometer, and a stirring device, C6SFA (a) 18.0 g, HEA 3 g, AE200 7*5 g dimethylamine ethyl methacrylate CH2-C (CH3) was added. C(=〇)〇-CH2CH2N(CH3)2 (lightester DM, hereinafter referred to as DM) 1.5g, 2_mercaptoethanol oxime. 3g, with MEK 45g, and ventilated with nitrogen 30 minutes. The internal temperature was raised to 5 〇 to 65 ° C under a nitrogen stream, and PERBUTYL PV (hereinafter referred to as pv) 〇.4 g, from 60 to 65 t: reaction 6 was added. The water is added to the solution. After the reaction is carried out, the solution is added to the residue. After 6 g, the internal temperature was maintained at about 80 ° C for 1 hour or more, the aqueous dispersion was cooled and adjusted so that the solid content concentration was about 20% by weight. [Comparative Synthesis Example 2] Synthesis of fluorinated copolymer C2: Comparative Synthesis Example 1 +, with methoxypolyethylene glycol #4(10) mercapto acrylate CH2=C(CH〇C(=〇)〇-( CH2CH2〇)n-CH3 (NK ester M-90G, manufactured by Shin-Nakamura Chemical Co., Ltd., the average value of n is 9) (hereinafter referred to as M-90G) is replaced by AE200' in the same manner as the comparative synthesis example. And adjusting the aqueous dispersion to have a solid concentration of about 2% by weight. [Example 1] 3. 0 parts 〇. 25 parts 96. 75 parts Synthesis of 20% aqueous dispersion of the fluorinated copolymer obtained in Synthesis Example 1. The aqueous dispersion of blocked isocyanate obtained in Example 2, tap water, and the aqueous dispersion of the blocked isocyanate obtained in Synthesis Example 2 were diluted with water in the above ratio to prepare a processing liquid. The obtained treatment liquid was immersed in 1% cotton cloth and 1%% PET cloth' and lightly twisted to make the wet water absorption rate (wet ^丨 叩; wpu) 60 mass%. Then, the cloth was clothed at 16 (TC drying and heat treatment for 3 minutes, thereby completing the soil release agent treatment. Measuring the water absorption of the cloths (drop method,

Wicking method), soil release (SR) and oil repellency (〇R). The results are shown in Table 3. [Example 2] 324129 35 201247717 The treatment liquid was prepared and the cloth was treated in the same manner as in Example 1 except that the amount of the 20% aqueous dispersion of the fluorinated copolymer obtained in Synthesis Example 1 was changed to 8.0 parts. The soil detachability and oil repellency were measured. The results are shown in Table 3. [Example 3] 20% moisture content of the fluorinated copolymer obtained in Synthesis Example 1 3.0 parts of aqueous dispersion I obtained in Synthesis Example 3 〇 Partial tap water 96. 75 fluorocopolymer obtained in Synthesis Example 1 in a ratio The dispersion liquid and the blocked aqueous isocyanuric acid dispersion obtained in Synthesis Example 3 were diluted with water and prepared into a treatment liquid. The 1GG% crepe cloth, 100 jPET cloth was impregnated in the treatment liquid thus obtained, and the wet water absorption rate was twisted by a roller (the evaluation was (9) leg%%. Then the cloth was dried at 160 c, heat treatment for 3 minutes. By this, the water repellency (water droplet method, [also method], dirt detachment property (SR), and oil repellency (〇R) of the cloths was completed. The results are shown in Table 3. [Examples] 4) The treatment liquid was prepared in the same manner as in Example 3 except that the amount of the 20% aqueous dispersion of the fluorinated copolymer obtained in Example 1 was changed to 6.0%, and the cloth was treated to measure the soil release property. The oil repellency. The results are shown in Table 3. [Example 5] 20% aqueous dispersion of the fluorinated copolymer of the synthesis example 1 3. The blocked isocyanuric acid aqueous dispersion obtained in the synthesis example 2 (4) 324129 36 201247717 ' Body should be NE-called E2, and the Japanese ink chemistry. 8.BECKAMINE X-8G (catalyst for ethylene bisphosphonate, Da Nippon ink chemistry) 2 Tap water 'β - χ 78· 35 parts of the fluorinated copolymer dispersion obtained in Synthesis Example 1 and the blocked isocyanuric acid aqueous dispersion obtained in Synthesis Example 2 in water Release, and modulation of processing solution. The thus obtained treatment liquid was impregnated with 1% cotton cloth, 65%/35, PET/cotton cloth (T/c)' and twisted so that the wet water absorption (wpu) was 6 〇 insaSS%. Next, the cloth was dried at l6 (rc was dried and heat-treated for 3 minutes to complete the soil release agent treatment. The water absorption of the cloths was measured (drop method,

Wicking method), soil release (SR) and oil repellency (〇R). The results are shown in Table 4. [Example 6] The amount of the 2% by weight aqueous dispersion of the fluorinated copolymer obtained in Synthesis Example 1 was changed to 6.0 parts, and the treatment liquid was prepared in the same manner as in Example 3, and the cloth was treated. Oily. The results are shown in Table 4. [Comparative Example 1] 20% aqueous dispersion of the fluorinated copolymer obtained in Comparative Example 3. 37.0 parts of tap water, 20% aqueous dispersion of the fluorine-containing copolymer in the above ratio, diluted with water Comparative Synthesis Example 1 A 20% aqueous dispersion of the obtained fluorinated copolymer was prepared into a processing liquid. The thus obtained treatment liquid was impregnated with 100% cotton cloth, 65% / 35% = PET / cotton cloth (T / C), and twisted by a roller to have a wet water absorption (WPU) of 60 mass%. Next, the cloth was dried at 160 ° C and heat-treated at 3 324 129 37 201247717 minutes, thereby ending the soil release agent treatment. The water absorption (drop method, Wicking method), soil release property, and oil repellency of the cloths were measured. The results are shown in Table 5. [Comparative Example 2] The treatment liquid was prepared in the same manner 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. The cloth was treated to measure the soil detachability and oil repellency. The results are shown in Table 5. [Comparative Example 3] The treatment liquid was prepared in the same manner as in Example 2 except that the 20% aqueous dispersion of the fluorinated copolymer was changed to the 20% aqueous dispersion of the fluorine-containing copolymer obtained in Comparative Synthesis Example 1. The cloth was treated to measure soil detachability and oil repellency. The results are shown in Table 5. [Comparative Example 4] The treatment liquid was prepared in the same manner 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. The cloth was treated to measure the soil detachability and oil repellency. The results are shown in Table 6. [Comparative Example 5] The same procedure as in Example 324129 38 201247717 to 6 was carried out 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. The treatment liquid was treated and the cloth was degreased and oil-repellent. The % results are shown in Table 6. [Comparative Example 6] The 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; The cloth was treated to measure the soil detachability and oil repellency. The results are shown in Table 5. [Comparative Example 7] The treatment liquid was prepared in the same manner 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, and The cloth was treated to measure the soil detachability and oil repellency. The results are shown in Table 5. [Comparative Example 8] The treatment liquid was prepared in the same manner 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, and The cloth was treated to measure the soil detachability and oil repellency. The results are shown in Table 6. [Comparative Example 9] The treatment was carried out in the same order as in Example 324129 39 201247717 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. The liquid was treated and the soil detachability and oil repellency were measured. The results are shown in Table 6. Table 3 Example 1 Example 2 Example 3 Example 4 Synthesis Example 1 3.0 6.0 3.0 6.0 Comparative Synthesis Example 1 Comparative Synthesis Example 2 Synthesis Example 2 Synthesis Example 3 0.25 0.25 1.0 1.0 NS-19 X-80 HL0 3.7 4.2 4 4.2 SR (Corn Oil) HL10 AATCC 3.5 3.5 3.5 3.8 HL20 3.5 3.5 3.5 3.5 HL0 3 3.5 3 3.5 SR (mineral oil) AATCC HL10 3 3.2 3 3.2 HL20 3 3.2 3 3.2 100% HL0 3.2 3.2 3 3.2 Cotton SR (Spicy Oil) HL10 2 2.7 2 2.7 (interlock yellow) AATCC HL20 2 2.5 2 2.5 HL0 2 4 2 4 WPU OR HL10 0 0 0 1 75% HL20 0 0 0 0 HL0 1 2 7 7 Water absorption droplet method (sec.) HL10 1>1>1>1> HL20 1>1>1>1> HL0 11.6 10.1 12.1 12.2 Water absorption Wicking method (cm @ 30mins) HL10 14.0 14.0 14.0 14.0 HL20 14.0 14.0 14.0 14.0 40 324129 201247717 Table 4 Example 5 Example & Synthesis Example 1 3.0 6.0 Comparative Synthesis Example 1 Comparative Synthesis Example 2 Synthesis Example 2 Synthesis Example 3 NS-19 X-80 0.25 8.0 2.4 25 8.0 2.4 100% cotton (twill beige) WPU 57% SR (玉求油) AATCC HLO HL10 HL20 4.5 3.5 3.5 4.5 3.5 3.2 SR (Dish oil J AATCC HLO HL10 HL20 4.5 3 2 4.5 3 2 SR (Spicy oil > AATCC HLO HL10 HL20 4 3 3 4 3 3 OR HLO HL10 HL20 5 0 0 5+ 0 0 Water absorption droplet method (sec.) HLO HL10 HL20 6 1>1> 5 1>1> Water absorption Wicking method (cm @ 30mins) HLO HL10 HL20 10 14.0 14.0 10 14.0 14.0 T/C (twill beige) WPU 56% SR (corn oil > AATCC HLO HL10 HL20 4.2 4 3.7 4.5 3.7 3.7 SR (smoked oil) AATCC HLO HL10 HL20 4 3.7 3.7 4.2 3.7 3.7 SR (spicy oil) AATCC HLO HL10 HL20 4.2 3.7 3.5 4.2 4 3.7 OR HLO HL10 HL20 6 0 0 6 0 0 Water-absorbing droplets Method (sec.) HLO HL10 HL20 17 2 2 11 3 3 Water absorption W丨eking method (cm @ 30mins) HLO HL10 HL20 9.0 14.0 14.0 8.0 14.0 14.0 41 324129 201247717 Table 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 6 Comparative Example 7 Synthesis Example 1 Comparative Synthesis Example 1 Comparative Synthesis Example 2 3.0 3.0 6.0 3.0 6.0 Synthesis Example 2 Synthesis Example 3 0.25 0.25 0.25 0.25 NS-19 X-80 HL0 3.0 3.5 4 3.5 3.7 SR (corn oil) AATCC HL10 0 3.2 3.5 3.2 3.5 HL20 0 3.2 3.2 3.2 3.2 HL0 3 3 3.5 3 3.5 SR (mine Oil) AATCC HL10 0 3 3.2 2 3.2 HL20 0 2 3 2 3 100% HL0 2.5 2.5 2.7 2.5 2.5 Cotton SR (Spicy Oil) HL10 0 2 2.5 2 2.5 (interlock yellow) AATCC HL20 0 2 2 2 2 HL0 2 2 4 0 1 WPU OR HL10 0 0 0 0 0 75% HL20 0 0 0 0 0 Water absorption droplet method (sec.) HL0 1>1> 2 15 180< HL10 1>1>1>1>1> HL20 1> 1&gt 1>1>1> HL0 10.0 12.2 10.8 10.0 4.8 Water Absorption Wicking Method (cm @ 30mins) HL10 10.8 14.0 14.0 14Ό 12.8 HL20 10.4 14.0 14.0 14.0 14.0 SR (Corn Oil) HL0 HL10 4 0 4.5 4.2 4.5 4 4 AATCC 4.2 4.2 4.2 HL20 0 4,2 4.2 4 4 HL0 4 4.5 4.5 4 4 SR (mineral oil) AATCC HL10 0 4.2 4.2 4 4 HL20 0 4.2 4.2 4 4 100% SR (spicy oil) HL0 4 4.5 4.5 2.5 2.5 PET HL10 0 4.5 4.5 3 2.5 (tropical white) AATCC HL20 0 4 4 2.5 2.5 HL0 6 6 6 0 0 WPU OR HL10 0 0 0 0 0 82 % HL20 0 0 0 0 0 Water absorption droplet method HL0 HL10 40 180< 55 180< 35 180 < 180 < (sec.) 180 < 180 < 180 < HL20 180 < 180 < 180 < 180 < 180 < Water absorption W Icking method (cm @ 30mins) HLO 6.8 7.2 7.2 2.7 0.2 HL10 0.0 6.8 7.0 6.0 7.2 HL20 0.0 0.0 0.0 0.0 0.0 42 324129 201247717 Table 6 Comparative Example 4 Comparative Example 5 Comparative Example 8 Comparative Example 9 Synthesis Example 1 Comparative Synthesis Example 1 Comparison Synthesis Example 2 3.0 6.0 3.0 6.0 Synthesis Example 2 Synthesis Example 3 0.25 0.25 0.25 0.25 NS-19 8.0 8.0 8.0 8.0 X-80 2.4 2.4 2.4 HLO 4.2 4.5 3.7 3.5 SR (corn oil) AATGC HL10 3.5 3.5 3.5 3.7 HL20 3 3.2 3.5 3.5 HLO 4 4.2 3.5 3 SR (mineral oil) HL10 2.5 3 3 3.5 AATCC HL20 2 2 2 2.5 100% HLO 3 3.5 3.7 4 cotton (twill beige) SR (spic oil) AATCC HL10 HL20 2.7 2.7 2.7 2.7 3 2.7 3.7 2.7 HLO 3 4 5 6 WPU OR HL10 0 0 0 0 57% HL20 0 0 0 0 HLO 6 6 180 <180< Water Absorbing Drop Method (sec.) HL10 1>1>180<180< HL20 1>1>180<180< HLO 9.3 8.6 0.0 0.0 Water absorption Wicking method (cm @ 30mins) HL10 14.0 14.0 0.0 0.0 HL20 14.0 14.0 0.0 0.0 HLO 4.2 4.5 4 4 SR (玉求油) AATCC HL10 3.7 3.7 4 4 HL20 3.5 3.7 3.7 3.7 HLO 4 4.2 3.5 3.5 SR (mineral oil) AATCC HL10 3.7 3.7 3.5 3.7 HL20 3.7 3.7 3.5 3.5 T/C (twill HLO • 3.7 4.2 3.7 4 SR (spicy oil) AATCC HL10 3.5 3.5 3.7 4 beige) HL20 3.7 3.5 3.7 3.7 HLO 4 5 5+ 6 WPU 56% OR HL10 HL20 0 0 0 0+ 0+ 0 0 0 HLO 17 11 180 <180< water absorption droplet method (sec.) HL10 11 14 180 < 180 < HL20 15 14 180 < 180 < HLO 8.6 8.4 0.0 0.0 Water absorption Wicking method (cm @ 30m ins) HL10 13.7 13.4 0.0 0.0 HL20 14.0 12.8 0.0 0.0 43 324129 201247717 (Industrial use possibility) The composition of the present invention can be used as having excellent water absorption, antifouling property and dirt Detachable dirt release agent. [Simple diagram description] None [Main component symbol description] None 324129 44

Claims (1)

201247717 VII. Patent Application Range: 1. A composition comprising: (1) a fluorine-containing copolymer which is a fluorine-containing copolymer having a monomer having an amine group, (a) represented by the formula (I) The fluorine-containing monomers (a) and (b) are essential components and do not contain ^%-Z-]p-(cH2)^Rf (I) fluorenyl group, fluorine atom, chlorine atom, CH2=C(-X) -C(=〇)-Y-[-(cH2)d] [wherein, X is a mouse atom, a bromine atom, an iodine atom, or a CFX!X2 group (but \1 and Χ2 are hydrogen atoms, fluorine atoms or gas atoms). a cyano group, a linear or branched fluoroalkyl group having 1 to 2 carbon atoms, a substituted or unsubstituted methyl group, a substituted or unsubstituted phenyl group; Y is -〇- or -NH-; Z is a direct bond, -s- or -S〇2 -; Rf is a fluoroalkyl group having 1 to 6 carbon atoms; m is 1 to l〇, n is 〇 to 10, p is 〇 or 1], (b An alkoxy group-containing monomer represented by the formula (II) CH2=C(X')-C(=0)-〇-(R〇)qH (II) [wherein, X' is a hydrogen atom or Methyl; R is an alkylene group having a carbon number of 2 to 4 which is partially or wholly substituted by a hydroxyl group; q is an integer from 1 to 50; (2) a blocked isocyanate compound; And liquid Media. 2. The composition according to claim 1, wherein in the fluorine-containing monomer 324129 1 201247717 (a), p is an integer of 〇. 3. ^ For the composition described in item i or item 2 of the patent application, in the fluorine-containing monomer (a), X is a hydrogen atom. The composition described in the above-mentioned item, wherein the gas-containing monomer (a) has a Rf of a perfluoroalkyl group having a carbon number of 6. 5·=申, the composition of the scope of the patent, the composition of the __ item, the medium containing the oxy group (7) in the 'q is i to 3 整 whole 5 ^ 〇 application (four) (four) the third to the fifth The composition described in the above-mentioned item 'where' contains (c) a crosslinkable monomer. 7. The composition according to claim 6, wherein the crosslinkable monomer (〇 is a non-fluorine crosslinkable monomer bis(meth) acrylate. 8) as claimed in claim 7 The composition wherein the crosslinkable monomer (c) is a di(meth)acrylate represented by the formula (ΠΙ), CH2=C(X»)-c(=〇)-o-( R» 〇)qc(=〇)-c(r χΗ2 (πΐ) [wherein 'each χ' is a hydrogen atom or a methyl group; R is a part or all of a hydrogen atom which can be substituted by a base 2 to 2 And a composition according to any one of the items 1 to 6 wherein the fluorine-containing copolymer is relative to the fluorine-containing copolymer. The non-fluorine non-crosslinking monomer (b) is 10 to 400 parts by weight of the fluoromonomer (a), and the composition according to any one of claims 6 to 9 The weight of the crosslinkable monomer (C) is from 0.1 to 30 by weight, based on 100 parts by weight of the total of the fluorinated monomer (a) and the alkoxy group-containing monomer (b) 324129 2 201247717 ^. 11. If you apply for the scope of patents 1 to 10 The composition according to the above, wherein, in the blocked isocyanate, the blocking agent is a quinone, a phenol, an alcohol, a thiol, a guanamine, a quinone, an imidazole or a urea. And a group selected from the group consisting of amines, imines, pyrazoles, and active methylene compounds. 12. The composition according to any one of claims 1 to 10, In the blocked isocyanate, the blocking agent is a pyrazole. The composition according to any one of claims 1 to 12, which is a solution, an emulsion or an aerosol. A method for treating a substrate, which is treated with the composition according to any one of claims 1 to 13. 15. A fibrous product which is patented The composition according to any one of the preceding claims, wherein the composition is a soil release agent. 17. The use of the composition of any one of claims 1 to 13 of the patent application, which is Dirt release agent. 324129 3 201247717 IV. Designated representative map: (1) The representative representative figure of this case is: () (in this case, there is no drawing) (2) The symbol of the representative figure is simple: (none) If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: CH2=C(-X)-C(=0)-Y-[-(CH2)nZ-]P-(CH2)n-Rf (I CH2=C(X, )-C(=0)-0-(R0)qH (II) 324129 4