JPS61209213A - Fluorine-containing copolymer - Google Patents

Abstract

PURPOSE:To provide the titled polymer having excellent water-repellency and oil-repellency and improved washability, and composed of a perfluoroalkyl- containing (meth)acrylate component and a (meth)acrylate component containing a specific functional group, etc. CONSTITUTION:The objective fluorine-containing copolymer can be produced by the emulsion polymerization of (A) a (meth)acrylic acid ester containing perfluoroalkyl group, (B) a compound of formula (R is H or methyl) (e.g. 2- hydroxy-3-chloropropyl acrylate) and (C) stearyl (meth)acrylate in the presence of e.g. a surfactant and a polymerization initiator. The contents of the components A, B and C in the obtained copolymer are preferably >=25(wt)%, 0.1-10%, and 5-74.9%, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a fluorine-containing copolymer useful as a water- and oil-repellent agent, more specifically, a fluorine-containing copolymer useful as a water- and oil-repellent agent that has excellent durability against home washing and dry cleaning. Regarding copolymers.

Conventionally, polymers of polymerizable compounds containing fluoroalkyl groups or copolymers of this compound and other polymerizable compounds, such as acrylic esters, methacrylic esters, chloroprene, vinyl chloride, maleic esters, vinyl ethers, etc. Water and oil repellents consisting of are known.

It is also known to use a copolymer of a polymerizable compound containing a fluoroalkyl group and an acrylic ester or methacrylic ester containing a hydroxyl group as a water and oil repellent component in order to improve durability against home washing and dry cleaning. be. (For example, see Japanese Patent Publication No. 50-3798). Furthermore, in addition to acrylic esters or methacrylic esters containing hydroxyl groups, copolymers with polymerizable compounds containing various functional groups are used to improve durability.

However, the durability of known copolymers of acrylic esters or methacrylic esters containing only hydroxyl groups or other functional groups is only slightly improved and has not reached a satisfactory level.

An object of the present invention is to improve the above-mentioned drawbacks, and to provide a fluorine-containing copolymer useful as a water and oil repellent agent, which has excellent water and oil repellency and improved durability against washing and dry cleaning.

According to the present invention, the object is (a) a structural unit derived from an acrylic ester or a methacrylic ester to which a perfluoroalkyl group is bonded, (b) the formula: %formula% [wherein R is Represents hydrogen or methyl. This is achieved by a copolymer consisting of a structural unit derived from the compound shown in ] and (C) a structural unit derived from stearyl acrylate or stearyl methacrylate.

Therefore, the fluorine-containing copolymer of the present invention has excellent water and oil repellency and excellent durability against washing and dry cleaning, but it also has other properties that are desirable as a water and oil repellent, such as The stability when diluted with water and the solubility in organic solvents are not impaired, and the texture of the object to be treated is not impaired.

Although it is not clear why the copolymer containing 2-hydroxy-3-chloropropyl acrylate or methacrylate as a constituent unit of the present invention has high durability,
Since the effect on cellulose fibers containing a large amount of active hydrogen is more remarkable than that on polyester, nylon, etc., it is presumed that some kind of chemical bond occurs between the hydroxyl group and terminal chlorine and the treated material. Ru.

In the present invention, the copolymerization ratio of 2-hydroxy-3-chloropropyl acrylate or methacrylate is usually 1.
It is desirable that the content be 0% by weight or less. Furthermore, if the copolymerization ratio is less than 0.1% by weight, a sufficient effect in terms of improving durability cannot be exhibited, which is disadvantageous. Therefore, it is usually used in a copolymerization ratio of 0.1 to 10% by weight, but especially in a ratio of 0.5 to 5% by weight, water and oil repellency, durability, and other properties are extremely improved. The range of 0.1-10% can be varied depending on the type and amount of the fluoroalkyl group-containing acrylic ester or methacrylic ester and the type and amount of other polymerizable compounds described below.

In the present invention, acrylic esters or methacrylic esters containing a fluoroalkyl group include various compounds including conventionally known ones,
For example, CF 3(CF Jt(CHI),,0COC
H=CH2,CF3(CFt)s CH,0COC
(CH3)=CH,, (CF3)tc P (CF
y)s(C')(t)tOCOCH= CHz, CF
3(CFz)e(CH2)tOcOc(CHs)=CH
t, C.F.

(CF Js(CHJtOCOCH= CHt, CF'
, (CFz)7sO2N(CH*XCHt)zOcO
cH=cHt, CF 3(CF ri?S OzN(Ct
HsXc Hz) to COC(CH3)=CH,, (
CF J2CF (CF t)ac HtCH(OCO
CH3) CHt OCOC(CH3) = CHt,
(CF 5)tCF (CF t)eCHtCH(OH
) There are unsaturated esters represented by acrylates or methacrylates containing a perfluoroalkyl group having 3 to 15 carbon atoms, such as CHtOC0CH=CH.

These acrylic esters or methacrylic esters containing fluoroalkyl groups generally have a copolymerization ratio of 25
Use it so that it is at least % by weight.

Furthermore, in the present invention, an acrylic ester or a methacrylic ester containing a fluoroalkyl group and a 2-
In addition to hydroxy-3-chloropropyl acrylate or methacrylate, ethylene, vinyl chloride, vinylidene halide, styrene, acrylic acid and its alkyl esters, methacrylic acid and its alkyl esters, benzyl methacrylate, cyclohexyl methacrylate, vinyl alkyl ketones, It is also possible to copolymerize one or more polymerizable compounds that do not contain fluoroalkyl groups, such as vinyl alkyl ether, butadiene, isoprene, chloroprene, and maleic anhydride, as constituent units of the copolymer. By copolymerizing these polymerizable compounds that do not contain fluoroalkyl groups, it is possible to create copolymers that are cost-effective and have excellent water and oil repellency, durability, and flexibility, as well as solubility, water pressure resistance, and other properties. Various properties can be improved appropriately.

The use of stearyl acrylate or methacrylate, in particular, as a polymerizable compound that does not contain a fluoroalkyl group has the advantage of improving water repellency, improving flexibility and roll-gumming properties, and improving solubility in organic solvents. do. Thus, when using stearyl acrylate or methacrylate, at least 25% by weight of acrylic or methacrylic ester containing fluoroalkyl groups, 0.1 to 10% by weight of 2-hydroxy-3-chloropropyl acrylate or methacrylate, Preferably 062-5% by weight
It is desirable to carry out the copolymerization so as to obtain a copolymer containing stearyl acrylate or methacrylate as a structural unit in a proportion of 5 to 74.9% by weight.

In order to obtain the copolymer of the present invention, various polymerization reaction methods and conditions can be arbitrarily selected, and any of various polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization can be adopted. For example, a method may be employed in which a mixture of compounds to be copolymerized is emulsified in water in the presence of a surfactant and copolymerized with stirring. A peroxide-based, azo-based, or persulfuric acid-based polymerization initiator may be added to the reaction system. As the surfactant, various anionic, cationic or nonionic emulsifiers can be used, and a mixed cationic and nonionic emulsifier is preferably used.

It is also possible to dissolve the raw material polymerizable compound in a suitable organic solvent and carry out solution polymerization by the action of a polymerization initiation source (peroxide, azo compound, ionizing radiation, etc. soluble in the organic solvent used).

The copolymer thus obtained is processed into an emulsion,
It can be adjusted to any form of water and oil repellent such as a solvent solution or aerosol.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. However, % represents weight % unless otherwise specified.

Note that water repellency and oil repellency shown in the following Examples and Comparative Examples are expressed using the following scale. That is, water repellency is expressed by oil repellency N01 (see Table 1 below) determined by the JISL-1005 spray method, and oil repellency is expressed by the composition of each mixing ratio of n-hebutane and Nujol as shown in Table 2 below. The oil repellency No. is determined by dropping 0.05 of the liquid onto the test cloth and determining whether or not the liquid is maintained at a contact angle of 30° or more for 3 minutes or more.

Table 2 The durability test was conducted as follows. That is, in the washing resistance test, the treated test cloth was washed at a temperature of 40% in water containing 0.3% by weight of detergent (product name: Zabukoso XK, Kao Soap Co., Ltd.).
℃, bath ratio 1:40 (fabric: treatment solution (9 ml)), washed in a domestic washing machine for 5 minutes, rinsed for 15 minutes, and dried at 80℃ for 3 minutes. This is one cycle. After repeating this procedure three times, the water and oil repellency was measured and used as a value for washing resistance.

The dry cleaning resistance test is conducted using a downstream tester. Tester container (volume 400) Perchlorethylene 300 containing 0.1% by weight of potassium oleate
mQ was added, 11 g of the test cloth to be treated was added thereto, and the mixture was heated at 30°C.
After stirring for 1 hour at 80° C., the mixture is air-dried once and then at 80° C. for 3 minutes.

After repeating this three times as one cycle, the water and oil repellency was measured and used as a value for dry cleaning resistance.

Reference Example 1 The method for producing the copolymer used in the present invention is exemplified using a terpolymer of a polymerizable compound containing a fluoroalkyl group, stearyl acrylate and 2-hydroxy-3-chloropropyl acrylate. explain.

Formula: (CF3)2CF(CP,CF2)nct12c
Compound 60 represented by t1200ccH"C11t (mixture of compounds with n=3.4.5 in a weight ratio of 5.3.1)
g, C+eH*700 CC[(-〇)(,38
g, CH2=CHC00CH2C1-1(OH)CH2
C (22g, deoxygenated pure water 250g1 acetone 50g
A flask was charged with 0.2 g of n-dodecylmercaptan, 3 g of dimethylalkylamine acetate, and 3 g of polyoxyethylene alkylphenol, and the
After stirring at 0° C. for 1 hour, a solution of 1 g of azobisisobutyramidine hydrochloride dissolved in 10 g of water was added, and the mixture was further stirred at 60° C. for 5 hours under a nitrogen stream to carry out a copolymerization reaction.

The conversion rate of the copolymerization reaction was determined by gas chromatography to be 99.
% or more. From this conversion rate, it was found that the ratio of each structural unit in the obtained copolymer almost matched the ratio of the charged monomers. The obtained emulsified dispersion was a copolymer having a solid content concentration of 25%.

Reference Example 2 The method for producing the copolymer used in the present invention by solution polymerization is exemplified using a terpolymer of a polymerizable compound containing a fluoroalkyl group, stearyl acrylate and 2-hydroxy-3-chloropropyl acrylate. I will list and explain.

Formula: (CF,)2CF(CF2CF2)nCH2CI
(60 g of a compound represented by 200CCH=CH2 (a mixture of compounds in a weight ratio of 5:3:1 with n=3.4.5)
, Cl8H3700CCH=CHt 38g S'CH
z=CHCOOCHzCH(OH) CHt CQ
2 g and 550 g of 1,], , l-)lichloroethane were placed in a flask and heated at 60°C under a nitrogen stream for 3
After stirring for 0 minutes, azobisisobutyronitrile Ig was added, and the mixture was heated and stirred for 12 hours under a nitrogen stream to carry out a copolymerization reaction. Gas chromatography showed that the conversion rate of the copolymerization reaction was 99% or more. It was found that the ratio of each structural unit in the copolymer obtained from this conversion rate almost matched the ratio of the charged monomers.

The resulting solution was a copolymer having a solid content concentration of 15%.

Examples 1-10 and Comparative Examples 1 to 7 A copolymer containing the monomers described in each of the following Examples and Comparative Examples as a constituent unit in the same proportion as the monomer type and proportion An emulsified dispersion was obtained by the same procedure as in Reference Example 1 except for changing , and diluted with water to give a solid content concentration of 0.
Prepare a 5% solution. A mixed cloth of 35% cotton and 65% polyester was dipped in this, squeezed with a roll, pre-dried at 80°C for 3 minutes, and heat-treated at 150°C for 3 minutes to perform water and oil repellent treatment.

This treated test cloth was subjected to a water and oil repellency test and a durability test by washing and dry cleaning, and the results are shown in Table 3.

The monomer composition in each Example and Comparative Example is as follows.

Example 1 (CF3)2cF (CF2CF2)ncH2cHzoO
ccH=cHt (weight ratio of compounds with n=3.4.5 5
・3:1 mixture)
60%C1aH3700CCH=Cft239%CI
+2=CIICOOCH2CH(OH)CH7CC'
I% Example 2 (CF3), cF(CF2CF2)ncH7cH200
cc=cH2 (weight ratio of compounds with n=3.4.5 5
:3 : mixture of I)
60%C, 8[13?0OCCIl=CH238
%CH,=C11C00C)12CH(OH)CI(
2C122% Example 3 (CF2CF2CFzCFz)ncH7cH200cc
H=cl(t(weight ratio of the compound with n=3.4.5 5.
3.1 mixture) 60
%C,,H3?0OCCH=CH236%CH2=C
HCOOCH, CH(01()Cl 2CQ
4% Example 4 (CF3)? CF(CF2CF2)nCH,CH20
0CC(CH3) = CH7 (mixture of compounds in weight ratio 5:3:I with n=3.4.5)
60%C,,H,700CCH=CI
, 38% CI, = CHCO
OCH,CH(OH)CH,C122% Example 5 (CFs)2cF(CF2CF2)ncHtcH200
ccH=CHt (mixture of compounds in a weight ratio of 5:3:1 with n=3.4.5)
60%C+5H3tOOCC(Ctl+)=CHt
38%CH,=C11C00C)1
．． cil(011) 2CH2Cf2 2%
Example 6 (CF3)2CF(CF-CF2)nC)l-CHtO
OCCH=CH2 (mixture of compounds with n=3.4.5 in a weight ratio of 5:3:1)
60%C,,H3700CCH=C11,38%C
L = C(CH3)C00C112CI(OH)CH
, CC2% Example 7 CF3CF-(CFtCF-)net(tcHyoOc
c(CHt) = CHt (mixture of compounds with n=3.4.5 in a weight ratio of 5:3:1)
60%C1aHsyOOCCH=CH23
8%CH,=CHCOOCH,CI(OH)CH,C
122% Example 8 00 CCH3 (CF, ), CF (CF, CF,) nCH, CHCH
,0OCC(C1,) = CHI(n=3.4.5
mixture of compounds in a weight ratio of 5:3:l)
60%C,,1 (3700CC
H=CH238%C112= C(CH3)C00CH
, CH(OH)CI, CC2% Example 9 CsF+7SOJ(CJ,)CJ400CCH=CHz
60%C,,H3700CC(CH,)=C
H, 38% CH2= CHCOOCH, CI(OH)C
H,CQ2% Example 1O (CF3), CF (CF, CF,)nCH,CH,0
OCCH=CI.

(Mixture of n=3.4.5 compounds in a weight ratio of 5:3:1) 98% CH2
= CHCOOCH, (Jl(OH)CH, CC2% Comparative Example 1 (CFa)tcF(CF2CF2)ncHtcH-00
CCH=CH- (mixture of compounds with n=3.4.5 in a weight ratio of 5:3:1)
60%C+aHstOOCCH=CH240% Comparative Example 2 (CF3)tcF(CFtCFJnCHtCHtOOC
Weight ratio of compounds with CH=CH2 (n=3.4.5: 5:
3:1 mixture) 6
0%C,,H3700CCH=C11,38%CI,
= C(CH3)C00CH2CH,OII
2% Comparative Example 3 (CF, ), CP (CF, CF2)nCH2CH,0O
CCH=CH.

(Mixture of n=3.4.5 compounds in a weight ratio of 5:3:1) 60%C,,H
3?0OCCH=CI(,38%CH,=C(CH3
)C00CR,CI(OH)C1,2% Comparative Example 4 (CF3)tcF(CFtCF-)ncH2cHtoO
ccH=cHt (weight ratio of compounds with n=3.4.5 5
:3:1 mixture)
60%Cl8H3?0OCCH=CH238%CH,=
C)] C00C11, CII(OH)CHt, ,
2% Comparative Example 5 (CF3), CF (CF, CF2) ncHtcHtoO
ccH=CHt (mixture of compounds with n=3.4.5 in a weight ratio of 5:3:l)
60%CIIIH3?0OCCH=CH238%CI
, = C(CH3)C00C2H4C122% Comparative Example 6 (CF3)2cF(CF2CF,)ncH2cHaoO
ccH”CH2 (weight ratio of compound with n=3.4.5 5
:3:I mixture)
60%Cl8H3?0OCCH=CH238%CH2=
C(C113)COOC2H401(1%C)I,
= C(CH3)C00CJ, CI2
1% Comparative Example 7 (CF3)2CF(CF,CF2)nCH2CH,0O
CCH=CH.

(Mixture of n = 3.4.5 compounds in a weight ratio of 5:3:I) 100% Example 11 and Comparative Example 8 A copolymer containing the following monomers as constituent units in the proportions was prepared. It was obtained and recovered by the same procedure as in Reference Example 2 except that the type and proportion of the monomers were changed, and this was dissolved in trifluorotrichloroethane to prepare a 0.4% by weight solution. A mixed cloth of 35% cotton and 65% polyester was dipped in this, squeezed with a roll, and pre-dried at 80°C for 3 minutes.
Water and oil repellency treatment was performed by heat treatment at 50° C. for 3 minutes.

This treated test cloth was subjected to a water and oil repellency test and a durability test by washing and dry cleaning, and the results are shown in Table 3.

The monomer compositions in Example 11 and Comparative Example 8 are as follows.

Example 1! (CF3)2CF(CF2CF2)nCH2CH,0O
CCH=CH.

(Mixture of n=3.4.5 compounds in a weight ratio of 5:3:1) 60% C, 8
H3700CCH=C11? 3
8% CH2= CHCOOCH, CI(OH)C1l,
Cσ 2% Comparative Example 8 (CF3), CF (CF2CF2) ncH, cH200
Weight ratio of the mixture of ccH-cH2 (n=3.4.5 5
:3:I mixture)
60%C+ +IH3?00CCH= CH238%
CH,=C(CH3)C00C2H,OHI%CHz
= C(CH3)C00C2H-Cri
1% Patent Applicant: Daikin Industries, Ltd. Procedural Amendment (family) April 3, 1986

Claims (1)

[Claims] 1. (a) A structural unit derived from an acrylic ester or a methacrylic ester to which a perfluoroalkyl group is bonded, (b) Formula: CH_2=CRCOOCH_2CH(OH)CH_2C
l [wherein R represents hydrogen or methyl. A copolymer comprising a structural unit derived from a compound represented by the following formula, and (c) a structural unit derived from stearyl acrylate or stearyl methacrylate. 2. At least 25% by weight of (a) and 0.1 to 0.1% of (b)
10% by weight and (c) in a proportion of 5 to 74.9% by weight.