JPH09183962A - Stainproofing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a stainproofing agent excellent in initial water repellency and stain removal and improved in durability by using as the effective constituent a copolymer consisting of a plurality of specified structural units and having a specified molecular weight. SOLUTION: This stainproofing agent contains as the effective constituent a copolymer consisting of 30-82wt.% structural units represented by formula I [wherein Rf is a 3-20C perfluoroalkyl; R<1> is a 1-10C alkylene, SO2 N(R<3> )R<4> (wherein R<3> is a 1-10C alkyl; and R<4> is a 1-10C alkylene), or CH2 CH(OR<5> )CH2 (wherein R<5> is H or a 1-10C acyl); and R<2> is H or CH3 ], 15-67wt.% structural units represented by formula II (wherein R<6> is R<2> ; R<7> is a 2-6C alkylene; R<8> is H or a 1-20C alkyl; and (n) is 3 to 50) and 3-55wt.% structural units represented by formula III (wherein R<9> is R<2> ; R<10> is a direct bond or R<4> ; and R<11> is H or R<3> ) and having a number-average molecular weight of 1,000 to 1,000,000.

Description

Detailed Description of the Invention

[0001]

[0001] The present invention relates to an antifouling agent.

[0002]

BACKGROUND ART Acrylic ester or methacrylic acid ester containing a fluoroalkyl group (as a stain-proofing agent for imparting water and oil repellency to textile fabrics, etc. and facilitating removal of stains attached to fibers by washing etc. Hereinafter, a copolymer of a fluorine-containing compound) and a hydrophilic group-containing compound is known. It is also known that a polymerizable compound is appropriately selected and copolymerized in order to improve various properties such as durability, flexibility, and feel (Japanese Patent Laid-Open No. 53-53113).
-134786 and 59-204980).

[0003]

However, the above-described conventional antifouling agents have insufficient water repellency and durability against washing, and have not yet achieved satisfactory performance. In addition, various polymerizable compounds for improving durability have been investigated, but an antifouling agent having improved durability has not been put on the market yet. An object of the present invention is to provide an antifouling agent which has improved the above-mentioned drawbacks, excellent initial water repellency and stain release property, and further improved durability.

[0004]

The present invention provides (a) a general formula:

Embedded image [Wherein Rf is a linear or branched perfluoroalkyl group having 3 to 20 carbon atoms, R ¹ is a linear or branched alkylene group having ¹ to 10 carbon atoms,
SO ₂ N (R ³ ) R ⁴ — group or —CH ₂ CH (OR ⁵ ) CH ₂ —
A group (provided that R ³ is an alkyl group having 1 to 10 carbon atoms, R ⁴ is a linear or branched alkylene group having 1 to 10 carbon atoms, R ⁵ is a hydrogen atom or 1 to 10) R ² is a hydrogen atom or a methyl group. ], A structural unit derived from an acrylic acid ester or a methacrylic acid ester containing a fluoroalkyl group, (b) a general formula:

Embedded image [In the formula, R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a carbon atom of 2
To 6 linear or branched alkylene groups, R ⁸ represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, and n represents an integer of 3 to 50. ], A structural unit derived from polyalkylene glycol acrylate or polyalkylene glycol methacrylate, and (c) a general formula:

[Chemical 6] [Wherein R ⁹ is a hydrogen atom or a methyl group, R ¹⁰ is a direct bond or a linear or branched alkylene group having 1 to 10 carbon atoms, and R ¹¹ is a hydrogen atom or 1 to 10 carbon atoms. A linear or branched alkyl group having an atom is shown. ] The copolymer which consists of the structural unit derived from the acrylic ester or methacrylic acid ester containing an epoxy group represented by these, and the quantity of a structural unit (a) is 30-82 with respect to a copolymer. Wt%, amount of structural unit (b) is 1
5 to 67% by weight, the amount of the structural unit (c) is 3 to 55% by weight, and the number average molecular weight of the copolymer is 1,000 to 10,000.
There is provided an antifouling agent containing a copolymer of No. 00 as an active ingredient.

The monomer forming the structural unit (a) has a general formula: RfR ¹ OCOC (R ² ) ═CH ₂ [wherein Rf is a straight chain or branched chain having 3 to 20 carbon atoms]. A perfluoroalkyl group of R ¹ is a linear or branched alkylene group having ¹ to 10 carbon atoms,
SO ₂ N (R ³ ) R ⁴ — group or —CH ₂ CH (OR ⁵ ) CH ₂ —
A group (provided that R ³ is an alkyl group having 1 to 10 carbon atoms, R ⁴ is a linear or branched alkylene group having 1 to 10 carbon atoms, R ⁵ is a hydrogen atom or 1 to 10) R ² is a hydrogen atom or a methyl group. ] It is a compound represented by these. Examples of such monomers include the following.

CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₁₀ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₁₀ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₆ CH ₂ OCOCH = _{CH 2 CF 3 (CF 2)} 6 CH 2 OCOC (CH 3) = CH 2 (CF 3) 2 CF (CF 2) 6 (CH 2) 2 OCOCH = CH 2 (CF 3) 2 CF (CF 2) 8 _{(CH 2) 2 OCOCH = CH} 2 (CF 3) 2 CF (CF 2) 10 (CH 2) 2 OCOCH = CH 2 (CF 3) 2 CF (CF 2) 6 (CH 2) 2 OCOC (CH 3) _{= CH 2 (CF 3) 2} CF (CF 2) 8 (CH 2) 2 OCOC (CH 3) = CH 2

(CF ₃ ) ₂ CF (CF ₂ ) ₁₀ (CH ₂ ) ₂ OCOC
_{(CH 3) = CH 2 CF} 3 CF 2 (CF 2) 6 (CH 2) 2 OCOCH = CH 2 CF 3 CF 2 (CF 2) 8 (CH 2) 2 OCOCH = CH 2 CF 3 CF 2 (CF 2 _{) 10 (CH 2) 2 OCOCH} = CH 2 CF 3 CF 2 (CF 2) 6 (CH 2) 2 OCOC (CH 3) = CH 2 CF 3 CF 2 (CF 2) 8 (CH 2) 2 OCOC (CH _{3) = CH 2 CF 3 CF} 2 (CF 2) 10 (CH 2) 2 OCOC (CH 3) = CH 2 CF 3 (CF 2) 7 SO 2 N (CH 3) (CH 2) 2 OCOCH = C
_{H 2 CF 3 (CF 2)} 7 SO 2 N (C 2 H 5) (CH 2) 2 OCOC (C
_{H 3) = CH 2 (CF} 3) 2 CF (CF 2) 8 CH 2 CH (OCOCH 3) CH 2 O
_{COC (CH 3) = CH 2} (CF 3) 2 CF (CF 2) 8 CH 2 CH (OH) CH 2 OCOCH
= CH ₂

The monomer forming the structural unit (b) has a general formula: CH ₂ = CR ⁶ COO (R ⁷ O) nR ⁸ [wherein R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a carbon number. Two
To 6 linear or branched alkylene groups, R ⁸ represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, and n represents an integer of 3 to 50. ] It is a compound represented by these.

Usually, --CH ₂ CH ₂ --is preferred as R ^7.

Embedded image

Embedded image And so on. Further, particularly good results are obtained when n is usually selected from an integer of 9 to 25. Of course, it may be adopted in the form of a mixture of two or more kinds in which R ⁷ is different and n is different. Examples of the monomer forming the structural unit (b) include the following.

CH ₂ ═CHCOO (CH ₂ CH ₂ O) pH (p = 3 to 9) CH ₂ ═C (CH ₃ ) COO (CH ₂ CH ₂ O) pH (p = 3 to 9) CH ₂ ═CHCOO _{(CH 2 CH 2 O) pCH} 3 (p = 3~9) CH 2 = C (CH 3) COO (CH 2 CH 2 O) pCH 3 (p = 3~9) CH 2 = C (CH 3) COO (CH ₂ CH ₂ O) ₂₃ CH ₃

[0011]

Embedded image

The monomer forming the structural unit (c) has the general formula:

Embedded image [Wherein R ⁹ is a hydrogen atom or a methyl group, R ¹⁰ is a direct bond or a linear or branched alkylene group having 1 to 10 carbon atoms, and R ¹¹ is a hydrogen atom or 1 to 10 carbon atoms. A linear or branched alkyl group having an atom is shown. ] It is a compound represented by these. Examples of such a monomer include the following.

[0013]

Embedded image

[0014]

Embedded image

Each of the structural units (a), (b) and (c) may be formed from a mixture of two or more kinds of monomers. The amount of the structural unit (a) is 30 with respect to the copolymer.
˜82 wt%, preferably 40-70 wt%. 3
If it is less than 0% by weight, the water and oil repellency is insufficient. Constituent units
The amount of (b) is 15 to 67% by weight, preferably 25 to 50% by weight, based on the copolymer. If it is less than 15% by weight, the stain releasability is not sufficient. The amount of the structural unit (c) is 3 to 55% by weight, preferably 5 to 20% by weight, based on the copolymer. If it is less than 3% by weight, stain releasability and durability are insufficient.

The copolymer in the present invention has the above-mentioned constitutional unit.
In addition to (a), (b) and (c), ethylene, vinyl chloride, vinylidene halide, styrene, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, benzyl methacrylate, vinyl alkyl ketone, vinyl alkyl It may have other constitutional units derived from a polymerizable compound containing no fluoroalkyl group such as ether, butadiene, isoprene, chloroprene and maleic anhydride. Thereby, in addition to water and oil repellency, durability and flexibility, a cost-effective copolymer can be obtained, or solubility, water pressure resistance and various other properties can be appropriately improved. However, the amount of such other structural units is preferably 5% by weight or less based on the copolymer.

In order to obtain the copolymer of the present invention, various polymerization reaction systems and conditions can be arbitrarily selected, and various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and radiation polymerization can be performed. Any of the polymerization methods can be adopted. For example, a method in which a mixture of compounds to be copolymerized is emulsified in water in the presence of a surfactant and copolymerized with stirring can be adopted. The polymerization initiator of the reaction system is a peroxide,
Various types of azo type and persulfate type may be used. Since polyalkylene glycol acrylates or methacrylates act as surfactants, it is not necessary to use surfactants, but various anionic, cationic or nonionic emulsifiers may optionally be added.

The raw material monomer is dissolved in a suitable organic solvent,
Solution polymerization can also be carried out by the action of a polymerization initiation source (peroxide, azo compound, ionizing radiation, etc. which is soluble in the organic solvent used). Suitable solvents for solution polymerization include isopropanol, ethyl cellosolve, trichlorotrifluoroethane, tetrachlorodifluoroethane and methyl chloroform. The number average molecular weight of the copolymer of the present invention is 1,000 to 1,000,000, preferably 200.
It is 0-400000.

The copolymer thus obtained can be prepared into an antifouling agent of any form such as an emulsion, a solvent solution and an aerosol according to a conventional method. The method of applying an antifouling agent containing the copolymer of the present invention as an active ingredient, depending on the type and purpose of use of the object to be treated, the preparation mode of the antifouling agent, etc.
Choose the most appropriate one. In the case of an aqueous emulsion or a solvent solution type, it may be adhered to the surface of the object to be treated by a known method such as spraying, dipping or coating, and dried, and if necessary, curing is performed. Further, in the case of the aerosol type, it suffices to spray and dry the object to be treated. Furthermore, if necessary, an antistatic agent, a flame retardant, a wrinkle-proofing agent, and other polymers may be added to the copolymer of the present invention.

Materials to be treated that can be treated with the copolymer of the present invention include natural animal and vegetable fibers such as cotton, hemp, silk and wool, synthetic fibers such as polyamide, polyester, polyacrylonitrile and polyvinyl alcohol, cellulose acetate and acetate. Examples thereof include yarns, woven fabrics, knitted fabrics, felts, non-woven fabrics, papers, and the like, as well as woods, leathers, and the like, which are produced by individual spinning of various fibers such as semi-synthetic fibers and the like, or by blending these. When the article to be treated is a thread or cloth, the coating amount of the copolymer is usually 0.1 to 10 parts by weight per 100 parts by weight of the article to be treated.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but it goes without saying that the description does not limit the present invention. In addition,% means% by weight unless otherwise specified.

The water repellency and oil repellency shown in the following Examples and Comparative Examples were measured by the following test methods. Water repellency is measured by JISL-1092 spray method.
(Refer to Table 1 below) The oil repellency is judged by placing the test solution shown in Table 2 below on a test cloth in an amount of 0.05 ml and seeping it for 30 seconds (AATCC-TM118-198).
3).

[0023]

[Table 1] Table 1 Water repellent No. State 100 No adhesion and wetting on surface 90 Slightly adhering and wetting on surface 80 Partially wetting on surface 70 Wetting on surface 50 Showing wetting on entire surface 0 Front and back completely Indicating wetness

[0024]

[Table 2] Table 2 Oil repellency test Solution surface tension dyne / cm, 25 ° C 8 n-heptane 20.0 7 n-octane 21.8 6 n-decane 23.5 5 n-dodecane 25.0 4 n-tetradecane 26.7 3 n-hexadecane 27.3 2 hexadecane 35 / 29.6 Nujol65 mixed solution 1 Nujol 31.2 0 1-

The dirt release property (SR property) is tested as follows. Spread the test cloth on the filter paper laid horizontally, drop 0.1 ml of waste motor oil, put a polyethylene sheet on it, put a weight of 2 kg on it, and remove the weight and polyethylene sheet after 60 seconds, After leaving for an hour, use an electric washing machine for detergent (Super Zab: product name) 60
g, bath volume 35 L, wash at 40 ° C. for 10 minutes, rinse, and air dry. Dried test cloths are represented by the appropriate judgment grade (see Table 3).

[0026]

[Table 3] Table 3 Judgment grade Judgment standard 1.0 Significantly spots remain 2.0 Spots equivalent to 2.0 3.0 Slight spots remain 4.0 Spots Inconspicuous 5.0 No stain remaining Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)
Was measured by a gel permeation chromatograph (GPC) method using tetrahydrofuran (THF) as a solvent. The measured values are polystyrene equivalent values.

Example 1 CF ₃ CF ₂ (CF ₂ CF ₂ ) nCH ₂ CH ₂ OCOCH = CH ₂
70 g of a compound represented by (a mixture of n = 3,4,5 compounds in a weight ratio of 5: 3: 1), CH ₂ ═C (CH ₃ ) COO (CH ₂ C
H ₂ O) ₉ CH ₃ 25 g,

Embedded image 5 g and 400 g of isopropanol were placed in a glass four-necked flask (internal volume 1 L) equipped with a mercury thermometer and a stirrer of polytetrafluoroethylene crescent moon type blade, and were sufficiently dispersed by stirring under a nitrogen stream. About 1 more
After cleaning by blowing nitrogen for an hour, 1.0 g of azobisisobutyronitrile was added, and the mixture was further washed under a nitrogen stream to give 7
The copolymerization reaction was carried out by stirring at 0 ° C. for 10 hours. It was shown by gas chromatography that the conversion of the copolymerization reaction was 99% or more. From this conversion, it was found that the ratio of each structural unit in the obtained copolymer was almost the same as the ratio of the charged monomers. The resulting dispersion contained 20% copolymer solids. Mn of the copolymer is 73
000 and Mw / Mn were 2.8.

Copolymer solids in this copolymer dispersion were
It was diluted with water to be 5% by weight. A polyester cloth, a blended cloth of 35% cotton and 65% polyester, a cotton cloth, and a nylon cloth were dipped in this and squeezed with a roll to obtain a wet pickup of 70%. Then, it was dried at 100 ° C. for 3 minutes and further heat-treated at 160 ° C. for 1 minute. The cloth treated in this way has a water-repellent property of 90 on polyester cloth.
The oil repellency was 8 and the stain release property was 5. The durability was measured by repeating the same washing as in the stain release performance test. As a result, the water repellency was 70, the oil repellency was 6, and the stain release property was 4 after 5 times of washing. The performance of the other fabrics is shown in Tables 5, 6 and 7 below.

Examples 2 to 8 Dispersions of copolymers having the compositions shown in Table 4 below, which were produced in the same manner as in Example 1, were diluted with water so that the copolymer solids were 0.5% by weight. did. Using these diluted solutions, a polyester cloth, a mixed cloth of 35% cotton and 65% polyester, a cotton cloth and a nylon cloth were treated in the same manner as in Example 1. The treated fabric had the performance shown in Tables 5, 6 and 7 below.

Comparative Examples 1 to 5 Copolymers having the compositions shown in Table 4 below produced in the same manner as in Example 1 were evaluated in the same manner as in Example 1. The results are shown in Tables 5, 6 and 7 below. Comparative Example 4 is Japanese Patent Publication Sho 5
It is a copolymer produced by the same procedure as the reference example of JP-A-2-35033, and is an example included in the publication. Further, Comparative Example 5 is a copolymer produced by the same procedure as Example 1 of JP-A-59-98113, and is an example included in this publication.

[0031]

[Table 4]

SFA is CF ₃ CF ₂ (CF ₂ CF ₂ ) nCH ₂
CH ₂ OCOCH = CH ₂ (mixture of n = 3,4,5 compounds in a weight ratio of 5: 3: 1), SFMA is CF ₃ CF ₂ (CF ₂ C
F ₂ ) nCH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ (n = 3,4,5)
Of the compound of 5: 3: 1 by weight), BrFA is (C
_{F 3) 2 CF (CF 2} CF 2) nCH 2 CH 2 OCOCH = CH
₂ (mixture of 5: 3: 1 weight ratio of n = 3,4,5 compounds), M
-90G _{is, CH 2 = C (CH 3} ) COO (CH 2 CH 2 O) 9
CH ₃ and PE-350 have CH ₂ = C (CH ₃ ) COO (CH
_{2 CH 2 O) 9 H,} M-40G is _{CH 2 = C (CH 3)} COO
_{(CH 2 CH 2 O) 4} CH 3, PE-200 is, CH ₂ = C (C
_{H 3) COO (CH 2 CH} 2 O) 5 H,

PP-800 is

Embedded image M-230G is CH ₂ ═C (CH ₃ ) COO (CH ₂ CH ₂
O) ₂₃ CH ₃ , PP-500 is

Embedded image GMA is

Embedded image GA is

Embedded image SFA (n = 3) is CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ CH ₂ C
H ₂ OCOCH = CH ₂ , MAN (methacrylonitrile)
Is CH ₂ ═C (CH ₃ ) CN, HEMA (hydroxyethyl methacrylate) is CH ₂ ═C (CH ₃ ) COOCH ₂ C
H ₂ OH and SASFA are C ₈ F ₁₇ SO ₂ N (CH ₃ ) C ₂ H ₄
OCOCH = CH ₂ , EEA is C ₂ H ₅ OC ₂ H ₄ OCO
CH = CH _2, DQ-100 _{is, CH 2 = C (CH 3} ) CO
OC ₂ H ₄ N ⁺ (CH ₃ ) ₃ Cl ⁻ .

[0034]

[Table 5]

[0035]

[Table 6]

[0036]

[Table 7]

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location D06M 15/273 D06M 15/273 15/277 15/277 // C09K 3/18 102 C09K 3/18 102 (72 Inventor Yuko Hirata 1-1-1 Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Inventor Koji Midori 4-23-1, Bunkyo, Fukui-shi, Fukui Prefecture

Claims (1)

[Claims] 1. A general formula: [Wherein Rf is a linear or branched perfluoroalkyl group having 3 to 20 carbon atoms, R ¹ is a linear or branched alkylene group having ¹ to 10 carbon atoms,
SO ₂ N (R ³ ) R ⁴ — group or —CH ₂ CH (OR ⁵ ) CH ₂ —
A group (provided that R ³ is an alkyl group having 1 to 10 carbon atoms, R ⁴ is a linear or branched alkylene group having 1 to 10 carbon atoms, R ⁵ is a hydrogen atom or 1 to 10) R ² is a hydrogen atom or a methyl group. ] A structural unit derived from an acrylic ester or a methacrylic ester containing a fluoroalkyl group, represented by: (b) General formula: [In the formula, R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a carbon atom of 2
To 6 linear or branched alkylene groups, R ⁸ represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, and n represents an integer of 3 to 50. A structural unit derived from polyalkylene glycol acrylate or polyalkylene glycol methacrylate, represented by the following formula: and (c) a general formula: [Wherein R ⁹ is a hydrogen atom or a methyl group, R ¹⁰ is a direct bond or a linear or branched alkylene group having 1 to 10 carbon atoms, and R ¹¹ is a hydrogen atom or 1 to 10 carbon atoms. A linear or branched alkyl group having an atom is shown. ] A copolymer composed of constitutional units derived from an acrylic acid ester or a methacrylic acid ester containing an epoxy group, wherein the amount of the constitutional unit (a) is 30 to 82 with respect to the copolymer. % By weight, the amount of constitutional unit (b) is 15 to 67% by weight, constitutional unit (c)
Is an amount of 3 to 55% by weight, and an antifouling agent containing a copolymer having a number average molecular weight of 1000 to 1,000,000 as an active ingredient.