JP2854567B2 - Antifouling agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art As an antifouling agent which imparts water repellency and oil repellency to textile fabrics and the like and makes it easy to remove stains attached to fibers by washing or the like, acrylic acid esters or methacrylic acid esters containing a fluoroalkyl group ( A copolymer of a compound containing a hydrophilic group and a compound containing a hydrophilic group 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 tactile sensation (Japanese Patent Application Laid-Open No.
-134786 and 59-204980).

[0003]

However, the conventional antifouling agents as described above have insufficient water repellency and durability against washing, and have not yet achieved satisfactory performance. Also, various polymerizable compounds for improving durability have been studied, but an antifouling agent having improved durability has not yet been put on the market. An object of the present invention is to provide an antifouling agent which improves the above-mentioned drawbacks, has excellent initial water repellency and dirt releasability, and has improved durability.

[0004]

The present invention provides (a) a compound represented by the following general formula:

Embedded image [In the formula, 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 carbon atoms) And R ² is a hydrogen atom or a methyl group. Represented by, a structural unit derived from an acrylate or methacrylate containing a fluoroalkyl group, (b) a general formula:

Embedded image [Wherein, R ⁶ is a hydrogen atom or a methyl group, and R ⁷ has 2 carbon atoms.
6 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. Represented by a structural unit derived from polyalkylene glycol acrylate or polyalkylene glycol methacrylate, and (c) a general formula:

Embedded image [In the formula, 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. It represents a linear or branched alkyl group having an atom. A copolymer comprising a structural unit derived from an acrylate ester or a methacrylic ester containing an epoxy group, wherein the amount of the structural unit (a) is 30 to 82 with respect to the copolymer. Weight%, the amount of constituent 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.
The present invention provides an antifouling agent containing a copolymer of No. 00 as an active ingredient.

The monomer forming the structural unit (a) is represented by the general formula: RfR ¹ OCOC (R ² ) = CH ₂ [wherein Rf is a linear or branched 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 carbon atoms) And 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) is represented by the following general formula: CH ₂ ＣＲCR ⁶ COO (R ⁷ O) nR ⁸ wherein R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a carbon atom 2
6 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, R ⁷ is preferably —CH ₂ CH ₂ —,

Embedded image

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

CH ₂ ＣＨCHCOO (CH ₂ CH ₂ O) pH (p = 3-9) CH ₂ C (CH ₃ ) COO (CH ₂ CH ₂ O) pH (p = 3-9) CH ₂ 2CHCOO (CH ₂ CH ₂ O) pCH ₃ (p = 3-9) CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH ₂ O) pCH ₃ (p = 3-9) CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH ₂ O) ₂₃ CH ₃

[0011]

Embedded image

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

Embedded image [In the formula, 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. It represents a linear or branched alkyl group having an atom. ] It is a compound represented by these. Examples of such monomers 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 monomers. The amount of the structural unit (a) is 30 to the copolymer.
-82% by weight, preferably 40-70% by weight. 3
If it is less than 0% by weight, the water / oil repellency is not sufficient. Constituent units
The amount of (b) is from 15 to 67% by weight, preferably from 25 to 50% by weight, based on the copolymer. If it is less than 15% by weight, the soil release property 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, the soil release property and durability are not sufficient.

The copolymer in the present invention has the above constitutional unit
(a), (b) and (c), in addition, 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 structural units derived from a polymerizable compound that does not contain a fluoroalkyl group, such as ether, butadiene, isoprene, chloroprene, and maleic anhydride. Thereby, in addition to water and oil repellency, durability and flexibility, a copolymer which is advantageous in cost can be obtained, or solubility, water pressure resistance and other various properties can be appropriately improved. However, the amount of such other constituent 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 reactions such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and radiation polymerization can be performed. Any of the polymerization systems can be employed. 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 includes peroxide,
Various azo type and persulfate type ones can be used. Since polyalkylene glycol acrylate or methacrylate acts as a surfactant, it is not necessary to use a surfactant, 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 or ionizing radiation 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
0 to 400,000.

The copolymer thus obtained can be prepared into an antifouling agent in any form, such as an emulsion, a solvent solution, or an aerosol, according to a conventional method. The method of applying the antifouling agent containing the copolymer of the present invention as an active ingredient depends on the type and purpose of the object to be treated, the preparation form of the antifouling agent, and the like.
Just select the most appropriate one. In the case of an aqueous emulsion or a solvent solution type, it may be attached to the surface of the object to be treated by a known method such as spraying, dipping, coating or the like and dried, and if necessary, curing is performed. In the case of an aerosol type, it is only necessary to spray the object to be processed and dry it. Further, an antistatic agent, a flame retardant, an anti-wrinkle agent, another polymer, and the like may be added to the copolymer of the present invention as needed.

The objects to be treated which can be treated with the copolymer of the present invention include animal and plant natural fibers such as cotton, hemp, silk and wool, synthetic fibers such as polyamide, polyester, polyacrylonitrile and polyvinyl alcohol, cellulose acetate and acetate. And yarns, woven fabrics, knitted fabrics, felts, non-woven fabrics, papers, etc., as well as wood, leather and the like, which are produced by spinning of various fibers such as semi-synthetic fibers or the like. When the object to be treated is a yarn or a cloth, the amount of the copolymer to be applied is usually 0.1 to 10 parts by weight based on 100 parts by weight of the object to be treated.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but it is needless to say that this description does not limit the present invention. Further, “%” 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 the spray method of JISL-1092
(Refer to Table 1 below.) The oil repellency was determined by placing 0.05 ml of the test solution shown in Table 2 below on a test cloth and determining the permeation state after 30 seconds (AATCC-TM118-198).
3).

[0023]

TABLE 1 Water repellency No. 1 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 Oil repellency test 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 Nujol 65 mixed solution 1 Nujol 31.2 0 Less than 1 −

Further, the test of the soil release property (SR property) is performed as follows. Spread the test cloth on the filter paper laid horizontally, drop 0.1 ml of waste motor oil, place a polyethylene sheet on it, put a 2 kg weight, remove the weight and the polyethylene sheet after 60 seconds, and remove After leaving for an hour, detergent (Super Zab: trade name) 60 with an electric washing machine
g, bath volume 35L, wash at 40 ° C for 10 minutes, rinse and air dry. Dried test cloths are indicated with the relevant rating (see Table 3).

[0026]

[Table 3] Judgment grade of Table 3 Judgment standard 1.0 Those with significant stains 2.0 Those with stains equivalent to 3.0 3.0 Those with slight stains 4.0 Inconspicuous 5.0 No stain remains Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)
Was measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. The measured values are in terms of polystyrene.

Example 1 CF ₃ CF ₂ (CF ₂ CF ₂ ) nCH ₂ CH ₂ OCOCH = CH ₂
70 g of a compound represented by the formula (mixture of n = 3, 4, 5 in a weight ratio of 5: 3: 1), CH ₂ ＣC (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 (1 L in internal volume) equipped with a mercury thermometer and a polytetrafluoroethylene crescent-shaped blade stirrer, and sufficiently dispersed by stirring under a nitrogen stream. About one more
After washing by blowing nitrogen for a period of time, 1.0 g of azobisisobutyronitrile was added, and the solution was further stirred for 7 hours under a nitrogen stream.
The copolymerization reaction was performed by stirring at 0 ° C. for 10 hours. Gas chromatography showed that the conversion of the copolymerization reaction was at least 99%. 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, Mw / Mn was 2.8.

This copolymer dispersion was prepared by mixing the copolymer solid with 0.1%.
It was diluted with water to 5% by weight. A polyester cloth, a blended cloth of 35% cotton and 65% polyester, a cotton cloth, and a nylon cloth were immersed, squeezed with a roll, and the wet pickup was set to 70%. Next, drying was performed at 100 ° C. for 3 minutes, and heat treatment was further performed at 160 ° C. for 1 minute. The fabric treated in this way is made of a polyester fabric with a water repellency of 90,
It showed oil repellency of 8 and soil release of 5. The durability was measured by repeating the same washing as in the stain removal performance test. As a result, the water repellency was 70, the oil repellency was 6, and the stain removal was 4 after 5 washes. The performance of other fabrics is shown in Tables 5, 6, and 7 below.

Examples 2 to 8 A dispersion of a copolymer having the composition shown in Table 4 below prepared in the same manner as in Example 1 was diluted with water so that the copolymer solid content was 0.5% by weight. did. Using these diluents, polyester cloth, blended cloth of 35% cotton and 65% polyester, cotton cloth and 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 was made by
It is a copolymer produced by the same procedure as that in Reference Example of JP-A-2-35033, and is an example included in the publication. Comparative Example 5 is a copolymer produced by the same procedure as in Example 1 of JP-A-59-98113, and is an example included in the publication.

[0031]

[Table 4]

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

The PP-800 is

Embedded image M-230G is CH ₂ ＣC (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 ＣC (CH ₃ ) CN, HEMA (hydroxyethyl methacrylate) is CH ₂ ＣC (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 ＣC (CH ₃ ) CO
OC ₂ H ₄ N ⁺ (CH ₃ ) ₃ Cl ^- is shown.

[0034]

[Table 5]

[0035]

[Table 6]

[0036]

[Table 7]

Continued on the front page (51) Int.Cl. ⁶ Identification code FI D06M 15/27 D06M 15/27 15/273 15/273 15/277 15/277 (72) Inventor Koji Midori 4-23 Bunkyo, Fukui City, Fukui Prefecture No. 1 Nichika Chemical Co., Ltd. (58) Field surveyed (Int. Cl. ⁶ , DB name) C09K 3/00 112 C08F 220/20-220/32 C09K 3/18 102

Claims (1)

(57) [Claims] (1) (a) a general formula: [In the formula, 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 carbon atoms) And 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, represented by the formula: (b) a general formula: [Wherein, R ⁶ is a hydrogen atom or a methyl group, and R ⁷ has 2 carbon atoms.
6 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: [In the formula, 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. It represents a linear or branched alkyl group having an atom. A copolymer comprising a structural unit derived from an acrylate or methacrylate containing an epoxy group, wherein the amount of the structural unit (a) is 30 to 82 with respect to the copolymer. % By weight, the amount of the structural unit (b) is 15 to 67% by weight, the structural unit (c)
Is an amount of 3 to 55% by weight, and a copolymer having a number average molecular weight of 1,000 to 1,000,000 as an active ingredient.