JPH1149825A - New copolymer and antifouling finishing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new copolymer capable of improving durability while keeping fouling-releasing properties by allowing the copolymer to have constituting units derived from a polymerizable monomer having a polyfluoroalkyl group, a polyalkylene glycol (meth)acrylate and a polymerizable monomer having acetoacetyl group. SOLUTION: This new copolymer has constituting units derived from (A) a polymerizable monomer having a polyfluoroalkyl group of formula I (Rf is a 3-21C polyfluoroalkyl group; R<1> is H or a 1-10C alkyl; R<2> is a 1-10C alkylene; R<3> is H or methyl), the formula Rf-(CH2 )n OCOCR<3> =CH2 [(n) is 1-10], formulas II to IV, or the formula Rf-O-Ar-CH2 OCOR<3> =CH2 [Ar is a (substituted) arylene], (B) a polyalkylene glycol (meth)acrylate and (C) a polymerizable monomer having acetoacetyl group [e.g. a (meth)acrylate ester having acetoacetyl group], and has 1,000-500,000 average molecular weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel copolymer and an antifouling agent containing the same.

[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 adhered to fibers by washing or the like, a (meth) acrylic acid ester containing a fluoroalkyl group ( A copolymer of a compound having a hydrophilic group and a compound having a hydrophilic group is known (hereinafter, also referred to as JP-A-53-134786 and JP-A-59-204).
980 and 62-7782).

Further, among polymers of fluorine-containing compounds,
In order to improve the water-repellent and oil-repellent durability to washing, copolymers comprising a fluorine-containing compound and a hydroxyl group-containing (meth) acrylate, and optionally an alkyl (meth) acrylate have been developed (for example, And JP-B-50-3798, U.S. Pat. No. 3,356,628).

[0004] However, a copolymer of a (meth) acrylate having a hydrophilic group such as a hydroxyl group or a polyethylene glycol group and a (meth) acrylate having a fluoroalkyl group has an initial property of removing soil and repelling. Although the water and oil repellency are somewhat good, the soil release and the durability of the water repellency are insignificant and not satisfactory. Also, (a) a (meth) acrylate having a fluoroalkyl group, (b) a polyalkylene glycol (meth) acrylate, (c) 3-chloro-2-
Copolymers containing structural units derived from hydroxypropyl (meth) acrylate and (d) glycerol mono (meth) acrylate have also been proposed (Japanese Patent Laid-Open Publication No. Hei 6-1994).
116340), however, with respect to the washing durability, particularly in the case of natural fibers and blended fibers mainly made of cotton, there is an even higher demand, and it cannot be said that they are always sufficiently satisfied.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an antifouling agent having improved durability while having an initial soil release property.

[0006]

The gist of the present invention is to provide (a) a polymerizable monomer having a polyfluoroalkyl group, (b) a polyalkylene glycol (meth) acrylate, and (c) a polymer having an acetoacetyl group. Having a structural unit derived from a hydrophilic monomer as an essential component, and having an average molecular weight of 1,000 to 50.
0000 copolymers. Another gist of the present invention resides in an antifouling agent containing the copolymer as an active ingredient.

As the polymerizable monomer (a) having a polyfluoroalkyl group, the following can be exemplified.

[0008]

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[0009]

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Wherein Rf is a polyfluoroalkyl group having 3 to 21 carbon atoms, R ¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ² is an alkylene group having 1 to 10 carbon atoms, and R ³ is hydrogen. Alternatively, a methyl group, Ar is an arylene group which may have a substituent, and n is an integer of 1 to 10. And (meth) acrylates containing a polyfluoroalkyl group. The polyfluoroalkyl group may be a perfluoroalkyl group.

More specifically, CF ₃ (CF ₂ ) ₇ (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 (CF 2) 7 (CH 2) 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 (CH 2) 2 OCOCH = 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 ) ₆ 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 , CF ₃ C ₆ F ₁₀ (CF ₂ ) ₂ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOC
H = CH ₂ ,

Embedded image Can be exemplified.

Of the above-mentioned polymerizable monomers (a) having a polyfluoroalkyl group, it is of course possible to use a mixture of two or more kinds.

The monomer (b) has the formula: CH ₂ ＣＲCR ¹¹ COO- (R ¹² O) _n -R ^{13 wherein} R ¹¹ and R ¹³ are a hydrogen atom or a methyl group;
¹² represents an alkylene group having 2 to 6 carbon atoms, and n represents an integer of 3 to 50. ] Is preferable.

As R ¹² , -CH ₂ CH _2- is usually preferred, but -CH (CH ₃ ) CH _2- , -CH (C ₂ H ₅ ) CH
_2- and so on. That is, in the present invention, R ¹²
Is particularly preferably a polyethylene glycol acrylate or methacrylate in which is —CH ₂ CH ₂ —. Further, n is selected from an integer of 3 to 50.
Is particularly selected when it is selected from the integers of 9 to 25. The monomer (b) may be in the form of a mixture of two or more.

Specific examples of the monomer (b) are shown below. CH ₂ ＝ C (CH ₃ ) COO (CH ₂ CH ₂ O) _3-9 H CH ₂ ＝ C (CH ₃ ) COO (CH ₂ CH ₂ O) ₉ H CH ₂ ＝ C (CH ₃ ) COO (CH ₂ CH ₂ O) ₆ H CH ₂ = CHCOO (CH ₂ CH (CH ₃ ) O) ₁₁ CH ₃ CH ₂ ＝ C (CH ₃ ) COO (CH ₂ CH ₂ O) ₉ H CH ₂ ＝ C (CH ₃ ) COO (CH ₂ CH ₂ O) ₅ (CH ₂ CH (CH ₃ ) O) ₃ H CH ₂ ＝ C (CH ₃ ) COO (CH ₂ CH ₂ O) ₉ CH ₃ CH ₂ ＝ C (CH ₃ ) COO (CH ₂ CH ₂ O) ₂₃ CH ₃ CH ₂ ＝ C (CH ₃ ) COO (CH ₂ CH ₂ O) ₄₀ H

The monomer (c) is a polymerizable monomer having an acetoacetyl group. The monomer (c) is preferably a compound having an acetoacetyl group and a carbon-carbon double bond. As the monomer (c), acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, acetoacetoxypropyl acrylate, acetoacetoxypropyl methacrylate, N- (2-acetoacetoxyethyl) acrylamide, N- (2-acetoacetoxyethyl) methacryl Examples include amide, vinyl acetoacetate, and allyl acetoacetate. Monomer (c)
Is preferably a (meth) acrylate ester having an acetoacetyl group.

In the copolymer of the present invention, a (meth) acrylic acid ester having a fluoroalkyl group (monomer
The amount of (a)) is preferably at least 25% by weight, more preferably 25-80% by weight, especially 30-70% by weight, based on the copolymer. If it is less than 25% by weight, the water / oil repellency is not sufficient.

The amount of the polyalkylene glycol (meth) acrylate (monomer (b)) is preferably at least 15% by weight, more preferably 15 to 70% by weight, based on the copolymer.
% By weight, in particular from 20 to 60% by weight. If it is less than 15% by weight, the dispersibility in water is not good, so that the durability is not sufficient.

Polymerizable monomer having acetoacetyl group
The amount of (monomer (c)) is at least 0.5% by weight, more preferably 0.5 to 40% by weight, especially 2 to 30% by weight, based on the copolymer. If it is less than 0.5% by weight, the soil release property and durability are not sufficient.

The average molecular weight of the copolymer of the present invention is 100
0-500000, preferably 5000-200000
It is. If it is less than 1,000, the durability is not sufficient, and 500
If it exceeds 000, the viscosity of the processing solution is too high, and the workability is reduced. The average molecular weight is a value determined by gel permeation chromatography in terms of polystyrene. The copolymer of the present invention may be a random copolymer or a block copolymer.

The copolymer of the present invention may contain, in addition to the monomers (a), (b) and (c), ethylene, vinyl chloride, vinylidene halide, styrene, acrylic acid and its alkyl ester, and methacrylic acid. Water and oil repellency and durability by copolymerizing polymerizable compounds that do not contain fluoroalkyl groups such as alkyl esters, benzyl methacrylate, vinyl alkyl ketone, vinyl alkyl ether, isoprene, chloroprene, maleic anhydride, and butadiene. In addition to the properties and flexibility, a copolymer can be obtained which is advantageous in terms of cost, or the solubility, water pressure resistance and other various properties can be appropriately improved. The amount of these copolymerizable compounds not containing a fluoroalkyl group is 0 to 40% by weight, preferably 0 to 20% by weight.

In order to obtain the copolymer of the present invention, various polymerization reaction systems and conditions can be arbitrarily selected, and any of various polymerization systems such as bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization can be used. Can also 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.

As the polymerization initiator of the reaction system, various compounds of peroxide, azo type or persulfate type can be used. When the surfactant contains polyethylene glycol acrylate or methacrylate as a constituent unit,
It does not need to be added separately as it works, but various anionic, cationic or nonionic emulsifiers may optionally be added.

It is also possible to dissolve the polymerizable compound as a raw material in an appropriate organic solvent and carry out solution polymerization by the action of a polymerization initiation source (peroxide, azo compound or ionizing radiation soluble in the organic solvent used). it can. A known mercapto group-containing compound can be used as a molecular weight regulator. Examples of the mercapto group-containing compound include alkyl mercaptans such as lauryl mercaptan, 2-mercaptoethanol, and mercaptopropionic acid.

The copolymer thus obtained can be prepared in an arbitrary form such as an emulsion, a solvent solution or an aerosol according to a conventional method, and can be used as an antifouling agent. The copolymer of the present invention can be applied to an article to be treated as an antifouling agent by any method according to the type of the article to be treated and the preparation form (solvent solution type, aerosol type, etc.). For example, in the case of an aqueous emulsion or a solvent solution type, a known method of coating such as dip coating or the like is a method of attaching and drying on the surface of an object to be treated (particularly, a textile). Can be adopted. If necessary, curing may be performed by applying together with a suitable crosslinking agent. The aerosol-type antifouling agent may be simply sprayed and sprayed on the object to be processed, and after drying immediately, it can exhibit sufficient water and oil repellency and soil release properties. Further, the copolymer of the present invention may be mixed with another polymer blender to form an antifouling agent.
Of course, it is also possible to obtain an antifouling agent by appropriately using other water repellents, oil repellents, insect repellents, flame retardants, antistatic agents, dye stabilizers, anti-wrinkle agents, anti-shrinkage agents and the like as additives. .

[0026]

Next, the present invention will be described in more detail with reference to Examples, Comparative Examples and Test Examples. However,%
"Parts" represent% by weight unless otherwise specified.

The water repellency and oil repellency shown in the following Examples and Comparative Examples are represented by the following scales. That is, the water repellency is measured by the spray method of JIS L-1005. (See Table 1) and the oil repellency is shown in Table 2.
Apply a few drops (about 4 mm in diameter) to the test cloth at two locations on the test cloth and judge by the permeation state after 30 seconds (AATCC
-TM118-1966).

[0028]

[Table 1] Water repellency No. state 100 No adhesion and wetting on the surface 90 One with slight adhesion and wetting on the surface 80 One with partial wetting on the surface 70 One with wetting on the surface 50 Wetting on the whole surface Indicating 0 Indicating completely wet front and back

[0029]

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 / nu 29.6 Joule 65 mixed solution 1 Nujol 31.2 0 Less than-

Further, the test of the soil release performance (SR property) was performed as follows. That is, the test cloth is spread on a blotter paper spread horizontally, and dirty motor oil (SAE20W-4
0, put it in the engine of a small passenger car, discharge it after running 4000 km), drop 5 drops, put a polyethylene sheet on it, put a weight of 2 kg, remove the weight and the polyethylene sheet after 60 seconds, remove excess oil And left at room temperature for 1 hour, then add a ballast cloth to the test cloth to make 1 kg, and 25 g of detergent (Super Zab: trade name)
Using an electric washing machine, bath volume 35 liters, liquid temperature 40
Treat at 10 ° C. for 10 minutes, rinse and air dry. The state of the remaining stain on the dried test cloth is compared with a judgment standard photographic plate, and the stain removal performance is indicated by an appropriate judgment grade (see Table 3).
The standard photographic plate was determined by AATCC-Test Method 130-
1970's were used.

[0031]

[Table 3] Judgment grade judgment standard 1.0 Those with significant stains 2.0 Those with considerable stains 3.0 Those with slight stains 4.0 Those with less noticeable stains 5. 0 No stain left 30 washes were performed according to JIS-L-1092.103.

Example 1 CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OCOCH = CH ₂
(Mixture of n = 3, 4, 5 in a weight ratio of 5: 3: 1)
20 g of a compound represented by (SFA), CH ₂ 2C (CH ₃ )
COO (CH ₂ CH ₂ O) ₉ CH ₃ (M-90G) 10 g, C
H ₂ ＣC (CH ₃ ) COO (CH ₂ CH (CH ₃ ) O) ₁₂ H (PP
_{-800) 4g, CH 3 COCH 2} COOCH 2 CH 2 OC
6 g of OCH = CH ₂ (AAEA), 0.08 g of 2-mercaptoethanol and 60 g of dipropylene glycol monomethyl ether were placed in a four-necked flask, and oxygen in the system was sufficiently replaced with nitrogen. A copolymerization reaction was carried out while adding 0.2 g of nitrile and stirring at 80 ° C. for 8 hours. Gas chromatography showed that the conversion of the copolymerization reaction was 97% or more. From this conversion, it was found that the ratio of each structural unit in the obtained copolymer almost coincided with the ratio of the charged monomers.
At the end of the polymerization reaction, deionized water was charged and diluted so that the concentration of the copolymer became 20%. The average molecular weight of the copolymer was 15000 (in terms of polystyrene) according to gel permeation chromatography.

Test Example 1 8% of the copolymer solution of Example 1, Sumitex Resin N
S-19 (Glyoxal resin, Sumitomo Chemical Co., Ltd.) 8
%, Sumitex Accelerator X-80 (Catalyst, Sumitomo Chemical Co., Ltd.) was diluted with water to a ratio of 2.4% to prepare a treatment bath. Dip a 35% cotton, 65% polyester blended broad cloth or a cotton broad cloth into this, and squeeze it with a roll to obtain a wet pickup of 55%.
%, 60%. Next, the cloth was dried at 110 ° C. for 2 minutes and heat-treated at 160 ° C. for 1 minute to complete the water / oil / oil repellent / antifouling treatment. The water-repellent, oil-repellent and soil-removal properties of the thus treated fabric were measured at the initial stage (before washing) and after washing 30 times. Table I shows the results for a 35% cotton and 65% polyester blended cloth, and Table II shows the results for a cotton broad cloth.

Examples 2 to 8 The procedure of Example 1 was repeated except that the monomers shown in Table 4 were used to obtain a copolymer solution. Table I shows the composition and average molecular weight of the copolymer.

Test Examples 2 to 8 Except that the copolymer solutions obtained in Examples 2 to 8 were used, a treatment bath was prepared in the same manner as in Test Example 1, and a water / oil / oil repellent / antifouling treatment was carried out in the same manner. Was evaluated. The results are shown in Tables I and II.

Comparative Examples 1 to 4 The procedure of Example 1 was repeated, except that the monomers shown in Table 4 were used, to obtain a solution of the copolymer. A treatment bath was prepared for each of them in the same manner as in Test Example 1 and subjected to water / oil / oil repellent / antifouling treatment in the same manner, and the same performance evaluation was performed. The results are shown in Tables I and II.

Comparative Example 5 CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OC was placed in a glass autoclave equipped with a thermocouple thermometer and a stirrer.
OCH = CH ₂ (n = 3, 4, 5 weight ratio of compounds 5: 3:
1 mixture) (SFA) 50 parts by weight, stearyl acrylate (StA) 40 parts by weight, CH ₃ COCH ₂ CO
5 parts by weight of OCH ₂ CH ₂ OCOCH ＝ CH ₂ (AAEA), 3 parts by weight of octadecyltrimethylammonium chloride, 7 parts by weight of polyoxyethylene nonylphenyl ether, 20 parts by weight of dipropylene glycol monomethyl ether, 0 parts by weight of lauryl mercaptan To the mixture, 1.1 parts by weight and 188 parts by weight of deionized water were added, and the mixture was emulsified with a high-pressure homogenizer at a temperature of 60 ° C. and a pressure of 400 kg / cm ² to obtain a milky white emulsion. Further, after adding 5 parts by weight of vinyl chloride (VCl) from the cylinder and sufficiently replacing with nitrogen, 2,2′-azobis (2-methylpropionamidine) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.)
V-50) was added and the polymerization was started. The polymerization reaction was performed at 60 ° C. for 15 hours. Gas chromatography showed that the conversion of the copolymerization reaction was 96% or more. At the end of the polymerization reaction, deionized water was charged and diluted so that the solid content concentration became 20%.
A treatment bath was prepared in the same manner as in Test Example 1, and water-repellent, oil-repellent, and antifouling treatment was performed in the same manner, and the same performance evaluation was performed. The results are shown in Tables I and II.

Comparative Example 6 The procedure of Comparative Example 5 was repeated, except that the monomers shown in Table I were used, to obtain an emulsion of a copolymer. A treatment bath was prepared in the same manner as in Test Example 1, and water-repellent, oil-repellent, and antifouling treatment was performed in the same manner, and the same performance evaluation was performed. The results are shown in Tables I and II.

[0039]

[Table 4]

[0040]

[Table 5]

[0041]

[Table 6]

[0042]

[Table 7]

In Tables I and II, the abbreviations have the following meanings. SFA is CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OCO
CH = CH ₂ (mixture of compounds with n = 3, 4, 5 in a weight ratio of 5: 3: 1) BrFA is (CF ₃ ) ₂ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ O
COCH = CH ₂ (n = 3, 4, 5: 5: 3: 1 mixture by weight)

PE-350 has a structure of CH ₂ ＣC (CH ₃ ) COO.
(CH ₂ CH ₂ O) ₉ HM-90G is CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH ₂ O)
₉ CH ₃ PP-500 is CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH
(CH ₃ ) O) ₈ HPP-800 is CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH
(CH ₃ ) O) ₁₂ H HCPMA is 3-chloro-2-hydroxypropyl methacrylate GLM is glycerol monomethacrylate N-MAM is N-methylol acrylamide THFA is tetrahydrofurfuryl acrylate AAEA is acetoacetoxyethyl acrylate AAEMA Is acetoacetoxyethyl methacrylate StA is stearyl acrylate VCl is vinyl chloride

[0045]

The antifouling agent using the copolymer of the present invention has a very high durability against soil release as compared with conventional antifouling agents.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09K 3/00 112 C09K 3/00 112D 3/18 102 3/18 102

Claims (5)

[Claims] 1. A structural unit derived from (a) a polymerizable monomer having a polyfluoroalkyl group, (b) a polyalkylene glycol (meth) acrylate, and (c) a polymerizable monomer having an acetoacetyl group. Having an average molecular weight of 1,000 to 500,000 as an essential component. 2. The monomer (a) having the formula: Embedded image Embedded image Embedded image [Wherein, Rf is a polyfluoroalkyl group having 3 to 21 carbon atoms, R ¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ²
Is an alkylene group having 1 to 10 carbon atoms, R ³ is hydrogen or a methyl group, Ar is an arylene group which may have a substituent, and n is an integer of 1 to 10. ] The copolymer according to claim 1 which is a polyfluoroalkyl group-containing (meth) acrylate represented by any one of the above. 3. A polyalkylene glycol (meth) acrylate (b) having the formula: CH ₂ ＣＲCR ¹¹ COO— (R ¹² O) _n —R ^{13 wherein} R ¹¹ and R ¹³ are hydrogen or methyl, R
¹² represents an alkylene group having 2 to 6 carbon atoms, and n represents an integer of 3 to 50. The copolymer according to claim 1, which is a compound represented by the formula: 4. The copolymer according to claim 1, wherein the monomer (c) is acetoacetoxyethyl acrylate and / or acetoacetoxyethyl methacrylate. 5. An antifouling agent containing the copolymer according to claim 1 as an active ingredient.