JP3300424B2 - New copolymer and antifouling agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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 durability against water- and oil-repellent washing, copolymers comprising a fluorine-containing compound, a (meth) acrylate ester containing a hydroxyl group, and optionally an alkyl (meth) acrylate have been developed (for example, JP-B-50-3798, U.S. Pat. No. 3,356,628.
No.).

[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 soil release property and repellency. Although the water and oil repellency are somewhat good, the soil release and the durability of the water repellency are insignificant and not satisfactory. To solve such issues, we
Previously (a) a (meth) acrylate having a fluoroalkyl group, (b) a polyalkylene glycol (meth) acrylate, (c) a (meth) acrylate having a hydroxyl group, and (d) an alkyl (meth) acrylate Alternatively, a copolymer containing a constitutional unit derived from butadiene was found, and a tentative solution was found (Japanese Patent Laid-Open No. Hei 3-
No. 103411). Unfortunately, there is still room for improvement in durability,
I am not satisfied enough.

[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) an acrylate or methacrylate having a fluoroalkyl group, (b) a polyalkylene glycol acrylate or a polyalkylene glycol methacrylate, and (c) 3-chloroamine. -2-hydroxypropyl acrylate or 3-chloro-2-hydroxypropyl methacrylate, and (d) a copolymer having a molecular weight of 1,000 to 500,000, containing a structural unit derived from glycerol monoacrylate or glycerol monomethacrylate. Another gist of the present invention resides in an antifouling agent containing the copolymer as an active ingredient.

[0007] The monomers providing each structural unit will be described below. Monomer (a), in general, the formula: RfROCOR ¹ C = CH ₂ [wherein, Rf is a linear or branched perfluoroalkyl group having 3 to 20 carbon atoms, R ¹ is a hydrogen atom or a methyl radical, R is a linear or branched alkylene group having 1 to 10 carbon ^{_{atoms, -SO 2 N (R 2)}} R 3
A group (R ² is an alkyl group having 1 to 10 carbon atoms,
R ³ represents a linear or branched alkylene group having 1 to 10 carbon atoms. ) Or -CH ₂ CH (OR ⁴⁾ C
Represents an H ₂ — group (R ⁴ represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms). ] It is a compound shown by these.

Specific examples of the monomer (a) are shown below. CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₁₀ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₆ CH ₂ OCOC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₈ (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 ) ₆ (CH ₂ ) ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₂ H ₅ ) (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH (OCOCH ₃ ) CH ₂ OCOC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH (OH) CH ₂ OCOCH = CH ₂

The monomer (b) has the formula: CH ₂ ＣＲCR ⁵ COO- (R ⁶ O) _n -R ^{7 wherein} R ⁵ and R ⁷ are hydrogen or methyl, R ⁶
Represents an alkylene group having 2 to 6 carbon atoms, and n represents an integer of 3 to 50. ] Is preferable.

As R ⁶ , -CH ₂ CH _2- is usually preferable, but -CH (CH ₃ ) CH _2- , -CH (C ₂ H ₅ ) CH
_2- and so on. That is, in the present invention, polyethylene glycol acrylate or methacrylate in which R ⁶ is —CH ₂ CH ₂ — can be particularly preferably used. 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. Of course, it may be in the form of a mixture of two or more kinds of R ⁶ and different n.

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) 3-chloro-2-hydroxypropyl (meth) acrylate has the formula:

Embedded image Wherein R ⁸ is a hydrogen atom or a methyl group. ].

The glycerol mono (meth) acrylate of the monomer (d) has the formula:

Embedded image Wherein R ⁹ is a hydrogen atom or a methyl group. ].

In the copolymer of the present invention, a (meth) acrylic ester having a fluoroalkyl group (monomer
The copolymerization ratio of (a)) is at least 25% by weight, preferably 30 to 70% by weight. If it is less than 25% by weight, the water / oil repellency is not sufficient.

The copolymerization ratio of the polyalkylene glycol (meth) acrylate (monomer (b)) is at least 15% by weight, preferably 20 to 60% by weight. 15% by weight
If it is less than 1, the dispersibility in water is not good, and the durability is not sufficient.

The copolymerization ratio of 3-chloro-2-hydroxypropyl (meth) acrylate (monomer (c)) is at least 0.5% by weight, preferably 0.5 to 30% by weight. Glycerol mono (meth) acrylate (monomer
The copolymerization ratio of (d)) is at least 0.5% by weight, preferably 0.5 to 30% by weight.

The total copolymerization ratio of 3-chloro-2-hydroxypropyl (meth) acrylate (monomer (c)) and glycerol mono (meth) acrylate (monomer (d)) is at least 5% by weight. , Preferably 8 to 30% by weight
It is preferable that If it is less than 5% by weight, the soil release property and durability are not sufficient. The ratio of 3-chloro-2-hydroxypropyl (meth) acrylate to the total of the monomer (c) and the monomer (d) is 10 to 90.
%, More preferably 20-80% by weight. If the content is less than 10% by weight or more than 90% by weight, the durability is not sufficient.

The molecular weight of the copolymer of the present invention is from 1,000 to 1,000.
500,000, preferably 5,000 to 200,000. If it is less than 1,000, the durability is not sufficient, and 50,000
If it is 0 or more, the viscosity of the treatment liquid is too high, and the workability is reduced.
The 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 comprises a monomer (a),
In addition to (b), (c) and (d), 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 ether In addition to water and oil repellency, durability and flexibility, copolymerization is achieved by copolymerizing a polymerizable compound that does not contain a fluoroalkyl group such as isoprene, chloroprene, maleic anhydride, and butadiene. It can be coalesced, or its solubility, water pressure resistance and other various properties can be improved as appropriate. The amount of these copolymerizable compounds not containing a fluoroalkyl group is from 0 to 40% by weight, preferably from 0 to 20% by weight.
% By weight.

In order to obtain the copolymer of the present invention, various polymerization 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 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. The polymerizable compound as a raw material can be dissolved in an appropriate organic solvent and subjected to solution polymerization by the action of a polymerization initiation source (eg, a peroxide, an azo compound, or ionizing radiation soluble in the organic solvent to be used).

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 method of attaching and drying on the surface of the object to be treated by a known method of coating such as dip coating may 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 and the like as additives.

[0023]

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).

[0025]

[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

[0026]

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-

In addition, 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 soil removal performance is indicated by an appropriate judgment grade (see Table 3). The standard photographic plate was determined by AATCC-Test method 13
0-1970 was used.

[0028]

[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

Example 1 CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OCOC (CH ₃ ) =
CH ₂ a compound represented by (n = 3, 4, 5 the weight ratio of the compound of the 5: 3: 1 _{mixture) 20g, CH 2 = C (} CH 3) COO
(CH ₂ CH ₂ O) ₉ CH ₃ 10 g, CH ₂ ＣC (CH ₃ ) COO
5 g of (CH ₂ CH (CH ₃ ) O) ₁₂ H, CH ₂ ＣC (CH ₃ ) CO
4 g of OCH ₂ CH (OH) CH ₂ Cl, CH ₂ ＣC (CH ₃ ) C
1 g of OOCH ₂ CH (OH) CH ₂ OH and 60 g of isopropanol were placed in a four-necked flask, and oxygen in the system was sufficiently replaced with nitrogen.
g was added and a copolymerization reaction was carried out while stirring at 70 ° C. for 10 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, a further 40 g of isopropanol,
60 g of deionized water was charged and diluted. The resulting copolymer solution contained 19.5% copolymer solids. Further, the molecular weight of the copolymer was 12000 (in terms of styrene) according to gel permeation chromatography.

Test Example 1 The copolymer dispersion of Example 1 was mixed with a copolymer solid content of 0.6.
The dilution was adjusted with water so as to be% by weight. A PET pongee cloth was immersed in this, squeezed with a roll, and the wet pickup was adjusted to 80%. Next, it was dried at 110 ° C. for 2 minutes, and further heat-treated at 180 ° C. for 30 seconds to complete the water / oil / oil repellent / antifouling treatment. For the cloth treated in this way,
The water repellency, oil repellency, and soil release properties were measured at the initial stage and after performing the same washing five times as in the soil release performance test. Table 4 shows the results.

Example 2 In the same manner as in Example 1, CF ₃ CF ₂ (CF ₂ CF ₂ ) nCH ₂
20 g of a compound represented by CH ₂ OOCCH ＝ CH ₂ (a mixture of n = 3, 4, 5 in a weight ratio of 5: 3: 1), and CH ₂ =
8 g of C (CH ₃ ) COO (CH ₂ CH ₂ O) ₆ H, CH ₂ ＣC (C
H ₃ ) COO (CH ₂ CH (CH ₃ ) O) ₁₂ H 7 g, CH ₂ ＣC
(CH ₃ ) COOCH ₂ CH (OH) CH ₂ Cl ₄ g, CH ₂ ＣC
1 g of (CH ₃ ) COOCH ₂ CH (OH) CH ₂ OH was copolymerized. The resulting dispersion contained 19.5% copolymer solids. Table 4 shows the composition and molecular weight of the copolymer.

Examples 3 to 7 The same procedure as in Example 1 was repeated except that the monomers shown in Table 4 were used, to obtain a dispersion of the copolymer. Table 4 shows the composition and molecular weight of the copolymer.

Test Examples 2 to 7 The dispersions prepared in Examples 2 to 7 were mixed with a copolymer solid of 0.6.
The dilution was adjusted with water so as to be% by weight. A PET pongee cloth was treated in the same manner as in Test Example 1 using these diluents. The treated fabric had the properties shown in Table 4.

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 dispersion of the copolymer. Table 4 shows the results of the evaluation of the dispersion in the same manner as in Example 1.

Example 8 CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OCOC (CH ₃ ) =
CH ₂ a compound represented by (n = 3, 4, 5 the weight ratio of the compound of the 5: 3: 1 _{mixture) 18g, CH 2 = C (} CH 3) COO
(CH ₂ CH ₂ O) ₉ CH ₃ 10 g, CH ₂ ＣC (CH ₃ ) COO
7 g of (CH ₂ CH (CH ₃ ) O) ₉ H, CH ₂ ＣC (CH ₃ ) CO
4 g of OCH ₂ CH (OH) CH ₂ Cl, CH ₂ ＣC (CH ₃ ) C
OOCH ₂ CH (OH) CH ₂ OH 1g, deoxygenated pure water 7
0 g, 80 g of isopropanol, and 0.04 g of n-laurylmercaptan in a glass four-necked flask equipped with a mercury thermometer and a polytetrafluoroethylene crescent-shaped impeller, and stirred under a nitrogen stream. Well dispersed. Furthermore, after blowing nitrogen for about 1 hour, 0.4 g of azobisisobutylamidine hydrochloride was used.
Was dissolved in 10 g of water, and the mixture was stirred at 60 ° C. for 10 hours under a nitrogen stream to carry out a copolymerization reaction. Conversion rate of copolymerization reaction was 99% by gas chromatography.
It was shown above. 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. The resulting dispersion contained 20% copolymer solids. Table 5 shows the composition and molecular weight of the copolymer.

Test Example 8 The copolymer dispersion of Example 7 was mixed with a copolymer solid content of 0.6.
The dilution was adjusted with water so as to be% by weight. 35 cotton
% And 65% of polyester were immersed and squeezed with a roll to obtain a wet pickup of 80%. Then 1
The antifouling treatment was completed by drying at 05 ° C for 3 minutes and further heat-treating at 150 ° C for 3 minutes. The water-repellent, oil-repellent and soil-removing properties of the cloth thus treated were measured at the initial stage and after the same washing was performed five times as in the soil-removing performance test. Table 5 shows the results.

Example 9 Similar to Example 8, CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ C
14 g of a compound represented by H ₂ OCOCH ＝ CH ₂ (a mixture of compounds having a weight ratio of 5: 3: 1 of n = 3, 4, 5), and CH ₂ ＣC
(CH ₃ ) COO (CH ₂ CH ₂ O) ₉ H 11 g, CH ₂ ＣC (C
_{H 3) COO (CH 2 CH} (CH 3) O) 12 H 10g, CH 2 =
C (CH ₃ ) COOCH ₂ CH (OH) CH ₂ Cl ₄ g, CH ₂ =
1 g of C (CH ₃ ) COOCH ₂ CH (OH) CH ₂ OH was copolymerized. The resulting dispersion contained 19.8% copolymer solids. Table 5 shows the composition and molecular weight of the copolymer.

Examples 10 to 13 The procedure of Example 8 was repeated except that the monomers shown in Table 5 were used to obtain a dispersion of the copolymer. Table 5 shows the composition and molecular weight of the copolymer.

Test Examples 9 to 13 The dispersions of the copolymers produced in Examples 9 to 13 were diluted with water so that the copolymer solid content was 0.6% by weight. Using these diluents, 35% cotton as in Test Example 8,
A mixed fabric of 65% polyester was treated. The treated fabric had the properties shown in Table 5.

Comparative Examples 5 to 10 The procedure of Example 8 was repeated, except that the monomers shown in Table 5 were used, to obtain a dispersion of the copolymer. Table 5 shows the results of the evaluation of the dispersion in the same manner as in Example 8.

[0041]

[Table 4]

[0042]

[Table 5]

In Tables 4 and 5, 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) SFMA is a compound of CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OC
OC (CH ₃ ) = CH ₂ (n = 3, 4, 5: 5: 3: 1 mixture by weight) BrFA is (CF ₃ ) ₂ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ O
COCH = CH ₂ (mixture of compounds with n = 3, 4, 5 in a weight ratio of 5: 3: 1) PE-200 is CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH ₂
O) ₆ H

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-700 is CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH
(CH ₃ ) O) ₉ 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 BAMA is CH ₂ ＣC (CH ₃ ) -CO-NH -CH ₂ O
-C ₄ H ₉ THFA is tetrahydrofurfuryl acrylate

[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.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Tsujimoto 4-231-1, Bunkyo, Fukui City, Fukui Prefecture Within Nichika Chemical Co., Ltd. (72) Inventor Motonobu Kubo 1-1-1, Nishiichitsuya, Settsu City, Osaka Daiki (72) Inventor Norimasa Uesugi 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (56) References JP-A-3-103411 (JP, A) JP Hei 4-68006 (JP, A) JP-A-59-98113 (JP, A) JP-A-64-56711 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 220 / 00-220/70 D06M 15/277 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. An acrylic or methacrylic ester having a fluoroalkyl group, (b) a polyalkylene glycol acrylate or a polyalkylene glycol methacrylate, (c) 3-chloro-2-hydroxypropyl acrylate or 3-chloro. -2-hydroxypropyl methacrylate, and (d) a molecular weight of 100 containing a constituent unit derived from glycerol monoacrylate or glycerol monomethacrylate
0 to 500,000 copolymer. 2. An antifouling agent containing the copolymer according to claim 1 as an active ingredient.