JPH08333546A - Coating composition - Google Patents

Abstract

PURPOSE: To obtain a coating composition consisting of a specific organopolysiloxane compound, an ultraviolet radiation absorbing agent and a radically copolymerizable monomer, having an excellent ultraviolet radiation absorbing capacity (in other words, weather resistance), surface smoothness and water repellency simultaneously. CONSTITUTION: This coating composition contains a copolymer obtained by copolymerizing (A) 5-69wt.% organopolysiloxane compound of formula I (R<1> is H or methyl; R<2> is a 1-22C divalent hydrocarbon which may contain O atom in its carbon chain; R<3> is a 1-6C monovalent hydrocarbon; m is 0-2; n is 10<=n<=200), (B) 1-40wt.% ultraviolet radiation absorbing agent having a radically copolymerizable group selected from acroyl group, methacroyl group, styryl group, allyl group, 3-butenyl group and 4-pentenyl group, preferably a compound of formula II (R<4> , R<7> are each an organic group containing the radically copolymerizable group, and others are H, a 1-8C alkyl, etc.), and (C) 30-49wt.% radically copolymerizable monomer selected from an acrylic acid ester, a methacrylic acid ester, styrene and their derivatives.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coating composition having both ultraviolet absorption (providing ultraviolet resistance), surface lubricity and water repellency.

[0002]

BACKGROUND OF THE INVENTION Benzotriazole-based, benzophenone-based, and diketone-based ultraviolet absorbers have been added to various plastic materials and various coating agents for the purpose of imparting weather resistance. In the case of a coating agent, it is necessary that it has film-forming properties and that the ultraviolet absorber stays in the coating film.
Therefore, a method has been proposed in which an acrylic resin copolymerized with an ultraviolet absorber is used and applied to a plastic material to improve the ultraviolet resistance for a long period of time (JP-A-4-106161).
(See the official gazette). However, this has no surface lubricity or water repellency, so that its field of use is limited. Further, in the cosmetics field, the ultraviolet absorbent has skin irritation, and is hardly soluble in an oil agent such as silicone oil or squalane as a component.
A method of improving skin irritation and solubility by modifying the ultraviolet absorber with silicone (for example, Japanese Examined Patent Publication No. 5-5856,
Japanese Patent Laid-Open No. 2-75634) are proposed. However, such a silicone-modified ultraviolet absorber has poor film-forming properties and cannot maintain long-term ultraviolet absorbability.
Further, silicone-based water-repellent agents are often used in the field of water repellents for fibers, but improvement in ultraviolet absorption is required.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and combines film forming properties, long-term UV absorption (providing UV resistance), surface smoothness, and water repellency. It has been made in an attempt to provide a coating composition of the above.

[0004]

The coating composition of the present invention has solved the above-mentioned problems, and has the general formula (A) 1

Embedded image (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a divalent hydrocarbon group having 1 to 12 carbon atoms which may contain an oxygen atom in the carbon chain,
R ³ is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms, m
Represents an integer of 0 to 2, and n represents an integer of 10≤n≤200. Organopolysiloxane compound represented by 5) to 69% by weight, and (B) UV absorption having a radical copolymerizable group selected from acryloyl group, methacryloyl group, styryl group, allyl group, 3-butenyl group and 4-pentenyl group. 1 to 40% by weight of an agent and (C) a copolymer obtained by copolymerizing 30 to 94% by weight of a radical copolymerizable monomer selected from acrylic acid ester, methacrylic acid ester, styrene and derivatives thereof. It is characterized by that. The present invention will be described in detail below.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The copolymer which is essential in the coating composition of the present invention is a copolymer of (A) to (C) as described above. Among these, the organopolysiloxane compound (A) (hereinafter referred to as a radical-polymerizable silicone macromonomer) is represented by the general formula 1,
This is a general formula

[Chemical 6] (In the formula, R ¹ , R ² , R ³ , and m are the same as above.) And a general formula of a (meth) acrylate-substituted chlorosilane compound.

[Chemical 7] (In the formula, R ³ and n have the same meanings as described above.) A terminal hydroxyl group-containing dimethylpolysiloxane compound is subjected to a dehydrochlorination reaction by a conventional method.

The above-mentioned (meth) acrylate-substituted chlorosilane compound and the general formula

Embedded image It can also be obtained by subjecting a dimethylpolysiloxane compound having a terminal lithium represented by the formula (wherein R ³ and n are the same as above) to a dechlorination reaction according to a conventional method.

Furthermore, one Si-H bond is added to the terminal or chain.
It can also be obtained by subjecting dimethylpolysiloxane having R ³ at the terminal to allyl (meth) acrylate, 2-allyloxyethyl (meth) acrylate or the like to a hydrosilylation reaction in the presence of a platinum catalyst. But,
The method for synthesizing the radically polymerizable silicone macromonomer is not limited to these.

A specific example of R ² in the general formula 1 is-(CH ₂ ).
_3- , -CH ₂ CH (CH ₃ ) CH ₂ -,-(CH ₂ ) ₆ -,-(CH ₂ ) ₂ O (CH ₂ ) ₃ -,-
(CH ₂ ) ₂ O (CH ₂ ) ₂ O (CH ₂ ) _3- and the like, and specific examples of R ³ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a phenyl group, and a tri group. Examples thereof include fluoropropyl group and the like. The repeating number n of siloxy units is 10 to 200. When n is less than 10, the performance as silicone, that is, slipperiness and water repellency becomes poor, and when it exceeds 200, the copolymer becomes cloudy. This is because it is not preferable.

Specific examples of the radical-polymerizable silicone macromonomer represented by the general formula 1 include the following, but the invention is not limited thereto.

[Chemical 9]

[0010]

[Chemical 10]

The radical-polymerizable silicone macromonomer used in the present invention has a diphenylsiloxy unit, a phenylmethylsiloxy unit, a methylvinylsiloxy unit and a trifluorosiloxy unit in the dimethylpolysiloxane chain within the range not impairing the object of the present invention. It may contain propylmethylsiloxy units, trimethylsiloxymethylsiloxy units and the like. In particular, the trifluoropropylmethylsiloxy unit has the advantage that the water repellency and the stain resistance are remarkably improved by containing the trifluoropropylmethylsiloxy unit. In order to introduce the siloxy unit, the terminal hydroxyl group-containing dimethylpolysiloxane compound, the terminal lithium dimethylpolysiloxane compound, the dimethylpolysiloxane compound having one Si—H bond at the terminal or in the chain is used as the raw material. The siloxy unit may be introduced by a known method.

As the ultraviolet absorber (B), those represented by the following general formulas 2 to 4 are preferable.

[Chemical 11] (In the formula, at least one of R ^{4 to} R ⁷ or R ^{4 to} R ⁶ is a radical copolymerizable group selected from acryloyl group, methacryloyl group, styryl group, allyl group, 3-butenyl group and 4-pentenyl group. Group-containing organic group, other is hydrogen atom, alkyl group having 1 to 8 carbon atoms, aralkyl group, aryl group, alkoxy group, aralkoxy group, aryloxy group, hydroxy group, halogen group, sulfonic acid group, sulfonic acid ester Group, a carboxy group, a carboxylic acid ester group, a phosphoric acid group, and a same or different atom or group selected from a phosphoric acid ester group.) Incidentally, at least one of R ^{4 to} R ⁷ or R ^{4 to} R ^6. Is industrially preferably an organic group containing an acryloyl group or a methacryloyl group.

Specific examples of the ultraviolet absorbers represented by the general formulas 2 to 4 include the following, but the invention is not limited thereto.

[Chemical 12]

[0014]

[Chemical 13]

[0015]

Embedded image

As the radical copolymerizable monomer (C), acrylic acid ester, methacrylic acid ester, styrene and derivatives thereof are preferable, and one or two thereof are preferable.
More than one seed is used. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate and n-.
Alkyl (meth) acrylates such as butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-
Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate; trifluoropropyl (meth) acrylate, perfluorobutylethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate Fluorine-substituted alkyl (meth) acrylates such as; glycidyl (meth) acrylate, epoxy group-containing (meth) acrylates such as 3,4′-epoxycyclohexylmethyl (meth) acrylate; styrene, α-
Methylstyrene, 4-methylstyrene, 3-methylstyrene, 4-vinylanisole, 2-chlorostyrene, 3
Examples include styrenes such as -chlorostyrene and 4-chlorostyrene.

Further, radical copolymerizable monomers other than those described above can be copolymerized within a range that does not impair the effects of the present invention. Examples of such a monomer include acids such as maleic acid, fumaric acid, acrylic acid and methacrylic acid; acrylamides such as acrylamide and N-methylolacrylamide; 3-trimethoxysilylpropyl (meth) acrylate, 3- Triethoxysilylpropyl (meth) acrylate, 3-dimethoxymethylsilylpropyl (meth) acrylate, vinyltriethoxysilane, 4-vinylphenyltrimethoxysilane, vinylmethyldimethoxysilane, 4-trimethoxysilyl-1
Radical polymerizable silane compounds such as butene and 6-trimethoxysilyl-1-hexene; acrylonitrile, vinyl pyridine, vinyl pyrrolidone, vinyl acetate, vinyl alkyl ethers, polyoxy having one radical polymerizable group in the molecule Radical-polymerizable macromonomers such as alkylene and polycaprolactone are included.

Further, it is also possible to use an antioxidant or a light stabilizer having radical copolymerizability for the purpose of further improving weather resistance. As such, 2, 2,
6,6-Tetramethyl-4-piperidinyl acrylate, 2,2,6,6-Tetramethyl-4-piperidinyl methacrylate, 1,2,2,6,6-Pentamethyl-
4-piperidinyl acrylate, 1,2,2,6,6-
Examples include pentamethyl-4-piperidinyl methacrylate and the like.

The compounding ratio in the copolymerization of the radically polymerizable silicone macromonomer (A), the ultraviolet absorber (B) and the radical copolymerizable monomer (C) described above is (A) / ( B) / (C) = (5 to 69) / (1 to 4)
0) / (30 to 94) (wt%). If the compounding amount of (A) is less than 5% by weight, the lubricity and water repellency will be poor, and if it exceeds 69% by weight, the film will be soft and the transparency will be poor. If the blending amount of (B) is less than 1% by weight, ultraviolet absorption becomes insufficient, and if it exceeds 40% by weight, the solubility becomes poor and the film becomes whitened, which is not preferable. If the content of (C) is less than 30% by weight, the film-forming property becomes poor, and if it exceeds 94% by weight, the properties of the acrylic resin become close to those of the acrylic resin itself, and the water repellency and the ultraviolet absorptivity are deteriorated.

As the polymerization initiator for copolymerizing (A) to (C), a usual radical polymerization initiator can be used, and organic peroxides such as benzoyl peroxide, dicumyl peroxide and lauroyl peroxide can be used. Goods; 2,
2'-azobis- (2-methylbutyronitrile), 2,
Examples thereof include azo compounds such as 2'-azobisisobutyronitrile. For the copolymerization, either a solution polymerization method or a bulk polymerization method can be applied. in this case,
As the molecular weight modifier, a chain transfer agent such as butyl mercaptan, dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, carbon tetrachloride or α-methylstyrene dimer may be used.

Solvents used in the case of the solution polymerization method include aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate, n-butyl acetate, isobutyl acetate and the like. Examples thereof include alcohols such as ethanol, isopropanol, n-butanol, and isobutanol. These solvents may be used alone or in combination of two or more.

The polymerization temperature is preferably in the range of 50 to 180 ° C., particularly 60 to 120 ° C. Under this temperature condition, the polymerization reaction can be completed in about 5 to 10 hours. The polystyrene produced weight average molecular weight of the copolymer thus produced by GPC is 5,000 to 500,000, particularly 10,000 to 10
It is preferably in the range of 10,000. Weight average molecular weight
If it is less than 5,000, the film strength is low and it becomes brittle.
When it exceeds 0, the viscosity of the copolymer solution becomes high, and the coating property deteriorates, which causes a problem in workability.

The copolymerization of (A) to (C) can be carried out by suspension polymerization or emulsion polymerization in an aqueous medium. In the case of emulsion polymerization, for example, a surfactant is added to the mixture of (A) to (C), the mixture is emulsified and dispersed in an aqueous medium, and then copolymerized in a state of emulsion dispersion using a water-soluble radical polymerization initiator. You can do it. Examples of the surfactant used include alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, alkylnaphthalene sulfonates, polyoxyethylene alkylaryl ether sulfonate monoester sodium, sodium lauryl sulfate and the like. Examples of the water-soluble radical polymerization initiator include inorganic peroxides such as potassium persulfate and sodium persulfate, organic peroxides such as t-butylperoxymaleic acid, succinic acid peroxide, and t-butylhydroperoxide. , 2'-Azobis- (2-N-benzylamidino) propane hydrochloride, 2,2'-azobis- [2-
(N-2-hydroxyethyl) amidino] propane,
Examples are azobis compounds such as 2,2′-azobis- (2-methyl-N-hydroxyethyl) propionamide.

Various coating compositions containing the copolymer produced as described above have excellent ultraviolet absorption,
Shows surface lubricity and water repellency. For example, a solution or emulsion of the copolymer can be used as the coating agent having the above characteristics. Further, the dispersion medium can be removed by spray drying, concentration under reduced pressure or the like to obtain a fine particle copolymer, and the copolymer can be added to cosmetics or the like to impart the above properties. As a specific example of the coating agent, the surface of various powders can be coated with a solution or emulsion of a copolymer to obtain a powder having high weather resistance, lubricity and water repellency. These treated powders can be used as pigments for cosmetics and paints. In addition, a water repellent agent for fibers containing this copolymer, car wax, etc. are excellent in the above-mentioned characteristics, and in various plastic surface protective coating agents, ultraviolet ray shielding agents, further hair care products, foundation products, etc. Is also the same.

[0025]

EXAMPLES Next, examples of the present invention will be described. All parts in the examples represent parts by weight. Example 1 A four-necked flask equipped with a cooling tube, a nitrogen introducing tube, a thermometer, and a stirrer was charged with 200 parts of isopropyl alcohol, 40 parts of methyl methacrylate, and a formula.

[Chemical 15] Radical polymerizable silicone macromonomer 40
Part, formula

Embedded image 20 parts of 2-hydroxy-5-methacryloxyethyl benzotriazole and 2,2'-azobis- (2
-Methylbutyronitrile) 2 parts, and under a nitrogen stream,
After polymerizing at 80 ° C. for 10 hours, 500 parts of methyl ethyl ketone was added to obtain a copolymer solution A. This solution A was applied to a glass plate and the physical properties of the dry film were measured, and the results are shown in Table 1. Further, isopropyl alcohol and methyl ethyl ketone were removed from the solution A, the obtained solid was dissolved in chloroform, and the ultraviolet absorption spectrum was measured.
It was shown to.

Example 2 2-hydroxy-5-methacryloxyethyl benzotriazole in Example 1 was replaced by the formula

[Chemical 17] A copolymer was prepared in the same manner as in Example 1 except that 2-hydroxy-4-methacryloxyethoxybenzophenone shown in was replaced by a copolymer solution B. The film physical properties were measured in the same manner as in Example 1, and the results are shown in Table 1.

Example 3 The 2-hydroxy-5-methacryloxyethylbenzotriazole in Example 1 was replaced by the formula

Embedded image A copolymer solution C was obtained in the same manner as in Example 1 except that the compound represented by The film physical properties were measured in the same manner as in Example 1, and the results are shown in Table 1.

Example 4 The 2-hydroxy-5-methacryloxyethylbenzotriazole in Example 1 was replaced by the formula

[Chemical 19] A copolymer solution D was obtained in the same manner as in Example 1 except that 2-hydroxy-4-acryloxyethoxybenzophenone represented by The film physical properties were measured in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 A copolymer solution E was prepared in the same manner as in Example 1 except that 60 parts of methyl methacrylate and 0 part of 2-hydroxy-5-methacryloxyethylbenzotriazole were used in Example 1. Obtained. The film physical properties were measured in the same manner as in Example 1,
The results are shown in Table 1.

Comparative Example 2 A copolymer solution F was obtained in the same manner as in Example 1 except that the radical-polymerizable silicone macromonomer in Example 1 was changed to 0 part and the methyl methacrylate was changed to 80 parts. The film physical properties were measured in the same manner as in Example 1, and the results are shown in Table 1.

[0031]

[Table 1]

The method for measuring the physical properties of the film is as follows. Contact angle of water: Kyowa Interface Science contact angle meter
Measured by. Dynamic friction coefficient: Measured by Kyowa Interface Science Co., Ltd. dynamic friction coefficient measuring device. (Friction element: SUS Ball, speed: 20 cm / min, load: 50 g) Accelerated weathering test: Iwasaki Electric Super UV tester was used. 10 cycles

[0033]

Industrial Applicability According to the present invention, a coating composition having excellent ultraviolet absorption (that is, weather resistance), surface lubricity and water repellency is provided. This property makes it possible to provide coating compositions which are very useful in a wide range of fields.

[Brief description of drawings]

FIG. 1 is a diagram showing an ultraviolet absorption spectrum of a solid chloroform solution obtained in Example 1.

Claims (4)

[Claims] 1. (A) General formula 1 (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a divalent hydrocarbon group having 1 to 12 carbon atoms which may contain an oxygen atom in the carbon chain,
R ³ is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms, m
Represents an integer of 0 to 2, and n represents an integer of 10≤n≤200. Organopolysiloxane compound represented by 5) to 69% by weight, and (B) UV absorption having a radical copolymerizable group selected from acryloyl group, methacryloyl group, styryl group, allyl group, 3-butenyl group and 4-pentenyl group. 1 to 40% by weight of an agent and (C) a copolymer obtained by copolymerizing 30 to 94% by weight of a radical copolymerizable monomer selected from acrylic acid ester, methacrylic acid ester, styrene and derivatives thereof. A coating composition comprising: 2. The coating composition according to claim 1, wherein the ultraviolet absorber (B) is represented by the following general formula 2. Embedded image (In the formula, at least one of R ^{4 to} R ⁷ is an organic group containing a radical copolymerizable group according to claim 1, and the others are hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, aralkyl groups, and aryl groups. Same or different atom selected from alkoxy group, aralkoxy group, aryloxy group, hydroxy group, halogen group, sulfonic acid group, sulfonic acid ester group, carboxy group, carboxylic acid ester group, phosphoric acid group and phosphoric acid ester group Or is a group.) 3. The coating composition according to claim 1, wherein the ultraviolet absorber (B) is represented by the following general formula 3. Embedded image (In the formula, at least one of R ^{4 to} R ⁶ is an organic group containing a radical copolymerizable group according to claim 1, and the others are hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, aralkyl groups, and aryl groups. Same or different atom selected from alkoxy group, aralkoxy group, aryloxy group, hydroxy group, halogen group, sulfonic acid group, sulfonic acid ester group, carboxy group, carboxylic acid ester group, phosphoric acid group and phosphoric acid ester group Or is a group.) 4. The coating composition according to claim 1, wherein the ultraviolet absorber (B) is represented by the following general formula 4. [Chemical 4] (In the formula, at least one of R ^{4 to} R ⁷ is an organic group containing a radical copolymerizable group according to claim 1, and the others are hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, aralkyl groups, and aryl groups. Same or different atom selected from alkoxy group, aralkoxy group, aryloxy group, hydroxy group, halogen group, sulfonic acid group, sulfonic acid ester group, carboxy group, carboxylic acid ester group, phosphoric acid group and phosphoric acid ester group Or is a group.)