JP2000034464A - Ultraviolet-absorbing formed article and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a formed article which has a layer having ultraviolet- absorbing ability, providing good effects on substrate protection, yellowing prevention, or the like and excellent in long-term weatherability, gloss, and solvent resistance by forming the layer from a copolymer formed by copolymerizing an ultraviolet-absorbing monomer, an unsatd. monomer, and an ultraviolet-stable monomer. SOLUTION: The layer is formed from a copolymer formed by copolymerizing an ultraviolet-absorbing monomer of formula I, an unsatd. monomer of formula II, and an ultraviolet-stable monomer of formula III and/or IV. In the formulas, R1 is H or a 1-8C hydrocarbon group; R2 is a 1-6C alkylene; R3 is H or methyl; X is H, a halogen, a 1-8C hydrocarbon group, a 1-4C alkoxy, cyano, or nitro; R10 is H or a 1-2C hydrocarbon group; Z is a (substd.) cycloalkyl; R6 is H or cyano; R7 and R8 are each H or a 1-2C hydrocarbon group; R9 is H or a 1-18C hydrocarbon group; and Y is oxygen or imino. After the layer is formed on the cavity surface of a mold by copolymerizing the monomers thereon, a substrate material is molded in the mold, thus giving an objective formed article having the layer transferred to the surface thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet-absorbed processed product having a copolymer layer having excellent ultraviolet-absorbing ability, excellent long-term weather resistance, and excellent gloss, water resistance and solvent resistance. It relates to a manufacturing method.

[0002]

2. Description of the Related Art Generally, for example, ABS (acrylonitrile-butadiene-styrene) resin, FRP (fiber reinforced plastic), PET (polyethylene terephthalate), polystyrene, PP (polypropylene), PC
Molded articles (processed articles) made of various plastics (substrates) such as (polycarbonate) and acrylic resin, when exposed to ultraviolet rays for a long time outdoors or the like, cause deterioration such as yellowing. Therefore, conventionally, the above-described deterioration is prevented by laminating a resin film having weather resistance on the surface of these molded products.

[0003]

However, the above-mentioned conventional resin film has a certain degree of weather resistance when exposed to ultraviolet rays for a short period of time, but has a certain degree of weather resistance when exposed to ultraviolet rays for a long period of time. Has a deterioration such as yellowing, and its weather resistance is insufficient. That is, the above-mentioned conventional resin film has a problem that the undercoat protection effect and the yellowing prevention effect are poor and the long-term weather resistance is poor.

Therefore, for example, Japanese Patent Application Laid-Open No. 4-31754 discloses the use of a fluororesin composition obtained by copolymerizing a benzotriazole-based ultraviolet-absorbing monomer and a fluorine-containing monomer. It has been proposed to impart weatherability to molded articles. However, the fluororesin composition is inferior in adhesiveness and adhesiveness to a molded plastic. Further, the fluororesin composition has a problem that it is expensive and is easily stained (easily stained).

Therefore, it has an ultraviolet absorbing ability, is excellent in long-term weather resistance, has good adhesion and adhesion to a substrate such as plastic, and is excellent in gloss, water resistance, solvent resistance and the like. There is a need for an ultraviolet-absorbing processed product having a coating (copolymer layer) and a method for producing the same.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and has as its object to have an ultraviolet absorbing ability, a good underlayer protection effect and a good yellowing prevention effect, and excellent long-term weather resistance. Another object of the present invention is to provide a UV-absorbed processed product having a copolymer layer having excellent gloss, water resistance, solvent resistance, and the like, and a method for producing the same.

[0007]

Means for Solving the Problems In order to achieve the above object, the inventors of the present invention have made intensive studies on an ultraviolet-absorbing processed product and a method for producing the same, and as a result, an ultraviolet-absorbing monomer having a specific structure, A copolymer obtained by copolymerizing an unsaturated monomer having a specific structure and a monomer composition containing an ultraviolet light-stable monomer having a specific structure has an ultraviolet absorbing ability, In addition to excellent weather resistance, it has been found that it has good adhesion and adhesion to the substrate, as well as an effect of protecting the underlayer and preventing yellowing, and has excellent gloss, water resistance, solvent resistance, etc. Was. That is, the ultraviolet-absorbing processed product having the copolymer layer has ultraviolet-absorbing ability, is excellent in long-term weather resistance, and is found to be excellent in gloss, water resistance, solvent resistance, etc. It was completed. Also,
After forming the above-mentioned copolymer layer on the molding surface of the mold, the above-mentioned mold is used to mold a substrate to be a processed product, and the above-mentioned performance is obtained by transferring the copolymer layer to the substrate side. It has been found that a UV-absorbing processed product having a copolymer layer having a smooth surface can be easily produced, and the present invention has been completed.

That is, in order to solve the above-mentioned problem, the ultraviolet absorbing processed product of the invention according to claim 1 has the general formula (1)

[0009]

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(Wherein R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms)
8 represents a hydrocarbon group, R ² represents a linear or branched alkylene group having 1 to 6 carbon atoms, R ³ represents a hydrogen atom or a methyl group, X represents a hydrogen atom or a halogen group. , A hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group), and a general formula (2)

[0011]

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(Wherein R ¹⁰ is a hydrogen atom or a group having 1 to 1 carbon atoms)
2 represents a hydrocarbon group, and Z represents a cycloalkyl group which may have a substituent);
General formula (3)

[0013]

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(Wherein, R ⁶ represents a hydrogen atom or a cyano group, R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, and R ⁹ represents a hydrogen atom or a carbon atom. Represents a hydrocarbon group of the formulas 1 to 18, Y represents an oxygen atom or an imino group) and / or a general formula (4)

[0015]

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(Wherein, R ⁶ represents a hydrogen atom or a cyano group, R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, and Y represents an oxygen atom or an imino group. And a copolymer layer obtained by copolymerizing a monomer composition containing an ultraviolet-stable monomer represented by the following formula:

[0017] Further, a method of manufacturing an ultraviolet-absorbing processed product according to the second aspect of the present invention is intended to solve the above problems.
After forming a copolymer layer obtained by copolymerizing the monomer composition according to claim 1 on a molding surface of a mold, a base material to be a processed product is formed using the mold, and a base material is formed. The method is characterized in that the copolymer layer is transferred to the side.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION A UV-absorbing processed product according to the present invention comprises a UV-absorbing monomer represented by the general formula (1) and an unsaturated monomer represented by the general formula (2). And a UV-stable monomer represented by the general formula (3) and / or
Alternatively, it has a copolymer layer obtained by copolymerizing a monomer composition containing the ultraviolet-stable monomer represented by the general formula (4). The above-mentioned monomer composition may contain a monomer other than each of the above monomers, if necessary, an acidic functional group-containing monomer, a hydroxyl group-containing monomer.

The ultraviolet absorbing monomer represented by the general formula (1) according to the present invention (hereinafter referred to as the ultraviolet absorbing monomer (1)) is a substituent represented by R ¹ in the formula. There is constituted a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ²
Is a linear or branched alkylene group having 1 to 6 carbon atoms, the substituent represented by R ³ is a hydrogen atom or a methyl group, and the substituent represented by X is Benzotriazoles whose group is a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group.

Specific examples of the ultraviolet absorbing monomer (1) include, for example, 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2-
[2'-hydroxy-5 '-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyhexyl) phenyl] -2H-benzotriazole, 2- [2 '-Hydroxy-3'-
t-butyl-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-
t-butyl-3 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-
(Methacryloyloxyethyl) phenyl] -5-chloro
-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-methoxy-2
H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl ] -5-t-butyl-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole, and the like, but are not particularly limited. Not something. One of these ultraviolet absorbing monomers (1) may be used alone, or two or more thereof may be appropriately mixed and used.

The unsaturated monomer represented by the above general formula (2) according to the present invention, wherein the substituent represented by R ¹⁰ is a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms. , Z is a compound composed of a cycloalkyl group which may have a substituent. The cycloalkyl group in the substituent represented by Z is, for example, a monocyclic saturated hydrocarbon residue such as a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group. And
The cycloalkyl group may have an alkyl group having 1 to 7 carbon atoms as a substituent. Specific examples of the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, and a heptyl group.

Specific examples of the unsaturated monomer (hereinafter, referred to as a cycloalkyl group-containing monomer) include, for example, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl Examples thereof include (meth) acrylate and cyclododecyl (meth) acrylate, but are not particularly limited. As the cycloalkyl group-containing monomer, only one type may be used, or two or more types may be appropriately mixed and used.

The present invention is represented by the above general formula (3).
UV-stable monomer (hereinafter referred to as UV-stable monomer)
(Described as (3)) is a compound represented by the formula:⁶The substituent represented by is hydrogen
Consisting of an atom or a cyano group,⁷, R⁸Indicated by
The substituents are each independently a hydrogen atom or carbon number 1-2
R comprises⁹The substituent represented by is hydrogen
Composed of an atom or a hydrocarbon group having 1 to 18 carbon atoms;
The substituent shown is composed of an oxygen atom or an imino group
Piperidines. R above⁷, R⁸A substituent represented by
Specifically, for example, a hydrogen atom, a methyl group or
An ethyl group, ⁹The substituent represented by is specifically
Represents, for example, a methyl group, an ethyl group, a propyl group,
Propyl group, butyl group, isobutyl group, t-butyl group, pen
Tyl, hexyl, heptyl, octyl, nonyl
Group, decyl group, undecyl group, dodecyl group, tridecyl
Group, tetradecyl group, pentadecyl group, hexadecyl
Group, heptadecyl group, octadecyl group, etc.
Is a branched hydrocarbon residue.

The above-mentioned UV-stable monomer (3) is, for example, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyl Amino-2,2,6,6-tetramethylpiperidine, 4-
(Meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6
-Pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-
Examples include crotonoyloxy-2,2,6,6-tetramethylpiperidine and 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, but are not particularly limited. As the UV-stable monomer (3), only one kind may be used, or two or more kinds may be appropriately mixed and used.

The UV-stable monomer represented by the general formula (4) according to the present invention (hereinafter referred to as UV-stable monomer (4)) has a substituent represented by R ⁶ in the formula. Is a hydrogen atom or a cyano group, and the substituents represented by R ⁷ and R ⁸ are each independently a hydrogen atom or a carbon atom having 1 to 2 carbon atoms.
And the substituent represented by Y is a piperidine comprising an oxygen atom or an imino group. The substituents represented by R ⁷ and R ⁸ are specifically, for example, a hydrogen atom, a methyl group or an ethyl group.

Specific examples of the above-mentioned UV-stable monomer (4) include, for example, 1- (meth) acryloyl-4-
(Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1 -Crotonoyl-4-crotonoyloxy-2,2,6,6
-Tetramethylpiperidine and the like, but are not particularly limited. As the UV-stable monomer (4), only one kind may be used, or two or more kinds may be appropriately mixed and used.

Further, the above-mentioned monomers (that is, the ultraviolet-absorbing monomer (1), the cycloalkyl group-containing monomer,
Monomers other than the UV-stable monomers (3) and (4)), that is, acidic functional group-containing monomers and hydroxyl group-containing monomers contained as necessary in the monomer composition; The monomers other than the acidic functional group-containing monomer and the hydroxyl group-containing monomer (hereinafter, referred to as other monomers) are added to a copolymer layer obtained by copolymerizing the monomer composition. Any compound that does not impair the required various physical properties may be used.

Specific examples of the acidic functional group-containing monomer include (meth) acrylic acid, crotonic acid,
Carboxyl group-containing unsaturated monomers such as itaconic acid, maleic acid, and maleic anhydride; sulfonic acid group-containing unsaturated monomers such as vinyl sulfonic acid, styrene sulfonic acid, and sulfoethyl (meth) acrylate; 2- (meth) Unsaturated acidic phosphate esters such as acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3-chloropropyl acid phosphate, and 2-methacryloyloxyethyl phenyl phosphate Examples thereof include, but are not particularly limited to, monomers. One kind of these acidic functional group-containing monomers may be used alone, or two or more kinds thereof may be appropriately mixed and used.

Specific examples of the hydroxyl group-containing monomer include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and caprolactone-modified hydroxy (meth) acrylate (for example, manufactured by Daicel Chemical Industries, Ltd.). Trade name (Placcel FM), mono (meth) acrylate of polyester diol obtained from phthalic acid and propylene glycol, and the like, but are not particularly limited thereto. One of these hydroxyl group-containing monomers may be used alone, or two or more of them may be appropriately mixed and used.

Specific examples of the other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl. (Meth) acrylate alkyl esters such as (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; epoxy such as glycidyl (meth) acrylate Group-containing monomers; Nitrogen-containing monomers such as (meth) acrylamide, N, N'-dimethylaminoethyl (meth) acrylate, vinylpyridine, vinylimidazole; halogen-containing monomers such as vinyl chloride and vinylidene chloride; Styrene, α-methylstyrene, bi Aromatic monomers such as Rutoruen; vinyl esters such as vinyl acetate; vinyl ethers; but (meth) polymerizable cyanide such as acrylonitrile and the like, but is not particularly limited. As the other monomer, only one kind may be used as necessary, or two or more kinds may be appropriately mixed and used.

The UV-absorbed processed product according to the present invention comprises:
It has a copolymer layer obtained by copolymerizing the above monomer composition. The method for forming the above-mentioned copolymer layer is not particularly limited. For example, by preparing a coating composition obtained by adding a crosslinking agent to a polymer composition containing a copolymer obtained by copolymerizing a monomer composition, and applying the coating composition or the like. A copolymer layer may be formed, or, after the coating composition is once formed into a film, the film may be fused, thermocompression bonded or bonded to form a copolymer layer, Furthermore, after a copolymer layer is once formed on the molding surface of the mold, the copolymer layer may be transferred to the substrate side.

Hereinafter, the coating composition for forming the copolymer layer will be described. First, a monomer composition containing an ultraviolet absorbing monomer (1), a cycloalkyl group-containing monomer, an ultraviolet stable monomer (3) and / or an ultraviolet stable monomer (4) An emulsion type coating composition (hereinafter referred to as coating composition (a)) obtained by emulsion polymerization of a product will be described.

In the coating composition (a), the content of each of the above monomers in the monomer composition is not particularly limited, but the content of the ultraviolet absorbing monomer (1) is 0.1% by weight. % To 30% by weight, preferably 1% to 20% by weight.
Is more preferable, and the range of 2 to 15% by weight is particularly preferable. The content of the cycloalkyl group-containing monomer is preferably in the range of 2% by weight to 95% by weight, and is preferably 5% by weight.
More preferably, it is in the range of from about 85% by weight to about 85% by weight, and particularly preferably in the range of from 10% by weight to 75% by weight. The combination of the ultraviolet absorbing monomer (1) and the cycloalkyl group-containing monomer in the monomer composition is not particularly limited.

By setting the content of the ultraviolet absorbing monomer (1) in the above range, it is possible to impart an ultraviolet absorbing ability to the coating film composed of the coating composition (a). Further, the dispersibility of an acidic pigment such as carbon black in the coating composition (a) and the stability of color mixing when a composite pigment is used can be improved. Further, by setting the content of the cycloalkyl group-containing monomer within the above range,
Performance such as long-term weather resistance, water resistance, gloss, and sharpness can be imparted to a coating film composed of the coating composition (a). In addition, beautiful feeling can be imparted to the coating film.

When the content of the ultraviolet absorbing monomer (1) in the monomer composition is less than 0.1% by weight, the resulting coating composition (a), that is, the ultraviolet absorbing ability of the coating film Is unsatisfactory. Further, when the content is more than 30% by weight, the appearance of the coating film composed of the coating composition (a), for example, the gloss and the sharpness are inferior, and the solvent resistance and chemical resistance are low. It is not preferable because the performance is lowered. Further, when the content is more than 30% by weight, polymerization stability at the time of emulsion polymerization becomes poor and aggregates may be increased.

When the content of the monomer having a cycloalkyl group in the monomer composition is less than 2% by weight, the coating film obtained when the obtained coating composition (a) is used as an emulsion coating Is not preferable because of poor performance such as weather resistance, gloss and hardness. Further, when the content is more than 95% by weight, the flexibility of the coating film composed of the coating composition (a) becomes poor, and the coating film is liable to crack due to aging, which is preferable. Absent.

Further, the above-mentioned UV-stable monomer (3)
The total amount of (4) is preferably in the range of 0.1% by weight to 15% by weight, more preferably in the range of 0.5% by weight to 10% by weight, and particularly preferably in the range of 1% by weight to 5% by weight. By setting the total amount of the UV-stable monomers (3) and (4) within the above range, the UV-absorbing ability of the coating film composed of the coating composition (a) can be maintained for a long time.
These UV-stable monomers (3) and (4) are used within a range that does not impair the physical properties of the coating composition (a) obtained. In addition, the weight ratio of the UV-stable monomer (3), the UV-stable monomer (4) and the cycloalkyl group-containing monomer in the monomer composition is not particularly limited.

When the total amount of the UV-stable monomers (3) and (4) in the monomer composition is less than 0.1% by weight, the weather resistance of the coating film comprising the coating composition (a) is reduced. May be reduced. On the other hand, when the total amount is more than 15% by weight, there is a possibility that a coating film comprising the coating composition (a) may have poor performance such as water resistance, gloss and sharpness.

The above-mentioned UV-absorbing monomer (1), cycloalkyl group-containing monomer, UV-stable monomer (3)
(4) The method of mixing the other monomer and the functional group-containing monomer (described later) is not particularly limited. For example, the above monomers may be mixed in advance before the emulsion polymerization, or the above monomers may be mixed in the reaction solution during the emulsion polymerization. In short, it is only necessary that the above monomers are charged in the reactor during the emulsion polymerization.

In the method for producing the coating composition (a), as an emulsifier for emulsion-polymerizing the above monomer composition, for example, an anionic surfactant, a nonionic surfactant, a cationic surfactant All conventionally known surfactants such as surfactants, amphoteric surfactants, and polymer surfactants can be used. Further, a polymer and / or a salt thereof described below can be used as an emulsifier. The polymerization method and reaction conditions of the emulsion polymerization will be described later.

Examples of the anionic surfactant include, for example, alkali metal alkyl sulfates such as sodium dodecyl sulfate and potassium dodecyl sulfate; ammonium alkyl sulfates such as ammonium dodecyl sulfate; sodium dodecyl polyglycol ether sulfate; Folicinoate; alkali metal salts of sulfonated paraffins, alkyl sulfonates such as ammonium salts of sulfonated paraffins; fatty acid salts such as sodium laurate, triethanolamine oleate, triethanolamine aviate; sodium dodecylbenzene sulfonate, alkali phenol Alkyl aryl sulfonates such as alkali metal sulfates of hydroxyethylene; high alkyl naphtha Nsuruhon salts; naphthalenesulfonic acid-formalin condensate; dialkyl sulfosuccinate, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylaryl sulfate salts.

Examples of the nonionic surfactant include, for example, polyoxyethylene alkyl ether; polyoxyethylene alkyl aryl ether; sorbitan fatty acid ester; polyoxyethylene sorbitan fatty acid ester; glycerol monolaurate and the like. Fatty acid monoglyceride; oxyethylene-oxypropylene copolymer; condensation products of ethylene oxide with aliphatic amines, amides or acids.

As the polymer surfactant, specifically,
For example, polyvinyl alcohol; sodium poly (meth) acrylate, potassium poly (meth) acrylate, ammonium poly (meth) acrylate, polyhydroxyethyl (meth) acrylate, polyhydroxypropyl (meth) acrylate; Examples include copolymers of two or more types of polymerizable monomers as structural units; or copolymers of a polymerizable monomer as a structural unit of these polymers with another monomer.

One of these surfactants may be used alone, or two or more of them may be appropriately mixed and used. Furthermore, so-called phase transfer catalysts such as crown ethers can also be used as emulsifiers.

In the method for producing the coating composition (a), an acid is obtained by polymerizing a monomer component containing an unsaturated carboxylic acid in the presence of an alkyl mercaptan having 6 to 18 carbon atoms as an emulsifier. Water-soluble or water-dispersible polymer having a terminal alkyl group of 200 mgKOH / g or more
It is more preferable to use a polymer having a terminal alkyl group) and / or a salt thereof. When the terminal alkyl group-containing polymer and / or salt is used as an emulsifier, the monomer composition further includes a functional group-containing monomer having a functional group having reactivity to a carboxyl group. It is preferable to include. The functional group-containing monomer will be described later.

By using the above-mentioned polymer having terminal alkyl group and / or salt as an emulsifier, a coating film which is excellent in initial drying property and further excellent in performance such as long-term weather resistance, water resistance, gloss and sharpness. Can be produced, that is, a coating composition (a).

The above-mentioned polymer having a terminal alkyl group is intended to satisfy the polymerization stability during emulsion polymerization and the properties such as water resistance, solvent resistance and strength of the coating film composed of the coating composition (a). In addition, it is necessary that the acid value be 200 mg KOH / g or more, and that it be water-soluble or water-dispersible. The acid value of the terminal alkyl group-containing polymer is 200 mg KOH
If it is less than / g, sufficient emulsifying ability cannot be obtained, so that the polymerization stability at the time of emulsion polymerization becomes poor and aggregates are generated. Further, the storage stability of the obtained coating composition (a) is poor.

The molecular weight of the terminal alkyl group-containing polymer is preferably in the range of 300 to 7,000, more preferably in the range of 400 to 4,000. If the molecular weight is outside the above range, sufficient emulsifying ability cannot be obtained, resulting in poor polymerization stability during emulsion polymerization.

The unsaturated carboxylic acid used in the synthesis of the polymer having a terminal alkyl group is not particularly limited as long as it has a carboxyl group and / or a salt thereof and a polymerizable unsaturated group in the molecule. Not something. Specific examples of the unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid; monoesters and salts of these compounds. One kind of these unsaturated carboxylic acids may be used alone, or two or more kinds thereof may be appropriately mixed and used.

By polymerizing a monomer component containing an unsaturated carboxylic acid, a carboxyl group can be introduced into a polymer having a terminal alkyl group. This makes it possible to impart hydrophilicity to the terminal alkyl group-containing polymer. Further, the carboxyl group acts as a functional group when the coating composition (a) is cured.

The above-mentioned monomer component may contain only an unsaturated carboxylic acid, but may contain a monomer other than the unsaturated carboxylic acid, if necessary. The monomer is not particularly limited as long as it is a compound copolymerizable with the unsaturated carboxylic acid. As the monomer,
Specifically, for example, styrene, vinyl toluene, α-
Styrene derivatives such as methylstyrene, chloromethylstyrene, styrenesulfonic acid or a salt thereof; (meth) acrylamide, N-monomethyl (meth) acrylamide,
(Meth) acrylamide derivatives such as N-monoethyl (meth) acrylamide and N, N-dimethyl (meth) acrylamide; (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate ) (Meth) acrylic esters synthesized by an ester forming reaction between acrylic acid and an alcohol having 1 to 18 carbon atoms;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate; hydroxyl group-containing (meth) acrylic synthesized by ester-forming reaction of (meth) acrylic acid with polypropylene glycol or polyethylene glycol, etc. Acid esters; (meth)
Ethyl acrylate-2-sulfonate or a salt thereof, vinyl sulfonic acid or a salt thereof, vinyl acetate, (meth) acrylonitrile and the like. One of these monomers may be used alone, or two or more of them may be appropriately mixed and used.

The monomers other than the unsaturated carboxylic acid in the above-mentioned monomer components may be used within a range such that the acid value of the resulting polymer having a terminal alkyl group does not become less than 200 mg KOH / g. Further, the type and amount of the monomer are determined in consideration of the compatibility between the polymer component produced when emulsion polymerization is performed using the polymer having an alkyl terminal group and the polymer having an alkyl terminal group. It is preferable to select.

The alkyl mercaptan used in the synthesis of the terminal alkyl group-containing polymer may have 6 to 18 carbon atoms. As the alkyl mercaptan, specifically,
For example, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, cetyl mercaptan, stearyl mercaptan and the like can be mentioned. One of these alkyl mercaptans may be used alone, or two or more of them may be appropriately mixed and used. In addition, the polymer containing a terminal alkyl group obtained by using an alkyl mercaptan having 5 or less carbon atoms has poor polymerization stability during emulsion polymerization. Further, the storage stability of the obtained coating composition (a) is poor.

Alkyl mercaptan is a molecular weight regulator and is used for introducing a terminal alkyl group into a polymer obtained by polymerizing a monomer component. Then, by polymerizing the monomer component in the presence of the alkyl mercaptan, the molecular weight of the terminal alkyl group-containing polymer is reduced to 300 to 7,00.
In addition to being able to be adjusted within the range of 0, the polymer having a terminal alkyl group can be provided with surface activity.

The amount of the alkyl mercaptan to be used is determined based on the desired molecular weight of the polymer having a terminal alkyl group, but is usually in the range of 2 to 300 parts by weight based on 100 parts by weight of the monomer component. Should be inside.

The polymerization method for polymerizing the monomer component is as follows:
There is no particular limitation, and various conventionally known polymerization methods such as bulk polymerization, solution polymerization, and suspension polymerization can be employed.

When polymerizing the monomer component, a conventionally known oil-soluble or water-soluble polymerization initiator such as a radical polymerization initiator can be used. The amount of the polymerization initiator to be used is not particularly limited, so that the terminal alkyl group-containing polymer can be efficiently synthesized.
The amount is preferably 1 mol or less, more preferably 0.1 mol or less, per 1 mol of the alkyl mercaptan. Solvents that can be used when polymerizing the monomer component are particularly limited as long as the compound dissolves the monomer component, the alkyl mercaptan, and the polymerization initiator, and does not inhibit the polymerization reaction. is not.

The reaction temperature is not particularly limited, but is preferably in the range of 50 ° C. to 150 ° C. The reaction time may be appropriately set so that the polymerization reaction is completed, depending on the reaction temperature, or the composition of the monomer component used, the type of the alkyl mercaptan, the type of the polymerization initiator, and the like. A range of up to 8 hours is preferred.

Although the terminal alkyl group-containing polymer has sufficient surface activity, during the emulsion polymerization, some or all of the carboxyl groups of the terminal alkyl group-containing polymer are neutralized with a neutralizing agent. It is preferable that the terminal alkyl group-containing polymer is converted into a salt. By converting the terminal alkyl group-containing polymer into a salt, the polymerization stability during emulsion polymerization and the storage stability of the obtained coating composition (a) can be further improved.

As the above neutralizing agent, a conventionally known neutralizing agent can be used. Examples of the neutralizing agent include alkali metal compounds such as sodium hydroxide and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide and calcium carbonate; ammonia; monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, Triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine,
And water-soluble organic amines such as diethylenetriamine. These neutralizing agents may be used alone,
Further, two or more kinds may be appropriately mixed and used.

The functional group-containing monomer is not particularly limited as long as it has a functional group having a reactivity to a carboxyl group of the polymer having a terminal alkyl group. Specific examples of the functional group-containing monomer include epoxy group-containing monomers such as glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and allyl glycidyl ether; ) Aziridinyl group-containing monomers such as acryloylaziridine and 2-aziridinylethyl (meth) acrylate; 2-isopropenyl-2
-Oxazoline group-containing monomers such as oxazoline and 2-vinyl-2-oxazoline. One of these neutralizing agents may be used alone, or two or more of them may be used by appropriately mixing.

When the monomer composition contains a functional group-containing monomer, the content of the functional group-containing monomer is preferably in the range of 0.5% by weight to 40% by weight, more preferably 0.5% by weight to 15% by weight. More preferably, it is in the range of% by weight. When the content of the functional group-containing monomer in the monomer composition is less than 0.5% by weight, a part of the carboxyl groups of the terminal alkyl group-containing polymer used as the emulsifier remains in an unreacted state. At the same time, the resulting polymer becomes insufficiently crosslinked. For this reason,
It is not preferable because the properties such as initial drying property, water resistance, solvent resistance, and strength of the coating film composed of the coating composition (a) are poor.
On the other hand, when the content is more than 40% by weight, polymerization stability during emulsion polymerization becomes poor. Further, the storage stability of the obtained coating composition (a) is poor.

The reaction method for emulsion polymerization of the monomer composition is not particularly limited, and various conventionally known methods can be employed. For example, at the start of polymerization, a method of collectively mixing a monomer composition, a polymerization initiator, and the like with water and performing polymerization; a so-called monomer dropping method; a pre-emulsion method, and the like can be used. Further, by performing multi-stage polymerization such as so-called seed polymerization, core-shell polymerization, and power feed polymerization, it is also possible to form a hetero-phase structure of emulsion particles.

In emulsion polymerization of the monomer composition, a conventionally known polymerization initiator can be used. Specific examples of the above polymerization initiator include, for example, persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; and organic peroxides such as t-butyl hydroperoxide, benzoyl peroxide, and peracetic acid. Radical-forming azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2-methylpropionamidine) dihydrochloride; and hydrogen peroxide. A redox initiator may be used by using sodium hydrogen sulfite, L-ascorbic acid, or the like as a reducing agent together with these polymerization initiators. Incidentally, the amount of the polymerization initiator used,
There is no particular limitation.

The reaction temperature is not particularly limited, but is preferably in the range of 0 ° C. to 100 ° C., and more preferably in the range of 40 ° C. to 95 ° C. The reaction time may be appropriately set so that the polymerization reaction is completed, depending on the reaction temperature, or the composition of the monomer composition to be used, the type of the emulsifier or the polymerization initiator, and the like. About 10 hours are preferable.

When the monomer composition is emulsion-polymerized, a hydrophilic solvent or an additive may be added to the reaction system as long as various physical properties required for the coating film are not impaired. The monomer composition may be emulsion-polymerized in the absence of an emulsifier, depending on the reaction conditions for the emulsion polymerization.

The polymer composition obtained by the above-mentioned emulsion polymerization can be used as it is as a coating composition (a). Known additives such as a film-forming aid and a pigment , Filler, toner, wetting agent, antistatic agent,
An antifoaming agent, a viscosity controlling agent and the like can be blended as required. As the pigment, an inorganic pigment or an organic pigment can be used. Examples of the inorganic pigment include white pigments such as titanium oxide, antimony trioxide, zinc white, lithopone, and lead white; and color pigments such as carbon black, graphite, molybdenum red, red iron oxide, yellow iron oxide, and yellow flower. . Examples of the organic pigment include azo compounds such as benzidine and Hansa Yellow; and phthalocyanines such as phthalocyanine blue. One of these pigments may be used alone, or two or more of them may be appropriately mixed and used. The polymer composition obtained by the above emulsion polymerization,
Excellent pigment dispersibility.

As described above, the coating composition (a) comprises the ultraviolet absorbing monomer (1), the cycloalkyl group-containing monomer, the ultraviolet stable monomer (3) and / or the ultraviolet light It can be easily obtained by emulsion-polymerizing a monomer composition containing the stable monomer (4). The coating composition (a) comprises:
Excellent UV absorption in the wavelength range of 300 nm to 400 nm and long-term weather resistance, water resistance, gloss, sharpness, solvent resistance, chemical resistance, discoloration resistance, crack resistance, blister resistance A coating film excellent in properties and the like can be formed. Further, according to the above-mentioned method, the coating composition (a) capable of forming a coating film having more excellent performance can be easily produced.

Next, the UV-absorbing monomer (1), the cycloalkyl group-containing monomer, and the UV-stable monomer (3)
And / or a coating composition containing a copolymer obtained by copolymerizing a monomer composition containing an ultraviolet-stable monomer (4) and an acidic functional group-containing monomer (hereinafter, referred to as ultraviolet light) (Absorbent lacquer composition) will be described.

In the ultraviolet absorbing lacquer composition, the content of each monomer in the monomer composition is not particularly limited, but the ultraviolet absorbing monomer (1) is
It is preferably in the range of 0.1% to 30% by weight, and 1% to
It is more preferably in the range of 20% by weight, particularly preferably in the range of 2% to 15% by weight. Further, the content of the cycloalkyl group-containing monomer is preferably in the range of 2% by weight to 95% by weight,
It is more preferably in the range of 5% to 85% by weight, particularly preferably in the range of 10% to 75% by weight. The content of the acidic functional group-containing monomer is preferably in the range of 0.1% to 15% by weight, more preferably in the range of 0.2% to 10% by weight, and particularly preferably in the range of 0.5% to 5% by weight. preferable.

When the content of the ultraviolet absorbing monomer (1) in the monomer composition is less than 0.1% by weight, the ultraviolet absorbing ability of the obtained ultraviolet absorbing lacquer composition becomes insufficient, which is not preferable. . On the other hand, when the content is more than 30% by weight, the resulting UV-absorbing lacquer composition may have poor appearance such as gloss and sharpness, solvent resistance and chemical resistance. Absent.

When the content of the cycloalkyl group-containing monomer in the monomer composition is less than 2% by weight, the weather resistance, gloss and hardness of the coating film comprising the obtained ultraviolet absorbing lacquer composition And the like are not preferred because the performance becomes insufficient. On the other hand, if the content is more than 95% by weight, the flexibility of the coating film becomes poor, and the coating film is liable to crack due to aging, which is not preferable.

Further, the fact that the monomer composition contains a monomer having an acidic functional group is that the UV-absorbing lacquer composition has
It is extremely effective in imparting adhesion to a substrate, particularly a substrate made of metal, and dispersing pigment. That is, it is possible to improve the dispersibility of various pigments, the color mixing stability in a composite pigment system, and the like. When the content of the acidic functional group-containing monomer in the monomer composition is less than 0.1% by weight, it is not preferable because pigment dispersibility cannot be sufficiently imparted to the ultraviolet absorbing lacquer composition. On the other hand, if the content exceeds 15% by weight, disadvantages such as poor polymerization stability and reduced water resistance of the obtained copolymer occur, which is not preferable.

Further, the above-mentioned UV-stable monomer (3)
The total amount of (4) is preferably in the range of 0.1% by weight to 15% by weight, more preferably in the range of 0.5% by weight to 10% by weight, and particularly preferably in the range of 1% by weight to 5% by weight. By setting the total amount of the UV-stable monomers (3) and (4) within the above range, a UV-absorbing lacquer composition capable of maintaining the UV-absorbing ability for a long time can be obtained.

When the total amount of the UV-stable monomers (3) and (4) in the monomer composition is less than 0.1% by weight,
It is not preferable because the ultraviolet absorbing ability of the obtained coating film composed of the ultraviolet absorbing lacquer composition cannot be maintained for a long time. On the other hand, if the total amount exceeds 15% by weight, the resulting coating film comprising the UV-absorbing lacquer composition is inferior in water resistance, gloss, sharpness, etc., which is not preferable. In addition, these UV-stable monomers (3)
(4) and other monomers are used within a range that does not impair the physical properties of the obtained ultraviolet absorbing lacquer composition.

The above-mentioned UV-absorbing monomer (1), cycloalkyl group-containing monomer, acidic functional group-containing monomer, UV-stable monomers (3) and (4), and other monomers The method for mixing the monomers is not particularly limited. For example,
The above-mentioned monomers may be mixed before copolymerization, or may be mixed in the reaction solution when the above-mentioned monomers are copolymerized. In short, it is only necessary that the above monomers are charged in the reactor at the time of polymerization.

The polymerization method for copolymerizing the monomer composition is not particularly limited, and various polymerization methods known in the art, such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, A bulk polymerization method or the like can be employed. Solvents that can be used when the monomer composition is copolymerized by employing a solution polymerization method, for example, toluene,
Xylene and other high-boiling aromatic hydrocarbons; acetates such as ethyl acetate, butyl acetate and cellosolve acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; isopropanol, n-butanol and iso-
Aliphatic alcohols such as butanol; and alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and diethylene glycol monoethyl ether, but are not particularly limited. One of these solvents may be used alone, or two or more of them may be appropriately mixed and used. Further, the amounts of these solvents used are not particularly limited.

When copolymerizing the monomer composition, a polymerization initiator can be used. Specific examples of the above polymerization initiator include, for example, ordinary radical polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, and di-t-butyl peroxide, but are particularly limited. Not something. The amount of the polymerization initiator to be used is not particularly limited, but it is preferable to use the polymerization initiator in the range of 0.1% by weight to 10% by weight based on the total amount of the monomer composition.

The reaction temperature is not particularly limited, but is preferably in the range of room temperature to 200 ° C., more preferably in the range of 40 ° C. to 140 ° C. The reaction time may be appropriately set according to the reaction temperature, the composition of the monomer composition to be used, the type of the polymerization initiator, and the like so that the polymerization reaction is completed.

Further, in the reaction system, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, carbon tetrachloride, carbon tetrabromide, or a polymerization regulator may be used for the purpose of controlling the molecular weight.

When the obtained copolymer is used for a water-soluble or water-dispersible ultraviolet absorbing lacquer composition, the copolymer may be neutralized with a basic compound, if necessary. You may. Specific examples of the basic compound that can be used include, but are not particularly limited to, ammonia, triethylamine, morpholine, and sodium hydroxide.

Further, a differential scanning calorimeter (D
SC), the glass transition temperature (Tg)
It is preferable to design so as to be within the range of 20 ° C to 80 ° C, and it is more preferable to design so as to be within the range of 30 ° C to 70 ° C. When the glass transition temperature of the copolymer is less than 20 ° C., the coating film composed of the UV-absorbing lacquer composition containing the copolymer is too soft and cannot maintain durability for a long period of time. Is not preferred.
On the other hand, if the above glass transition temperature exceeds 80 ° C., the coating film is too hard and too brittle, so that it is not possible to sufficiently exhibit crack resistance and blister resistance.

The number average molecular weight (Mn) of the copolymer is 1
It is preferable to design so as to be in the range of from 000 to 40,000, and more preferably to be in the range of from 15,000 to 30,000. When the number average molecular weight is less than 10,000, it is not preferable because a coating film having sufficient durability cannot be obtained. On the other hand, the number average molecular weight is 40,0
If it exceeds 00, the polymerization stability is inferior, and the viscosity becomes too high, which results in the inconvenience of lack of suitability for coating work. Furthermore, even if the number average molecular weight is 10,000 or more, if the number average molecular weight is 5,000 or less components in the copolymer is 10% or more, it is not possible to obtain a coating film having sufficient durability, The disadvantage of lacking solvent resistance results. Therefore, in the copolymer, a component having a number average molecular weight of 5,000 or less is contained.
Preferably it is less than 10%.

The ultraviolet absorbing lacquer composition according to the present invention is a one-pack non-crosslinkable composition and can be used as it is as a coating composition. If necessary, an organic solvent and / or water, Agents, leveling agents, dispersants,
You may mix | blend and use additives for various coatings, such as a plasticizer, a stabilizer, a dye, and a pigment. Examples of the pigment used in the ultraviolet absorbing lacquer composition include the pigments described above. One of these various additives may be used alone, or two or more of them may be appropriately mixed and used. Further, the amounts of these additives used are not particularly limited.

The ultraviolet-absorbing monomer (1) has a polymerizable unsaturated double bond in the molecule, and is different from a monomer having a cycloalkyl group or a monomer having an acidic functional group. Copolymerize. Therefore, the obtained ultraviolet-absorbing copolymer has good compatibility between the monomers and no extractable unreacted ultraviolet-absorbing monomer (1), so that no elution or bleed-out occurs. , Its effect can be maintained for a long time. Further, coloring caused by the ultraviolet absorbing monomer (1) hardly occurs. For this reason, the ultraviolet absorbing lacquer composition containing the ultraviolet absorbing copolymer has the same performance as the ultraviolet absorbing copolymer.

Further, the ultraviolet absorbing lacquer composition comprises an ultraviolet absorbing monomer (1), a cycloalkyl group-containing monomer, an ultraviolet stable monomer (3) and / or an ultraviolet stable monomer. By dispersing various pigments such as carbon black by including an ultraviolet absorbing copolymer obtained by copolymerizing a monomer composition containing a monomer (4) and an acidic functional group-containing monomer; Also, the effect of improving the color mixing stability in the composite pigment system is remarkably exhibited. From this, it is also possible to disperse various pigments by a known pigment dispersion method to obtain a colored paint. By using the ultraviolet absorbing lacquer composition, a coating film excellent in performance such as weather resistance, gloss, hardness, crack resistance, water resistance and adhesion to a substrate can be obtained. That is, the ultraviolet-absorbing lacquer composition is remarkably excellent in maintaining the ultraviolet-absorbing ability for a long period of time and weather resistance, and has no elution, bleed-out, coloring and discoloration of the ultraviolet-absorbing component from the copolymer. Further, by using the ultraviolet absorbing lacquer composition, a coating film having excellent physical properties such as glossiness, sharpness, solvent resistance, chemical resistance and water resistance can be obtained. Further, the ultraviolet absorbing lacquer composition has excellent workability.

Next, the UV-absorbing monomer (1), the cycloalkyl group-containing monomer, and the UV-stable monomer (3)
And / or a coating composition obtained by copolymerizing a monomer composition containing a UV-stable monomer (4) and a hydroxyl group-containing monomer (hereinafter referred to as coating composition (b)) Will be described.

In the coating composition (b), the content of each of the above monomers in the monomer composition is not particularly limited, but the content of the ultraviolet absorbing monomer (1) is ,
It is preferably in the range of 0.1% to 30% by weight, and 1% to
It is more preferably in the range of 20% by weight, particularly preferably in the range of 2% to 15% by weight.

If the amount of the UV-absorbing monomer (1) in the monomer composition is less than 0.1% by weight, the UV-absorbing ability of the obtained coating composition (b) becomes insufficient. Not preferred. On the other hand, when the amount of the UV-absorbing monomer (1) is more than 30% by weight, the coating film composed of the coating composition (b) has insufficient gloss and solid feeling, resulting in poor appearance. In addition, the solvent resistance and the chemical resistance are inferior.

The content of the cycloalkyl group-containing monomer in the monomer composition is preferably in the range of 5% by weight to 98.9% by weight, more preferably in the range of 5% by weight to 80% by weight. Particularly preferred is in the range from 10% to 70% by weight.

When the amount of the cycloalkyl group-containing monomer in the monomer composition is less than 5% by weight, the gloss and the feeling of holding the coating film formed from the coating composition (b) are insufficient. Or the synergistic effect with the ultraviolet absorbing monomer (1) is weakened, and the weather resistance is not sufficiently exhibited, which is not preferred. On the other hand, when the amount of the cycloalkyl group-containing monomer is more than 98.9% by weight, the contents of the ultraviolet absorbing monomer (1) and the hydroxyl group-containing monomer become too small, and the The weather resistance of the coating film composed of (b) becomes insufficient,
It is not preferable because solvent resistance and chemical resistance are inferior.

The content of the hydroxyl group-containing monomer in the monomer composition is preferably in the range of 1% by weight to 45% by weight, more preferably in the range of 2% by weight to 40% by weight.
Particularly preferred is in the range of from 35% to 35% by weight.

When the amount of the hydroxyl group-containing monomer in the monomer composition is less than 1% by weight, the number of active hydroxyl groups contained in the obtained copolymer decreases, and the crosslink density decreases. Is not preferable because the coating film performance cannot be obtained. On the other hand, when the amount of the hydroxyl group-containing monomer is more than 45% by weight, the polymerization stability becomes poor and the water resistance of the obtained coating film is undesirably reduced. In addition, storage stability after blending a polyisocyanate compound or a modified product thereof described below, or an aminoplast resin or a block polyisocyanate compound described later is deteriorated, which is not preferable.

The amount of the UV-absorbing monomer (1), the amount of the cycloalkyl group-containing monomer, the amount of the UV-stable monomers (3) and (4) and the amount of the hydroxyl group-containing monomer in the monomer composition By setting the amount of the monomer in the above range, it is possible to form a coating film having excellent physical properties such as mechanical properties and acid resistance and long-term weather resistance from the obtained coating composition (b). it can.

The UV-stable monomers (3) and (4) are used within a total content of 20% by weight or less in the monomer composition.
The UV stability of the obtained coating composition (b) is sufficient, and long-term weather resistance is realized. The weight ratio of the UV-stable monomer (3) to the UV-stable monomer (4) is not particularly limited, and both may be used or only one may be used. It is particularly preferable to use only the UV-stable monomer (3).

When the above monomer composition is obtained, the UV-absorbing monomer (1), the cycloalkyl group-containing monomer, the hydroxyl group-containing monomer, the acidic functional group-containing monomer, and the UV-stable monomer The method of mixing the monomers (3) and (4) and other monomers is not particularly limited. That is, the method for preparing the monomer composition is not particularly limited.

The polymerization method for copolymerizing the monomer composition is not particularly limited, and various polymerization methods known in the art, such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, and the like. Although a polymerization method or the like can be employed, a solution polymerization method is preferably employed.

Solvents that can be used when the monomer composition is copolymerized by employing the solution polymerization method include the above-mentioned organic solvents and water, but are not particularly limited. One of these solvents may be used alone, or two or more of them may be appropriately mixed and used. Further, the amount of the solvent used is not particularly limited. However, in the case of blending a cross-linking agent comprising a polyisocyanate compound or a modified product thereof with the copolymer in the coating composition (b), among the organic solvents mentioned above, aliphatic alcohols, alkylene glycol monoalkyl Solvents that are active toward isocyanate groups, such as ethers and water, are not preferred.

Further, when copolymerizing the monomer composition, a polymerization initiator can be used. Examples of the polymerization initiator include, for example, 2,2′-azobis (2-methylbutyronitrile), t-butylperoxy-2-ethylhexanoate, 2,2′-azobisisobutyronitrile, Examples include ordinary radical polymerization initiators such as benzoyl peroxide and di-t-butyl peroxide, but are not particularly limited. Further, the amount of the polymerization initiator used is not particularly limited.

When copolymerizing the monomer composition, the reaction temperature is not particularly limited, but is preferably in the range of room temperature to 200 ° C., more preferably in the range of 40 ° C. to 140 ° C. . The reaction time may be appropriately set according to the reaction temperature, the composition of the monomer composition to be used, the type of the polymerization initiator, and the like so that the polymerization reaction is completed.

Further, in the reaction system, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, carbon tetrachloride, carbon tetrabromide or a polymerization regulator may be used for the purpose of controlling the molecular weight. That is, the molecular weight of the obtained copolymer is determined by the reaction time, reaction temperature, or the composition of the monomer composition to be used, the type of polymerization initiator, and, if necessary, a chain transfer agent or a polymerization regulator. It can be adjusted using an appropriate amount. The weight average molecular weight (Mw) of the copolymer thus obtained is preferably 2,000 to 300,000,
More preferably, it is 8,000 to 100,000.

The crosslinking agent to be incorporated into the coating composition (b) is not particularly limited as long as it has two or more functional groups capable of reacting with a hydroxyl group in one molecule.
In addition, as the crosslinking agent, only one type may be used, or two or more types may be appropriately mixed and used.

When a polyisocyanate compound having two or more isocyanate groups in one molecule or a modified product thereof is used as the above crosslinking agent, a two-part crosslinking type room temperature curing type curing at room temperature or a relatively low heating temperature. A coating composition is suitably obtained. When an aminoplast resin or a blocked polyisocyanate compound is used as the crosslinking agent, a one-part crosslinking type coating composition can be suitably obtained. In the following description, for convenience of description, when it is necessary to distinguish the coating composition (b) by a crosslinking agent, the coating composition using a polyisocyanate compound or a modified product thereof as a crosslinking agent is coated with the coating composition. Composition (b1)
And a coating composition using an aminoplast resin or a blocked polyisocyanate compound as a crosslinking agent is referred to as a coating composition (b2).

The polyisocyanate compound or a modified product thereof is not particularly limited as long as it has two or more isocyanate groups in the molecule. Examples of the polyisocyanate compound or a modified product thereof include trimethylene diisocyanate, 1,6-hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, meta-xylylene diisocyanate, and 4,4′-methylene bis. (Cyclohexyl isocyanate) and adduct polyisocyanate compounds such as trimethylolpropane adducts, burettes and isocyanurates which are derivatives of these diisocyanates. In the coating composition (b1), the blending amount of the polyisocyanate compound or its modified product with respect to the copolymer is not particularly limited.

Examples of the above aminoplast resins include aminoplast resins such as methyletherified melamine resin, butyletherified melamine resin, butyletherified benzoguanamine resin, butyletherified cyclohexylbenzoguanamine resin, and water-soluble products thereof. However, there is no particular limitation. These aminoplast resins may be used alone,
Further, two or more kinds may be appropriately mixed and used. In the above-mentioned coating composition (b2), the amount of the aminoplast resin or its water-soluble compound with respect to the copolymer is not particularly limited.

The above-mentioned blocked polyisocyanate compound is not particularly limited as long as it has two or more blocked isocyanate groups in the molecule. Examples of the blocked polyisocyanate compound include trimethylene diisocyanate, 1,6-hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, meta-xylylene diisocyanate, and 4,4′-methylene bis (cyclohexyl isocyanate). ) And trimethylolpropane adducts that are derivatives of these diisocyanates;
Adduct polyisocyanate compounds such as burettes and isocyanurates, that is, blocked polyisocyanates obtained by blocking the isocyanate group of the polyisocyanate compound or a modified product thereof with a compound such as ε-caprolactam, phenol, cresol, oxime, or alcohol. And the like. One of these blocked polyisocyanate compounds may be used alone, or two or more of them may be appropriately mixed and used. In the coating composition (b2), the blending amount of the blocked polyisocyanate compound with respect to the copolymer is not particularly limited.

Further, in addition to the copolymer and the crosslinking agent, the coating composition (b) may be used in a crosslinking reaction between a hydroxyl group in the copolymer and a crosslinking agent (for example, a urethanization reaction between a hydroxyl group and an isocyanate group). Known catalysts (e.g.,
Organic tin compounds such as di-n-butyltin dilaurate and tertiary amines), organic solvents, and various paint additives such as fillers, leveling agents, dispersants, plasticizers, stabilizers, dyes, and pigments. It may be included as appropriate.

Examples of the above-mentioned pigments include the pigments described above. One of these various additives may be used alone, or two or more of them may be appropriately mixed and used. Further, the amounts of these additives used are not particularly limited. The coating composition (b) can be used as a colored coating by dispersing various pigments by a known pigment dispersing method, and is excellent in dispersibility of a pigment such as carbon black. Also,
Also excellent in color mixing stability in the composite pigment system. In addition, the method of compounding the copolymer, the crosslinking agent, and the various additives is not particularly limited. In addition, the composition for coating (b2)
In, the copolymer may be in the form of a solution or dispersion, a powder, and a cross-linking agent or the like may be blended. Is preferred.

As described above, the coating composition (b) comprises an ultraviolet absorbing monomer (1), a cycloalkyl group-containing monomer, an ultraviolet stable monomer (3) and / or A crosslinking agent is mixed with a copolymer obtained by copolymerizing a monomer composition containing a stable monomer (4) and a hydroxyl group-containing monomer. The coating composition (b) is excellent in transparency, gloss, stickiness, mechanical strength, acid resistance, solvent resistance, etc.
It is particularly excellent in ultraviolet absorption in the wavelength region of 300 nm to 400 nm, hardly causes coloring due to the ultraviolet absorbing monomer (1), and retains gloss during long-term outdoor use.
A coating film excellent in long-term weather resistance such as discoloration resistance can be formed. The coating composition (b1) is obtained by blending a crosslinking agent comprising a polyisocyanate compound or a modified product thereof with the above copolymer. Therefore, it is possible to obtain a two-part crosslinkable room temperature-curable coating composition having excellent drying properties and coating workability. The coating composition (b2) is obtained by blending the above copolymer with a crosslinking agent comprising an aminoplast resin or a blocked polyisocyanate compound.
Accordingly, a one-part crosslinking type coating composition can be obtained.

As described above, the coating composition for forming the copolymer layer, that is, the coating composition (a).
(B) and an ultraviolet absorbing lacquer composition are obtained.
Next, a method for forming a copolymer layer using the above various coating compositions will be described.

The method for forming the copolymer layer is not particularly limited, and various conventionally known methods can be employed. That is, as a method for forming the copolymer layer, for example, a coating method such as brush coating, spray coating, roll coater coating, etc .; A method of laminating the base material with a film to form a copolymer layer by sticking or thermocompression bonding to the base material.

Next, the base material used for the ultraviolet absorbing product according to the present invention will be described. As the base material according to the present invention, for example, ABS (acrylonitrile-butadiene-styrene) resin, FRP (fiber reinforced plastic), PET (polyethylene terephthalate), polystyrene, PP (polypropylene), PC (polycarbonate), acrylic resin, Various plastics such as vinyl chloride resin and polyester resin; various metals such as steel plate; glass; wood such as hinoki and plywood, etc., are not particularly limited. Further, the shape and size of the substrate are not particularly limited.

The adhesion between the coating film composed of the coating composition and the substrate is good. Therefore, it is necessary to protect the substrate from ultraviolet rays by forming a copolymer layer on the surface of the substrate. Can be. Note that two or more copolymer layers having different compositions may be laminated on the surface of the base material. Further, another resin layer, an adhesive layer, a protective layer, a decorative layer, and the like (described later) may be laminated between the base material and the copolymer layer.

For example, when the base material is FRP, by forming a copolymer layer, even when the ultraviolet absorbent processed product is used for a long time, the glass fiber or calcium carbonate in the FRP can be used. No particles (filler) and the like are exposed on the surface of the processed product, and the weather resistance, solvent resistance, and the like are improved. Therefore, the UV-absorbing processed product can withstand long-term use, and is suitable for a wide range of uses, for example, containers such as tanks and containers, and various building materials.

For example, when the base material is PC or PET, by forming a colored copolymer layer,
The weather resistance and the solvent resistance of the UV-absorbing processed product are improved, and the base material, that is, the processed product surface can be easily colored. Further, for example, when the substrate is glass, by forming a colored copolymer layer,
The surface of the UV-absorbing processed product can be easily colored.

Next, regarding the method for producing a UV-absorbing processed product using the above-mentioned coating composition, a method of applying the coating composition; a method of forming the coating composition into a film and fusing; A method of forming a film of the composition for use and then thermocompression bonding; a method of transferring a copolymer layer using a mold will be described as an example.

First, a method for producing an ultraviolet-absorbing processed product by applying a coating composition will be described. As shown in FIG. 1, first, an adhesive is applied to the surface of a substrate 1 and dried at a predetermined temperature to form an adhesive layer 2.
To form Next, a decorative layer 3 made of, for example, decorative paper, titanium paper, wood board, or the like is laminated on the surface of the adhesive layer 2. That is, the decorative layer 3 is attached to the surface of the adhesive layer 2. In addition, substrate 1
The material of the decorative layer 3 is not particularly limited, and conventionally known materials can be used. The adhesive may be appropriately selected according to the materials of the base material 1 and the decorative layer 3, and is not particularly limited.

Next, a coating composition is applied to the surface of the decorative layer 3 and dried at room temperature or a predetermined temperature.
Alternatively, the copolymer layer 4 is baked at a relatively low temperature.
To form Thereby, an ultraviolet-absorbing processed product is manufactured. In addition, the above-mentioned composition for coating may be an optimal composition according to the material of the decorative layer 3 and the use of the ultraviolet absorbing processed product. The formation of the adhesive layer 2 and / or the decorative layer 3 may be omitted depending on the material of the base material 1 and the use of the ultraviolet absorbent processed product.

However, when the copolymer layer 4 is formed on the surface of the base material 1 and the base material 1 is made of polypropylene, a primer is applied to the surface of the polypropylene before forming the copolymer layer 4. It is preferable to apply. The above-mentioned primer may be uniformly applied to the substrate so that the film thickness is 1 μm to 50 μm. As a method for applying the primer, for example, a general method such as brush coating, spray coating, roll coater coating, or the like can be employed. The substrate made of polypropylene may be produced by a conventionally known molding method, for example, an extrusion molding method, a hollow molding method, an injection molding method, a compression molding method, or the like.

Next, after the coating composition was formed into a film,
A method for producing an ultraviolet-absorbing processed product by fusing will be described. First, by extruding a coating composition under predetermined conditions using a T-die method or the like,
The film has a predetermined thickness. Next, as shown in FIG. 2, the above-mentioned film 5 is placed on the surface of a base material 1 made of a fusible material, for example, an unsaturated polyester resin or the like,
By heating at a predetermined temperature, both opposing surfaces of the film 5 and the substrate 1 are melted and bonded to each other. A specific example of the unsaturated polyester resin is a composition obtained by adding 1.5% of cumyl peroxide (polymerization initiator) to Epolac G-153AL manufactured by Nippon Shokubai Co., Ltd. It is not something to be done. That is, the base material 1 may be made of a material that can be fused to the film 5 and is not particularly limited.

As a result, a copolymer layer is formed on the surface of the substrate 1, and an ultraviolet absorbing processed product is manufactured. In addition, the above-mentioned composition for coating may be an optimal composition according to the melting property of the film 5, the material of the substrate 1, the use of the ultraviolet absorbing processed product, and the like. The method for forming the film 5 is not particularly limited.

Next, after the coating composition was formed into a film,
A method for producing an ultraviolet absorbing processed product by thermocompression bonding will be described. First, a coating composition is extruded under predetermined conditions using a T-die method or the like to form a film having a predetermined thickness. Next, as shown in FIG. 3, an adhesive is applied to the surface of the substrate 1 and dried at a predetermined temperature to form an adhesive layer 2. Next, a decorative layer 3 made of, for example, decorative paper, titanium paper, wood board, or the like is laminated on the surface of the adhesive layer 2. That is, the decorative layer 3 is attached to the surface of the adhesive layer 2. The materials of the base material 1 and the decorative layer 3 are as follows:
There is no particular limitation, and conventionally known ones can be used. The adhesive may be appropriately selected according to the materials of the base material 1 and the decorative layer 3, and is not particularly limited.

Next, a protective layer 6 made of, for example, an unsaturated polyester resin is formed on the surface of the decorative layer 3.
In addition, the material and the forming method of the protective layer 6 are not particularly limited. As a specific example of the unsaturated polyester resin, EPORAC P-5 manufactured by Nippon Shokubai Co., Ltd.
A composition obtained by adding 1% of methyl ethyl ketone peroxide (polymerization initiator) to 12Y may be mentioned, but is not particularly limited.

Subsequently, the film 5 is placed on the surface of the protective layer 6 and bonded by thermocompression at a predetermined temperature and pressure. As a result, a copolymer layer is formed, and an ultraviolet absorbing processed product is manufactured. In addition, the above-mentioned composition for coating may be an optimal composition according to the adhesiveness of the film 5, the material of the protective layer 6, the use of the ultraviolet absorbing processed product, and the like. The method for forming the film 5 is not particularly limited. Further, the formation of the decorative layer 3 and / or the protective layer 6 may be omitted depending on the material of the base material 1 and the use of the ultraviolet absorbent processed product. However, when the formation of the protective layer 6 is omitted, the film 5 may be attached to the decorative layer 3 using an adhesive.

Next, a method for producing an ultraviolet-absorbing processed product by transferring a copolymer layer using a mold will be described. As shown in FIG. 4A, first, a mold release agent 11 is applied to a molding surface of a mold 10 such as a mold. In addition, release agent 1
One type is not particularly limited, and a conventionally known release agent can be used.

Next, as shown in FIG. 13B, after the coating composition is applied to the molding surface, the mold 10 is heated to a predetermined temperature, for example, 40.degree. The composition for heating is heat-cured to form a copolymer layer 7. In addition, the above-mentioned composition for coating may be an optimal composition according to the material of the gel coat layer 8 and the base material 9 described later, the use of the ultraviolet absorbing processed product, and the like.

Thereafter, as shown in FIG. 13C, for example, an unsaturated polyester resin is applied on the copolymer layer 7 and then the mold 10 is heated to a predetermined temperature, whereby the unsaturated polyester resin is applied. The gel coat layer 8 is formed by heating and curing the polyester resin. That is, the gel coat layer 8 is laminated on the copolymer layer 7. In addition, the material and the forming method of the gel coat layer 8 are not particularly limited.

Next, on the gel coat layer 8, a resin composition such as FRP (fiber reinforced plastic) to be the base material 9 is backed and laminated. As a specific example of the resin composition, Epolac G-1 manufactured by Nippon Shokubai Co., Ltd.
12 is a resin composition obtained by impregnating glass fiber (chopped strand mat FEM-380-M-WN; manufactured by Fuji Fiberglass Co., Ltd.) with a laminating resin obtained by adding 1% of methyl ethyl ketone peroxide to 12. However, there is no particular limitation. That is, the substrate 9 is not particularly limited as long as it is made of a material that can be subjected to a heat curing treatment.

Then, as shown in FIG. 11D, the resin composition is heated and cured by heating the mold 10 to form the base material 9 and the surface of the base material 9 is formed. The above-mentioned copolymer layer 7 is transferred via the gel coat layer 8. Thereafter, by removing the mold, an ultraviolet absorbing processed product as shown in FIG. Note that the formation of the gel coat layer 8 may be omitted depending on the material of the base material 9 and the use of the ultraviolet absorbent processed product.

When the base material 9 is made of FRP, it is preferable to form the gel coat layer 8. By providing the gel coat layer 8 between the base material 9 and the copolymer layer 7,
Volatilization during heat molding and so-called foam sticking are reduced, and the releasability and dimensional stability are improved.

As described above, the UV-absorbing processed product according to the present invention comprises the UV-absorbing monomer (1), the cycloalkyl group-containing monomer, the UV-stable monomer (3) and / or Alternatively, the composition has a copolymer layer obtained by copolymerizing a monomer composition containing the ultraviolet-stable monomer (4).

The above-mentioned copolymer layer is composed of a UV-absorbing monomer (1) having a benzotriazole skeleton, a cycloalkyl group-containing monomer, and a UV-stable monomer (3).
(4) is obtained by copolymerizing a monomer composition containing (A) and (B), which has an ultraviolet absorbing ability, is excellent in long-term weather resistance, and has an adhesive property and an adhesive property to a base material, and further has a base protecting effect and a yellow color. It has a good anti-change effect and is excellent in gloss, water resistance, solvent resistance and the like. Therefore, the UV-absorbing processed product of the present invention has UV-absorbing ability and is excellent in long-term weather resistance,
Excellent in gloss, water resistance, solvent resistance, etc. Here,
The “benzotriazole skeleton” refers to a structure in which a phenol ring is bonded to the nitrogen atom at the 2-position of the benzotriazole ring.

Further, as described above, in the method for producing an ultraviolet-absorbing processed product according to the present invention, a copolymer layer formed by copolymerizing the above monomer composition was formed on a molding surface of a mold. Thereafter, a method is used in which a base material to be a processed product is formed using the above-described mold, and the copolymer layer is transferred to the base material side. Thereby, it is possible to easily produce an ultraviolet-absorbing processed product having the above-described performance and having a copolymer layer having a smooth surface.

Examples of the UV-absorbing processed product according to the present invention include plastic molded products such as tanks and containers, home appliances, steel products, large structures, automobile interior and exterior parts, building materials, wood products, glass products, and the like. Although it is mentioned, it is not particularly limited.

According to the above construction, there is provided an ultraviolet-absorbing processed product having a copolymer layer having excellent ultraviolet absorbing ability, excellent long-term weather resistance, and excellent gloss, water resistance, solvent resistance and the like. be able to. Also, according to the above method,
It is possible to easily produce an ultraviolet-absorbing processed product having the above-mentioned performance and having a copolymer layer having a smooth surface.

[0136]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the examples, "parts" indicates "parts by weight", and "%" indicates "% by weight".

Example 1 In a four-necked flask equipped with a thermometer, a gas injection tube, a dropping funnel, a reflux condenser and a stirrer, 24.3 parts of toluene as a solvent and 19.0 parts of butyl acetate were charged. Thereafter, the temperature of the solution was raised to 90 ° C. while stirring under a nitrogen gas flow.

On the other hand, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole (hereinafter referred to as benzotriazole) as an ultraviolet absorbing monomer (1) was added to the dropping funnel. (Indicated as (A)) 2.5
Parts, cyclohexyl methacrylate (hereinafter, referred to as CHMA) as a cycloalkyl group-containing monomer, 20.0 parts, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine as an ultraviolet light-stable monomer (3) (Hereinafter referred to as piperidine (C)) 1.2 parts, methacrylic acid 0.3 parts as an acidic functional group-containing monomer, hydroxyethyl acrylate 6.0 parts as a hydroxyl group-containing monomer, butyl acrylate 10.0 as other monomers Of a monomer composition (50 parts) consisting of 1 part by mass and 10.0 parts of methyl methacrylate, 4.5 parts of toluene and 2.2 parts of xylene as a solvent, and 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator
And a mixture consisting of 0.8 parts.

Next, while stirring the solution in the flask at 90 ° C., the above mixture was added dropwise to the solution over 3 hours.
After completion of the dropwise addition, while stirring the reaction solution under a nitrogen gas stream,
Hold at 90 ° C. for 5 hours. After the completion of the polymerization reaction, the reaction solution was cooled. As a result, a solution containing an acrylic polyol as a reaction product (hereinafter, referred to as an acrylic polyol solution) was obtained. The nonvolatile content of this acrylic polyol solution was 50%, the hydroxyl value was 29 mg KOH / g, the acid value was 2.0 mg KOH / g, and the viscosity measured by a Gardner-type foam viscometer was Z2 (viscosity standard solution symbol). Met. Further, the weight average molecular weight (M
w) was 11,000. The composition of the monomer composition, and
Table 1 summarizes the various measurement results of the acrylic polyol solution.
Shown in

Next, a paint to be used as a copolymer layer was prepared using the above-mentioned acrylic polyol solution. That is, a polyfunctional isocyanate (Sumidur N-3200; manufactured by Sumitomo Bayer Urethane Co., Ltd.) was weighed into the above acrylic polyol solution in an amount such that the equivalent ratio of isocyanate groups to hydroxyl groups in the solution was 1: 1. And mixed. Further, a thinner was added to the obtained mixture to dilute it, and the viscosity of the mixture was adjusted to a viscosity that allows air spraying. In this way, a paint (paint composition (b1)) to be a copolymer layer was obtained.

Next, an ultraviolet-absorbing processed product was prepared using the above-mentioned paint. That is, first, a wax-based mirror glaze MGH-8 (M
After spraying EGUIAR'S Incorporated) and polyvinyl alcohol (manufactured by Showa Polymer Co., Ltd.),
The above paint was spray painted. Next, the coating was heated and cured by heating the mold to 40 ° C. to 60 ° C. in a heating furnace to form a copolymer layer. After the mold was taken out, the copolymer layer was laminated by spray coating a gel coat resin (Epolac N-300T; Nippon Shokubai Co., Ltd.) of an unsaturated polyester resin to be a gel coat layer. The resin for gel coating was heated and cured by heating the mold in a heating furnace to form a gel coat layer.

After removing the mold, at room temperature, on the gel coat layer, a base material, that is, a resin for laminating a general-purpose unsaturated polyester resin to be an FRP molded product (Epolac G-773PTMY; Japan Co., Ltd.) A catalyst) and a glass fiber (CM455FA; manufactured by Asahi Fiber Co., Ltd.) were backed and laminated (3-ply). 1% of methyl ethyl ketone peroxide as a polymerization initiator was added to the lamination resin.

Then, by heating the above-mentioned mold in a heating furnace, the laminating resin is heat-cured to form FRP as a base material, and the surface of the FRP molded body is subjected to the above-mentioned co-loading. The coalesced layer was transferred. Thereafter, the mold was removed to obtain an FRP molded article as an ultraviolet absorbing processed product. The surface of the obtained FRP molded article, that is, the surface of the copolymer layer was smooth.

Next, a fluorescent UV condensation test (QUV test), which is a weather resistance test, was carried out using the above-mentioned FRP molded article.
The degree of yellowing (Δb value) was measured. The measurement is based on JIS K5
400-1979. As a measuring device, manufactured by Toyo Seiki Seisakusho Co., Ltd .;
C-1 type was used. As a measurement condition, a cycle of irradiating 70 ° C. × 4 hours and wet 50 ° C. × 4 hours as one set was repeated, and the yellowing degree after 2000 hours of QUV was measured using a color difference meter.

As a result, the yellowing degree after 2000 hours of QUV was 2. Further, an FRP molded article having no copolymer layer formed on its surface, that is, FRP which is a conventional processed product,
When the degree of yellowing of the molded product was measured in the same manner,
The yellowing degree after 2000 hours was 20.

As is clear from the above results, the FRP molded article according to the present invention has better weather resistance than the conventional FRP molded article.

Example 2 A four-necked flask equipped with a thermometer, gas injection tube, dropping funnel, reflux condenser and stirrer was charged with 3.0 parts of benzotriazole (A), 25.2 parts of toluene and 18.2 parts of butyl acetate. It is. afterwards,
This solution was heated to 90 ° C. while stirring under a nitrogen gas stream.

On the other hand, 1.5 parts of benzotriazole (A), 2 parts of CHMA, 1.0 part of piperidine (C), 0.3 part of methacrylic acid, 5.5 parts of hydroxyethyl acrylate, 9.0 parts of butyl acrylate and 9.7 parts of methyl methacrylate were added to the above dropping funnel. Part of the monomer composition (47 parts
Parts), 4.5 parts of toluene and 2.1 parts of xylene, and 2,
A mixture consisting of 0.9 parts of 2'-azobis (2-methylbutyronitrile) was added. The monomer composition was used in a total of 50 parts, including 47 parts in a dropping funnel and 3.0 parts of benzotriazole (A) charged in the flask.

Next, while stirring the solution in the flask at 90 ° C., 20% of the above mixture was added at once to the solution, and the remaining (80%) was added dropwise over 3 hours. After the completion of the dropwise addition, the reaction solution was maintained at 90 ° C. for 5 hours while stirring under a nitrogen gas stream. After the completion of the polymerization reaction, the reaction solution was cooled. Thereby, an acrylic polyol solution was obtained. The nonvolatile content of this acrylic polyol solution is 50%, the hydroxyl value is 27 mgKOH / g, and the acid value is 2.0 mgKO.
H / g, and the viscosity measured by a Gardner-type foam viscometer was Z (viscosity standard liquid symbol). The weight average molecular weight (Mw) of the acrylic polyol was 10,000. Table 1 summarizes the composition of the monomer composition and various measurement results of the acrylic polyol solution.

Next, the same operation as in Example 1 was carried out, and a paint (paint composition (b1)) to be a copolymer layer was prepared using the above-mentioned acrylic polyol solution. This paint was extruded under predetermined conditions using a T-die method to form a film having a thickness of 20 μm. The extrudability of the paint was extremely good.

Subsequently, this film was thermocompression-bonded to one side of a PC sheet extruded under predetermined conditions, that is, a PC sheet immediately after being discharged from an extruder. As a result, a PC board as an ultraviolet-absorbing processed product was obtained in which the above-mentioned film as a copolymer layer was laminated on the surface of a PC sheet as a base material. The adhesion between the PC sheet and the film was extremely good.

Next, the same operation as in Example 1 was carried out and a weather resistance test was carried out. As a result, the PC board according to the present invention was obtained by coating a generally used PC film coated with a conventional resin film.
It was found to have extremely excellent weather resistance as compared with the plate. In addition, the PC board according to the present invention hardly caused discoloration and decrease in gloss even when used for a long time. Furthermore, the PC board according to the present invention had the same impact resistance as a PC board having no copolymer layer formed on its surface, that is, a PC sheet.

Reference Example 1 Instead of 50 parts of the monomer composition in Example 1, 2.5 parts of benzotriazole (A) and C
A monomer composition consisting of 20.0 parts of HMA, 0.3 part of methacrylic acid, 6.0 parts of hydroxyethyl acrylate, 10.0 parts of butyl acrylate and 11.2 parts of methyl methacrylate (50 parts)
Except for using (Part), the same reaction and operation as in Example 1 were performed to obtain an acrylic polyol solution. The nonvolatile content of this acrylic polyol solution was 50%, and the hydroxyl value was 29%.
mgKOH / g, the acid value was 2.0 mgKOH / g, and the viscosity measured by a Gardner-type foam viscometer was Z2 (viscosity standard solution symbol). The weight average molecular weight (Mw) of the acrylic polyol was 11,000. Table 1 summarizes the composition of the monomer composition and various measurement results of the acrylic polyol solution.

Next, the same operation as in Example 1 was performed, and a coating material (composition for coating material) to be a copolymer layer was prepared using the above-mentioned acrylic polyol solution. Next, an ultraviolet-absorbing processed product was prepared using the above-mentioned paint. That is,
First, a primer (Supercron 822; manufactured by Nippon Paper Industries Co., Ltd.) is sprayed on a PP plate (manufactured by Nippon Test Panel Co., Ltd.) so as to have a film thickness of 5 μm. Dried for minutes. Next, the paint was spray-coated on the primer layer so as to have a thickness of 20 μm, and the paint was dried at 80 ° C. for 60 minutes. As a result, a PP plate was obtained as a UV-absorbing processed product in which the primer layer and the copolymer layer (top coat) were laminated on the PP plate surface. The adhesion between the PP plate and the primer layer and the adhesion between the primer layer and the copolymer layer were extremely good.

Next, the same operation as in Example 1 was carried out and a weather resistance test was carried out. As a result, the PP plate according to this reference example showed a conventional resin paint (eg, a polyurethane paint, As compared with a PP plate coated and coated with an acrylic resin-based paint and an epoxy resin-based paint), it was found to have extremely excellent weather resistance. In addition, the PP plate according to this reference example hardly caused discoloration and fading and a decrease in gloss even when used for a long period of time. Further, the PP plate according to the present reference example had the same impact resistance as the PP plate having no copolymer layer formed on the surface.

[0156]

[Table 1]

[Reference Example 2] Internal volume equipped with a thermometer, gas injection tube, dropping funnel, reflux condenser and stirrer
In a 0.5 L separable flask, 70.0 parts of deionized water, 1.5 parts of Nonipol 200 (trade name; polyoxyethylene nonyl phenyl ether manufactured by Sanyo Chemical Industries, Ltd.) as an emulsifier (surfactant) and Newpol PE-
68 (trade name; manufactured by Sanyo Chemical Industries, Ltd., polyoxyethylene glycol-polyoxypropylene glycol-
0.3 part of polyoxyethylene glycol / triblock copolymer) was charged. Thereafter, the temperature of the solution was raised to 65 ° C. while stirring under a nitrogen gas flow.

On the other hand, 5.0 parts of benzotriazole (A), 45.0 parts of CHMA, and 1.0 part of acrylic acid were added to the dropping funnel.
A monomer composition (100 parts) consisting of 14.0 parts, 14.0 parts of methyl methacrylate, 25.0 parts of n-butyl methacrylate, and 10.0 parts of 2-ethylhexyl acrylate;
00 (3.0 parts) and New Pole PE-68 (0.8 parts)
Was added to 25.0 parts of deionized water to obtain a pre-emulsion mixture.

Next, the solution in the separable flask was heated to 65 ° C.
While stirring at, the above pre-emulsion mixture was added dropwise to the solution over 2 hours. Until the dropping operation is completed, 6.0 parts and 5.0 parts of a 5.0% ammonium persulfate aqueous solution constituting a redox initiator are added to the above solution.
3.0 parts of a 30% aqueous sodium bisulfite solution were added in portions every 10 minutes.

After completion of the dropwise addition, the reaction solution was aged at 65 ° C. for 1 hour while stirring under a nitrogen gas stream. After the completion of the polymerization reaction, the reaction solution is cooled, and then 25% aqueous ammonia is added.
0.5 parts was added for neutralization. Thus, an emulsion polymer solution, that is, an aqueous dispersion was obtained. The nonvolatile content of this aqueous dispersion was 50%, and the viscosity was 1500 cps.

Next, a coating material to be used as a copolymer layer was prepared using the above aqueous dispersion. That is, the above aqueous dispersion 1
In 50.0 parts, 15.0 parts of deionized water, Nopco 80 which is an antifoaming agent
34 (trade name; manufactured by San Nopco Co., Ltd.) 0.3 parts, CS-12 (trade name; manufactured by Chisso Corporation) 10.0 which is a film forming aid
Part, and 5% adecanol UH-
420 (trade name; manufactured by Asahi Denka Kogyo KK) By mixing 1.0 part, paint (176.3
Parts) was prepared.

Next, a UV-absorbed processed product was prepared using the above-mentioned paint (paint composition). That is, first, an impact-resistant (HI) polystyrene plate (H865)
2; Asahi Kasei Kogyo Co., Ltd.) and an acrylic resin as a primer (Alloset 5210; Nippon Shokubai Co., Ltd.)
Was spray-coated so that the film thickness became 3 μm, and then the acrylic resin was dried at 60 ° C. for 10 minutes. Next, the above-mentioned paint was applied on the acrylic resin layer so as to have a thickness of 10 μm, and the paint was dried at 60 ° C. for 30 minutes. As a result, a polystyrene plate was obtained as an ultraviolet-absorbing processed product in which the acrylic resin layer and the copolymer layer were laminated on the surface of the polystyrene plate.

Next, the same operation as in Example 1 was performed and a weather resistance test was performed. The polystyrene plate according to this reference example was obtained by coating a general-purpose acrylic emulsion under the same conditions and method as described above. It was found to have extremely excellent weather resistance as compared with the plate. Further, the polystyrene plate according to the present reference example hardly caused discoloration and deterioration in gloss even when used for a long period of time.

Reference Example 3 To a four-necked flask equipped with a thermometer, a gas injection tube, a dropping funnel, a reflux condenser and a stirrer, 100.0 parts of toluene was charged. Thereafter, the temperature was raised to 80 ° C. while stirring this toluene under a nitrogen gas stream.

On the other hand, 5.0 parts of benzotriazole (A), 45.0 parts of CHMA, methacrylic acid
1.0 part, methyl methacrylate 14.0 parts, n-butyl methacrylate 25.0 parts and 2-ethylhexyl acrylate 1
0.0 part of a monomer composition (100 parts) and t-butylperoxy-2-ethylhexanoate as a polymerization initiator
0.2 part of the mixture.

Next, while stirring the solution in the flask at 80 ° C., the above mixture was added dropwise to the solution over 2 hours.
After completion of the dropwise addition, while stirring the reaction solution under a nitrogen gas stream,
It was kept at 80 ° C. for 6 hours. After the completion of the polymerization reaction, the reaction solution was cooled. As a result, a copolymer solution as a reaction product was obtained. The nonvolatile content of this copolymer solution was 49.8%. The number average molecular weight (Mn) of the copolymer was 18,0
The glass transition temperature (Tg) calculated by a predetermined method was 55 ° C. Subsequently, a thinner was added to the obtained copolymer solution until the viscosity reached a predetermined value, and the mixture was diluted to obtain a paint (ultraviolet absorbing lacquer composition) to be used as a copolymer layer.

Next, an ultraviolet-absorbing processed product was prepared using the above-mentioned paint. That is, first, the above-mentioned paint was brush-coated on a hinoki material as a base material so that the film thickness after drying was 25 μm, and the paint was dried at room temperature for 7 days. As a result, a hinoki material as an ultraviolet-absorbing processed product having a copolymer layer on the surface was obtained.

Next, the same operation as in Example 1 was performed, and a weather resistance test was performed.
Compared with a cypress material coated with a general-purpose acrylic paint under the same conditions and method as above, it was found that the material had extremely excellent weather resistance. In addition, the hinoki material according to the present reference example hardly caused discoloration and deterioration in gloss even when used for a long time.

Example 3 First, the same reaction and operation as in Example 1 were performed to obtain a paint to be a copolymer layer.
Next, this paint was extruded under predetermined conditions using a T-die method to form a film having a thickness of 20 μm.
The extrudability of the paint was extremely good.

Subsequently, a solution-type copolymerized polyester-based adhesive (Vylon 50AS; manufactured by Toyobo Co., Ltd.) and an isocyanate-based crosslinking agent (Coronate HL;
Nippon Polyurethane Industry Co., Ltd.)
Was applied so that the film thickness became 8 μm, and the mixed solution was dried at 60 ° C. to 80 ° C. to remove the solvent. Thus, a film having an adhesive layer on the surface was obtained.

This film was adhered to a PET plate (manufactured by Nippon Test Panel Co., Ltd.) as a substrate, and left at 80 ° C. for 30 minutes. Thus, a PET plate was obtained as a UV-absorbing processed product in which the above-mentioned film as a copolymer layer was stuck on the surface of the PET plate. The adhesion between the PET plate and the film was extremely good.

Next, the same operation as in Example 1 was performed and a weather resistance test was performed. As a result, the PET plate according to the present invention was compared with a PET plate having no copolymer layer adhered on the surface. It turned out to have extremely excellent weather resistance.
Further, the PET plate according to the present invention hardly caused discoloration and decrease in gloss even when used for a long period of time.

[0173]

As described above, the UV-absorbing processed product of the present invention comprises the UV-absorbing monomer represented by the general formula (1) and the unsaturated monomer represented by the general formula (2). Monomers and
A copolymer obtained by copolymerizing a monomer composition containing the UV-stable monomer represented by the general formula (3) and / or the UV-stable monomer represented by the general formula (4). It has a configuration having a polymer layer.

Thus, it is possible to provide a UV-absorbed processed product having a copolymer layer having UV-absorbing ability, excellent long-term weather resistance, and excellent gloss, water resistance, solvent resistance and the like. It works.

Further, the method for producing an ultraviolet-absorbing processed product of the present invention comprises, after forming a copolymer layer obtained by copolymerizing the above-mentioned monomer composition on the molding surface of a mold, as described above. A method of molding a substrate to be a processed product by the above mold, and transferring the copolymer layer to the substrate side.

As a result, there is an effect that an ultraviolet-absorbing processed product having the above-mentioned performance and having a copolymer layer having a smooth surface can be easily produced.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing an example of a method for producing a UV-absorbing processed product according to the present invention.

FIG. 2 is a cross-sectional view showing another example of the method for producing the ultraviolet absorbent processed product according to the present invention.

FIG. 3 is a cross-sectional view showing still another example of the method for producing the ultraviolet absorbent processed product according to the present invention.

FIG. 4 is a cross-sectional view showing still another example of the method for producing the ultraviolet absorbent processed product according to the present invention, wherein (a) is
It is sectional drawing which shows the state which applied the mold release agent to the type | mold, (b)
Is a cross-sectional view showing a state in which a copolymer layer is formed,
(C) is a sectional view showing a state in which a gel coat layer is laminated, (d) is a sectional view showing a state in which a base material is laminated, and (e) is a sectional view showing an ultraviolet absorbing processed product. It is.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base material 2 Adhesive layer 3 Decorative layer 4 Copolymer layer 5 Film 6 Protective layer 7 Copolymer layer 8 Gel coat layer 9 Base material 10 Type 11 Release agent

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Takao Minami, Inventor 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (72) Inventor Masaya Yoshi ▼ 5-8, Nishi-Maburi-cho, Suita-shi, Osaka No. Nippon Shokubai Co., Ltd. (72) Inventor Naka ▲ Saki Mitsuo 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd.

Claims (2)

[Claims] 1. A compound of the general formula (1) (Wherein, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ² represents a linear or branched alkylene group having 1 to 6 carbon atoms, and R ³ represents a hydrogen atom. X represents a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group). And the general formula (2) (Wherein, R ¹⁰ represents a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, and Z represents a cycloalkyl group which may have a substituent); General formula (3) (Wherein, R ⁶ represents a hydrogen atom or a cyano group, R ^7,
R ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, and R ⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
Wherein Y represents an oxygen atom or an imino group) and / or an ultraviolet-stable monomer represented by the general formula (4): (Wherein, R ⁶ represents a hydrogen atom or a cyano group, R ^7,
R ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, and Y represents an oxygen atom or an imino group). An ultraviolet-absorbing processed product having a copolymer layer obtained by copolymerizing 2. After forming a copolymer layer obtained by copolymerizing the monomer composition according to claim 1 on a molding surface of a mold, a substrate to be a processed product is molded by the mold. And transferring the copolymer layer to the substrate side.