JPH093135A - Ultraviolet-absorbing molded article and its production - Google Patents

Abstract

PURPOSE: To obtain an ultraviolet-absorbing molded plastic article which is weather- resistant for a long term by forming, on the surface of a molded plastic article, an ultraviolet-absorbing layer comprising a copolymer obtd. by the copolymn, of an ultraviolet-absorbing benzotriazole monomer with a specific unsatd. monomer. CONSTITUTION: An ultraviolet-absorbing copolymer is produced by copolymerizing a monomer represented by formula I (wherein R<1> is H or a 1-8C hydrocarbon group; R<2> is a 1-6C alkylene; R<3> is H or methyl; and X is H, a halogen, a 1-8C hydrocarbon group, cyano, etc.) with an unsatd. monomer represented by formula II (wherein R<10> is H or a 1-2C hydrocarbon group; and Z is a cycloalkyl), if necessary together with an ultraviolet-stable monomer represented by formula III (wherein R<6> is H or cyano; R<7> and R<8> are each H or a 1-2C hydrocarbon group; R<9> is H or a 1-18C hydrocarbon group; and Y is O or imino) and other monomers. A layer of the copolymer is formed on the surface of a molded article, giving an ultraviolet-absorbing molded article. The surface layer is formed e.g. by forming the layer on a mold and molding a molding material with the mold to transfer the layer to the surface of resultant molded article, by thermally transferring a film made of the copolymer, or by coating a molded article with the copolymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention has an ultraviolet absorbing ability,
The present invention relates to an ultraviolet-absorbing processed product having a copolymer layer having excellent long-term weather resistance and excellent gloss, water resistance, solvent resistance, and the like, and a method for producing the product.

[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.
A molded product (processed product) made of various plastics (base material) such as (polycarbonate) and acrylic resin is deteriorated such as yellowing when exposed to ultraviolet rays for a long period of time outdoors. Therefore, conventionally, the 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 some weather resistance when exposed to ultraviolet rays for a short period of time, but when it is continuously irradiated with ultraviolet rays for a long period of time. Has deteriorated, such as yellowing, and its weather resistance is insufficient. That is, the above-mentioned conventional resin film has a problem that the effect of protecting the base and the effect of preventing yellowing are poor, and the long-term weather resistance is poor.

Therefore, for example, in Japanese Patent Application Laid-Open No. 4-311754, a fluororesin composition obtained by copolymerizing a benzotriazole-based UV absorbing monomer and a fluorine-containing monomer is used, and It has been proposed to impart weather resistance to molded articles. However, the fluororesin composition is inferior in adhesiveness and adhesiveness to a plastic which is a molded product. Further, the fluororesin composition is expensive and has a problem of being easily soiled (prone to stain).

Therefore, it has an ultraviolet absorbing ability, is excellent in long-term weather resistance, and is excellent in adhesion and adhesion to a substrate such as plastic, and is also 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.

The present invention has been made in view of the above-mentioned problems of the prior art, and its purpose is to have an ultraviolet absorbing ability, a good undercoat protection effect, a yellowing prevention effect, etc., and an excellent long-term weather resistance. Another object of the present invention is to provide an ultraviolet-absorbing processed product having a copolymer layer having excellent gloss, water resistance, solvent resistance and the like, and a method for producing the product.

[0007]

MEANS FOR SOLVING THE PROBLEMS The inventors of the present invention have made earnest studies on an ultraviolet-absorbing processed product and a method for producing the same in order to achieve the above-mentioned object, and as a result, an ultraviolet-absorbing monomer having a specific structure, A copolymer obtained by copolymerizing a monomer composition containing an unsaturated monomer having a specific structure has an ultraviolet absorbing ability and is excellent in long-term weather resistance, and has good adhesion to a substrate and It has been found that the adhesiveness is good, the undercoat protection effect and the yellowing prevention effect are good, and the gloss, water resistance and solvent resistance are excellent. That is, the ultraviolet-absorbing processed product having the copolymer layer has an ultraviolet-absorbing ability,
The inventors have found that they are excellent not only in long-term weather resistance but also in gloss, water resistance, solvent resistance, etc., and have completed the present invention. Further, after forming the above-mentioned copolymer layer on the molding surface of the mold, by molding the base material to be a processed product with the above-mentioned mold, and transferring the copolymer layer to the base material side, It was found that an ultraviolet-absorbing processed product having the above-mentioned performance and having a copolymer layer having a smooth surface can be easily produced, and completed the present invention.

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

[0009]

Embedded image

(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. Represents 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]

[Chemical 6]

(In the formula, R ¹⁰ represents a hydrogen atom or a carbon number of 1 to
2 represents a hydrocarbon group, and Z represents a cycloalkyl group which may have a substituent) and a copolymerization product obtained by copolymerizing a monomer composition containing an unsaturated monomer. It is characterized by having a united layer.

In order to solve the above-mentioned problems, an ultraviolet-absorbing processed product according to a second aspect of the present invention is the ultraviolet-absorbing processed product according to the first aspect, wherein the monomer composition is represented by the general formula (3).

[0014]

[Chemical 7]

(In the formula, 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 number 1 to 18, Y represents an oxygen atom or an imino group) and / or a UV stable monomer represented by the general formula (4)

[0016]

Embedded image

(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. Which further comprises a UV-stable monomer.

Further, in order to solve the above-mentioned problems, the method for producing an ultraviolet-absorbing processed product according to the third aspect of the present invention,
After forming a copolymer layer obtained by copolymerizing the monomer composition according to claim 1 or 2 on the molding surface of the mold, while molding a base material to be a processed product with the mold, It is characterized in that the copolymer layer is transferred to the substrate side.

Hereinafter, the present invention will be described in detail. The ultraviolet absorbing processed product according to the present invention is a monomer containing the ultraviolet absorbing monomer represented by the general formula (1) and the unsaturated monomer represented by the general formula (2). It has a copolymer layer formed by copolymerizing the composition. The above-mentioned monomer composition, if necessary, contains the UV stable monomer represented by the general formula (3) and / or the UV stable monomer represented by the general formula (4). It may contain, and may further contain an acidic functional group-containing monomer, a hydroxyl group-containing monomer, and a monomer other than the above monomers.

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. Is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ²
The substituent represented by is composed of a linear or branched alkylene group having 1 to 6 carbon atoms, the substituent represented by R ³ is composed of a hydrogen atom or a methyl group, and the substituent represented by X is substituted. A benzotriazole group 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 UV absorbing monomer (1) include 2- [2'-hydroxy-5 '-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [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 not limited to Not a thing. One of these ultraviolet absorbing monomers (1) may be used alone, or two or more thereof may be appropriately mixed and used.

In the unsaturated monomer represented by the general formula (2) according to the present invention, 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 or 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 above unsaturated monomers (hereinafter referred to as cycloalkyl group-containing monomers) include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate and 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 UV stable monomer represented by the general formula (3) according to the present invention (hereinafter referred to as UV stable monomer (3)) is 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 number of 1 to 2.
And a substituent represented by R ⁹ is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and a substituent represented by Y is an oxygen atom or an imino group. Is. The substituents represented by R ⁷ and R ⁸ are, for example, a hydrogen atom, a methyl group or an ethyl group, and the substituent represented by R ⁹ is, for example, a methyl group. Group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group It is a linear or branched hydrocarbon residue such as a group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group.

Specific examples of the UV-stable monomer (3) include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine and 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 thereof 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)) is 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 number of 1 to 2.
And a substituent represented by Y is composed of an oxygen atom or an imino group. The above-mentioned substituents represented by R ⁷ and R ⁸ are, for example, a hydrogen atom, a methyl group or an ethyl group.

Specific examples of the UV stable monomer (4) include 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
Examples include, but are not limited to, tetramethylpiperidine and the like. 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, and
Monomers other than the UV-stable monomers (3) and (4)), that is, acidic functional group-containing monomers and hydroxyl group-containing monomers that are optionally contained in the monomer composition, and further A monomer other than the acidic functional group-containing monomer and the hydroxyl group-containing monomer (hereinafter referred to as other monomer) is added to the 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 above-mentioned acidic functional group-containing monomer include (meth) acrylic acid, crotonic acid,
Carboxyl group-containing unsaturated monomers such as itaconic acid, maleic acid, maleic anhydride; Sulfonic acid group-containing unsaturated monomers such as vinyl sulfonic acid, styrene sulfonic acid, sulfoethyl (meth) acrylate; 2- (meth) Acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3-chloropropyl acid phosphate, 2-methacryloyloxyethyl phenyl phosphate, etc. Examples include, but are not limited to, a monomer and the like. These acidic functional group-containing monomers may be used alone or in a suitable mixture of two or more kinds.

Specific examples of the above-mentioned hydroxyl group-containing monomer include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate (for example, manufactured by Daicel Chemical Industries Ltd.). A trade name of Praxel FM), a mono (meth) acrylate of polyester diol obtained from phthalic acid and propylene glycol, and the like, but not limited thereto. These hydroxyl group-containing monomers may be used alone or in a suitable mixture of two or more kinds.

Specific examples of the above-mentioned other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate and isobutyl. (Meth) acrylic acid alkyl ester such as (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; epoxy such as glycidyl (meth) acrylate Group-containing monomer; nitrogen-containing monomer such as (meth) acrylamide, N, N'-dimethylaminoethyl (meth) acrylate, vinylpyridine and vinylimidazole; halogen-containing monomer such as vinyl chloride and vinylidene chloride; Styrene, α-methylstyrene, vinyl 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 ultraviolet absorbing processed product according to the present invention is
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, a coating composition is prepared by adding a crosslinking agent to a polymer composition containing a copolymer obtained by copolymerizing a monomer composition, and the coating composition is applied. A copolymer layer may be formed, or after the coating composition is once formed into a film, the copolymer layer may be formed by fusing, thermocompressing or adhering this film, Further, after the copolymer layer is once formed on the molding surface of the mold, the copolymer layer may be transferred to the substrate side.

The coating composition used for forming the copolymer layer will be described below. First, an emulsion-type coating composition obtained by emulsion-polymerizing a monomer composition containing an ultraviolet absorbing monomer (1) and a cycloalkyl group-containing monomer (hereinafter referred to as coating composition (a )) Will be described.

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

By setting the content of the ultraviolet absorbing monomer (1) within the above range, the coating film made of the coating composition (a) can have ultraviolet absorbing ability. Further, the dispersibility of an acidic pigment such as carbon black in the coating composition (a) and the color mixing stability 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). Also, a 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 ultraviolet absorbing ability of the obtained coating composition (a), that is, the coating film Is insufficient, which is not preferable. On the other hand, when the content is more than 30% by weight, the appearance of the coating film comprising the coating composition (a), such as gloss and sharpness, is poor, and solvent resistance, chemical resistance, etc. It is not preferable because the performance is lowered. Further, if the content is more than 30% by weight, the polymerization stability during emulsion polymerization may be poor and the aggregates may increase.

When the content of the cycloalkyl group-containing monomer in the monomer composition is less than 2% by weight, a coating film obtained when the resulting coating composition (a) is used as an emulsion type coating material Is inferior in weather resistance, gloss, hardness and the like, which is not preferable. Further, when the content is more than 95% by weight, flexibility of the coating film comprising the coating composition (a) becomes poor and cracks are likely to occur in the coating film due to aging, which is preferable. Absent.

When the monomer composition contains the UV stable monomer (3) and / or the UV stable monomer (4), the above UV stable monomers (3) and (4) )
The total amount of is preferably in the range of 0.1 wt% to 15 wt%, more preferably in the range of 0.5 wt% to 10 wt%,
The range of 1% by weight to 5% by weight is particularly preferable. 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 comprising the coating composition (a) can be maintained for a long period of time. still,
These UV stable monomers (3) and (4) are used within a range that does not impair the physical properties of the resulting coating composition (a). Further, the weight ratio of the UV stable monomer (3), the UV stable monomer (4) and the cycloalkyl group-containing monomer in the above 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) May deteriorate. If the total amount is more than 15% by weight, the coating film comprising the coating composition (a) may be inferior in water resistance, gloss, image clarity and the like.

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

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

Specific examples of the anionic surfactant include 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; sodium sulfate. Holycinoate; Alkali metal salts of sulfonated paraffins, ammonium salts of sulfonated paraffins; Fatty acid salts of sodium laurate, triethanolamine oleate, triethanolamine abietate; Sodium dodecylbenzene sulfonate, alkali phenols Alkyl aryl sulfonates such as alkali metal sulphates of hydroxyethylene; High alkyl naphtha Nsuruhon salts; naphthalenesulfonic acid-formalin condensate; dialkyl sulfosuccinate, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylaryl sulfate salts.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether; polyoxyethylene alkylaryl ether; sorbitan fatty acid ester; polyoxyethylene sorbitan fatty acid ester; glycerol monolaurate and the like. Fatty acid monoglycerides; oxyethylene-oxypropylene copolymers; condensation products of ethylene oxide with aliphatic amines, amides or acids.

Specific examples of the polymeric surfactant include:
For example, polyvinyl alcohol; sodium poly (meth) acrylate, potassium poly (meth) acrylate, ammonium poly (meth) acrylate, polyhydroxyethyl (meth) acrylate, polyhydroxypropyl (meth) acrylate; Examples thereof include two or more kinds of copolymers of a polymerizable monomer which is a structural unit; or a copolymer of a polymerizable monomer which is a structural unit of these polymers and another monomer.

These surfactants may be used alone or in a suitable mixture of two or more kinds. 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 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. A water-soluble or water-dispersible polymer having a terminal alkyl group having a valence of 200 mgKOH / g or more (hereinafter,
It is more preferable to use a terminal alkyl group-containing polymer) and / or a salt thereof. When the terminal alkyl group-containing polymer and / or salt is used as an emulsifier, the monomer composition further contains a functional group-containing monomer containing a functional group having reactivity with a carboxyl group. It is preferable to include. The functional group-containing monomer will be described later.

By using the above-mentioned terminal alkyl group-containing polymer and / or salt as an emulsifier, a coating film having excellent initial drying properties and further excellent properties such as long-term weather resistance, water resistance, gloss, and sharpness is obtained. It is possible to produce an emulsion capable of forming, that is, a coating composition (a).

The above-mentioned terminal alkyl group-containing polymer satisfies the polymerization stability during emulsion polymerization and the water resistance, solvent resistance, strength and other properties of the coating film comprising the coating composition (a). In addition, it must have an acid value of 200 mgKOH / g or more and be water-soluble or water-dispersible. Acid value of polymer containing terminal alkyl group is 200mgKOH
If it is less than / g, the emulsifying ability cannot be sufficiently obtained, so that the polymerization stability during emulsion polymerization becomes poor and aggregates are generated. In addition, 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. When the molecular weight is out of the above range, sufficient emulsifying ability cannot be obtained, and thus the polymerization stability during emulsion polymerization becomes poor.

The unsaturated carboxylic acid used in the synthesis of the polymer containing a terminal alkyl group is not particularly limited as long as it is a compound having a carboxyl group and / or its salt and a polymerizable unsaturated group in the molecule. Not a thing. Specific examples of the unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid; and monoesters or salts of these compounds. Only one kind of these unsaturated carboxylic acids may be used, 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 the terminal alkyl group-containing polymer. This makes it possible to impart hydrophilicity to the terminal alkyl group-containing polymer. Further, the above-mentioned carboxyl group acts as a functional group when curing the coating composition (a).

The above-mentioned monomer component may contain only an unsaturated carboxylic acid, but may contain a monomer other than the unsaturated carboxylic acid as the case requires. The monomer is not particularly limited as long as it is a compound copolymerizable with the above unsaturated carboxylic acid. As the monomer,
Specifically, for example, styrene, vinyltoluene, α-
Styrene derivatives such as methylstyrene, chloromethylstyrene, styrenesulfonic acid or salts thereof; (meth) acrylamide, N-monomethyl (meth) acrylamide,
(Meth) acrylamide derivatives such as N-monoethyl (meth) acrylamide and N, N-dimethyl (meth) acrylamide; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc. ) (Meth) acrylic acid 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) acryl synthesized by ester formation reaction of (meth) acrylic acid with polypropylene glycol or polyethylene glycol Acid esters; (meth)
Examples thereof include acrylic acid-2-ethyl 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 unsaturated carboxylic acid in the above-mentioned monomer components may be used within the range such that the acid value of the obtained terminal alkyl group-containing polymer does not become less than 200 mgKOH / g. Furthermore, the monomer is used in consideration of the compatibility between the polymer component produced when the terminal alkyl group-containing polymer is emulsion-polymerized and the terminal alkyl group-containing polymer, and the type and the amount thereof are used. It is preferable to select.

The above-mentioned alkyl mercaptan used for the synthesis of the terminal alkyl group-containing polymer may have 6 to 18 carbon atoms. As the alkyl mercaptan, specifically,
Examples thereof include n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, cetyl mercaptan, stearyl mercaptan and the like. These alkyl mercaptans may be used alone or in a suitable mixture of two or more kinds. The terminal alkyl group-containing polymer obtained by using an alkyl mercaptan having 5 or less carbon atoms has poor polymerization stability during emulsion polymerization. In addition, the storage stability of the obtained coating composition (a) is poor.

Alkyl mercaptan is a molecular weight modifier 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 300 to 7,00.
It can be adjusted within the range of 0, and at the same time, the surface-active ability can be imparted to the terminal alkyl group-containing polymer.

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

The polymerization method for polymerizing the monomer components is as follows:
The method is not particularly limited, and various conventionally known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization and the like can be adopted.

When polymerizing the monomer component, a conventionally known oil-soluble or water-soluble polymerization initiator, for example, a radical polymerization initiator can be used. The amount of the polymerization initiator 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, relative to 1 mol of the alkyl mercaptan. The solvent that can be used when polymerizing the monomer component is particularly limited as long as it is a compound that 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, the composition of the monomer components used, the type of alkyl mercaptan, the polymerization initiator, etc., but it is 1 hour. A range of up to 8 hours is preferred.

The terminal alkyl group-containing polymer has sufficient surface-active ability, but during emulsion polymerization, a part or all of the carboxyl groups of the terminal alkyl group-containing polymer are neutralized with a neutralizing agent. Then, the terminal alkyl group-containing polymer is preferably salted. By making the terminal alkyl group-containing polymer into a salt, the polymerization stability during emulsion polymerization and the storage stability of the resulting coating composition (a) can be further improved.

As the above-mentioned neutralizing agent, conventionally known ones 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,
Examples thereof include 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 reactive with the carboxyl group of the terminal alkyl group-containing polymer. Specific examples of the functional group-containing monomer include epoxy group-containing monomers such as glycidyl (meth) acrylate, -2-methylglycidyl (meth) acrylate, and allylglycidyl ether; ) Acryloylaziridine, aziridinyl group-containing monomers such as -2-aziridinylethyl (meth) acrylate; 2-isopropenyl-2
Examples include oxazoline group-containing monomers such as oxazoline and 2-vinyl-2-oxazoline. Only one type of these neutralizing agents may be used, or two or more types may be appropriately mixed and used.

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, and 0.5% by weight to 15% by weight. The range of wt% is more preferable. 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 an emulsifier remains in an unreacted state. At the same time, the resulting polymer is insufficiently crosslinked. For this reason,
The coating film comprising the coating composition (a) is inferior in initial drying properties, water resistance, solvent resistance, strength and the like, which is not preferable.
If the content is more than 40% by weight, the polymerization stability during emulsion polymerization becomes poor. In addition, the storage stability of the obtained coating composition (a) is poor.

The reaction method for emulsion-polymerizing the above-mentioned monomer composition is not particularly limited, and various conventionally known methods can be adopted. For example, at the time of initiation of polymerization, a method in which water is mixed with a monomer composition, a polymerization initiator, and the like to perform polymerization; a so-called monomer dropping method; a pre-emulsion method or the like can be used. In addition, it is also possible to make the emulsion particles have a different phase structure by carrying out multistage polymerization such as Iwayu seed polymerization, core-shell polymerization, and power feed polymerization.

When emulsion-polymerizing the monomer composition, a conventionally known polymerization initiator can be used. Specific examples of the above-mentioned polymerization initiator include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate; 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; hydrogen peroxide. Further, by using sodium bisulfite, L-ascorbic acid or the like as a reducing agent together with these polymerization initiators, a redox type initiator may be used. The amount of the polymerization initiator used is
There is no particular limitation.

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

When emulsion-polymerizing the monomer composition, 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 of the emulsion polymerization.

The polymer composition obtained by the above-mentioned emulsion polymerization can be used as it is as the coating composition (a), but known additives for the polymer composition, such as film-forming aids and pigments, can be used. , Filler, toner, wetting agent, antistatic agent,
An antifoaming agent, a viscosity controlling agent and the like can be added as necessary. An inorganic pigment or an organic pigment can be used as the above-mentioned pigment. Examples of the inorganic pigment include white pigments such as titanium oxide, antimony trioxide, zinc white, lithopone, and white lead; colored pigments such as carbon black, yellow lead, molybdenum red, red iron oxide, yellow iron oxide, and yellow flower. . Examples of organic pigments include azo compounds such as benzidine and Hansa Yellow; phthalocyanines such as phthalocyanine blue. Only one type of these pigments may be used, or two or more types may be appropriately mixed and used. The polymer composition obtained by the emulsion polymerization,
Excellent pigment dispersibility.

As described above, the coating composition (a) can be easily prepared by emulsion-polymerizing the monomer composition containing the ultraviolet absorbing monomer (1) and the cycloalkyl group-containing monomer. Can be obtained. The coating composition (a) is particularly excellent in UV absorption in the wavelength range of 300 nm to 400 nm, and has long-term weather resistance, water resistance, gloss, sharpness, solvent resistance, chemical resistance, and It is possible to form a coating film having excellent discoloration resistance, crack resistance, blister resistance, and the like. Further, according to the above method, the coating composition (a) capable of forming a coating film having further excellent performance can be easily produced.

Next, a copolymer obtained by copolymerizing a monomer composition containing the ultraviolet absorbing monomer (1), a cycloalkyl group-containing monomer, and an acidic functional group-containing monomer. A coating composition containing (hereinafter, referred to as an ultraviolet absorbing lacquer composition) will be described.

In the ultraviolet absorbing lacquer composition, the content of each of the above monomers in the monomer composition is not particularly limited, but the ultraviolet absorbing monomer (1) is
It is preferably within the range of 0.1% by weight to 30% by weight, more preferably within the range of 1% by weight to 20% by weight, and within the range of 2% by weight to
A range of 15% by weight is particularly preferred. The cycloalkyl group-containing monomer is preferably in the range of 2% by weight to 95% by weight, more preferably in the range of 5% by weight to 85% by weight,
A range of 10% by weight to 75% by weight is particularly preferable. The content of the acidic functional group-containing monomer is preferably 0.1% by weight to 15% by weight, more preferably 0.2% by weight to 10% by weight, and particularly preferably 0.5% by weight 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 exceeds 30% by weight, the appearance of the coating film made of the ultraviolet absorbing lacquer composition to be obtained, such as gloss and image clarity, solvent resistance and chemical resistance may be deteriorated, which is preferable. Absent.

Further, 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 made of the obtained ultraviolet absorbing lacquer composition. It is not preferable because the performance such as becomes insufficient. On the other hand, if the content exceeds 95% by weight, the flexibility of the coating film becomes poor and cracks are likely to occur in the coating film due to aging, which is not preferable.

The fact that the monomer composition contains an acidic functional group-containing monomer means that the ultraviolet absorbing lacquer composition has
It acts extremely effectively in providing adhesion to a substrate, particularly a substrate made of metal, and pigment dispersibility. That is, it is possible to improve the dispersibility of various pigments and the color mixing stability in a composite pigment system. If the content of the acidic functional group-containing monomer in the monomer composition is less than 0.1% by weight, it is not possible to sufficiently impart pigment dispersibility to the ultraviolet absorbing lacquer composition, which is not preferable. On the other hand, if the content exceeds 15% by weight, there are disadvantages such as poor polymerization stability and reduced water resistance of the resulting copolymer, which is not preferable.

When the monomer composition contains the UV stable monomer (3) and / or the UV stable monomer (4), the UV stable monomer (3). (4) )
The total amount of is preferably in the range of 0.1 wt% to 15 wt%, more preferably in the range of 0.5 wt% to 10 wt%,
The range of 1% by weight to 5% by weight is particularly preferable. By setting the total amount of the UV stable monomers (3) and (4) within the above range, it is possible to obtain a UV absorbing lacquer composition capable of maintaining the UV absorbing ability for a long period of time.

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 preferred because the coating film made of the obtained ultraviolet absorbing lacquer composition cannot maintain the ultraviolet absorbing ability for a long period of time. On the other hand, if the total amount exceeds 15% by weight, the coating film made of the ultraviolet absorbing lacquer composition obtained is inferior in water resistance, gloss, sharpness and the like, 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 monomer (3) and (4), and other monomer. The method for mixing the monomers is not particularly limited. For example,
The above monomers may be mixed in advance before being copolymerized, or may be mixed in the reaction solution when the above monomers are copolymerized. In short, it is sufficient that each of the above monomers is charged in the reactor during the polymerization.

The polymerization method for copolymerizing the above-mentioned monomer composition is not particularly limited, and various conventionally known polymerization methods such as solution polymerization method, emulsion polymerization method, suspension polymerization method, A bulk polymerization method or the like can be adopted. Examples of the solvent that can be used when the monomer composition is copolymerized by employing the solution polymerization method include, for example, toluene and
Xylene and other high-boiling aromatic hydrocarbons; Acetates such as ethyl acetate, butyl acetate, cellosolve acetate; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Isopropanol, n-butanol, iso-
Aliphatic alcohols such as butanol; alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether and the like can be mentioned, but 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 the monomer composition is copolymerized, a polymerization initiator can be used. Specific examples of the above-mentioned polymerization initiator include, but are not limited to, ordinary radical polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, and di-t-butyl peroxide. Not a thing. The amount of the polymerization initiator used is not particularly limited, but it is preferably used within 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, for the purpose of controlling the molecular weight, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, carbon tetrachloride or carbon tetrabromide or a polymerization regulator may be used in the reaction system.

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

Further, a differential scanning calorimeter (D
The glass transition temperature (Tg) measured using SC) is
It is preferably designed to be in the range of 20 ° C to 80 ° C, and more preferably designed to be in the range of 30 ° C to 70 ° C. When the glass transition temperature of the copolymer is less than 20 ° C., the coating film made of the ultraviolet absorbing lacquer composition containing the copolymer is too soft and the durability cannot be maintained for a long period of time. , Not preferable.
On the other hand, if the glass transition temperature exceeds 80 ° C., the coating film becomes too hard and too brittle, so that crack resistance and blister resistance cannot be sufficiently exhibited, which is not preferable.

The number average molecular weight (Mn) of the copolymer is 1
The design is preferably within the range of 0,000 to 40,000, more preferably within the range of 15,000 to 30,000. If the number average molecular weight is less than 10,000, a coating film having sufficient durability cannot be obtained, which is not preferable. On the other hand, the number average molecular weight is 40,0
When it exceeds 00, it is not preferable because the polymerization stability is inferior and the viscosity becomes too high, resulting in a poor coating workability. Furthermore, even if the number average molecular weight is 10,000 or more, if a component having a number average molecular weight of 5,000 or less is present in the copolymer in an amount of 10% or more, a coating film having sufficient durability cannot be obtained, or This causes the inconvenience of lacking solvent resistance. Therefore, in the copolymer, a component having a number average molecular weight of 5,000 or less is
It is preferably less than 10%.

The ultraviolet absorbing lacquer composition of the present invention is a one-pack non-crosslinking type composition and can be used as it is as a coating composition, but if necessary, it may be filled with an organic solvent and / or water or a filler. Agents, leveling agents, dispersants,
You may mix and use additives for various paints, 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 exemplified above. Only one kind of these various additives may be used, or two or more kinds thereof may be appropriately mixed and used. Moreover, the amount of these additives used is not particularly limited.

The above-mentioned UV absorbing monomer (1) has a polymerizable unsaturated double bond in the molecule, and is different from the cycloalkyl group-containing monomer and the acidic functional group-containing monomer. Copolymerize. Therefore, the resulting UV-absorbing copolymer has good compatibility between the monomers and there is no extractable unreacted UV-absorbing monomer (1), so that elution or bleed-out does not occur. , Can maintain its effect over a long period of time. Further, coloring due to the ultraviolet absorbing monomer (1) hardly occurs. Therefore, the ultraviolet absorbing lacquer composition containing the ultraviolet absorbing copolymer also has the same performance as the ultraviolet absorbing copolymer.

Further, the ultraviolet absorbing lacquer composition is a monomer composition containing the ultraviolet absorbing monomer (1), a cycloalkyl group-containing monomer, and an acidic functional group-containing monomer. The inclusion of the UV-absorbing copolymer formed by copolymerization remarkably exhibits the effect of improving the dispersibility of various pigments such as carbon black and the color mixing stability in a composite pigment system. From this, by the known pigment dispersion method,
It is also possible to disperse various pigments to obtain a colored paint. Using the ultraviolet absorbing lacquer composition, weather resistance, gloss,
It is possible to obtain a coating film having excellent properties such as hardness, crack resistance, water resistance, and adhesion to a substrate. That is, the ultraviolet absorbing lacquer composition is remarkably excellent in the maintenance of the ultraviolet absorbing ability for a long period of time and the weather resistance, and is free from the elution of the ultraviolet absorbing component from the copolymer, bleed-out, coloring and discoloration. Further, by using the ultraviolet absorbing lacquer composition, it is possible to obtain a coating film having excellent physical properties such as gloss, image clarity, solvent resistance, chemical resistance and water resistance. Furthermore, the UV absorbing lacquer composition has excellent workability.

Next, a coating composition obtained by copolymerizing a monomer composition containing the ultraviolet absorbing monomer (1), a cycloalkyl group-containing monomer and a hydroxyl group-containing monomer ( The coating composition (b) will be described below.

In the coating composition (b), the content of each monomer 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% by weight to 30% by weight, and 1% by weight to
The range of 20% by weight is more preferable, and the range of 2% by weight to 15% by weight is particularly preferable.

When the amount of the ultraviolet absorbing monomer (1) in the monomer composition is less than 0.1% by weight, the ultraviolet absorbing ability of the obtained coating composition (b) becomes insufficient. Not preferable. On the other hand, when the amount of the ultraviolet absorbing monomer (1) is more than 30% by weight, the gloss and the feeling of flesh of the coating film comprising the coating composition (b) are insufficient and the appearance is ugly. In addition, the solvent resistance and the chemical resistance are poor, which is not preferable.

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, A range of 10% by weight to 70% by weight is particularly preferable.

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 longevity of the coating film comprising 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 preferable. 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 are too small, and the coating composition The weather resistance of the coating film comprising (b) becomes insufficient, and
It is not preferable because it has poor solvent resistance and chemical resistance.

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 2% by weight to 40% by weight.
Particularly preferably, it is within the range of 35% by weight 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 is small and the crosslinking density is low. It 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 lowered, which is not preferable. Further, the storage stability after compounding the below-described polyisocyanate compound or a modified product thereof, or the below-described aminoplast resin or blocked polyisocyanate compound is not preferable.

By obtaining the amount of the ultraviolet absorbing monomer (1), the amount of the cycloalkyl group-containing monomer, and the amount of the hydroxyl group-containing monomer in the monomer composition within the above ranges, it can be obtained. A coating film having various physical properties such as mechanical properties and acid resistance and long-term weather resistance can be formed from the coating composition (b).

The UV stable monomers (3) and (4) are used, if necessary, within a total content of 20% by weight or less in the monomer composition, but 0.1% by weight or more. By this, the ultraviolet stability of the resulting coating composition (b) will be sufficient and long-term weather resistance will be realized. The weight ratio of the UV stable monomer (3) and 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).

In obtaining the above-mentioned monomer composition, the ultraviolet absorbing monomer (1), the cycloalkyl group-containing monomer, the hydroxyl group-containing monomer, the acidic functional group-containing monomer, and the ultraviolet stability monomer are used. The method for mixing the monomers (3) and (4) and the other monomers is not particularly limited. That is, the method for preparing the monomer composition is not particularly limited.

The polymerization method at the time of copolymerizing the monomer composition is not particularly limited, and various conventionally known polymerization methods such as solution polymerization method, emulsion polymerization method, suspension polymerization method, and bulk polymerization method can be used. Although a polymerization method or the like can be adopted, it is preferable to adopt a solution polymerization method.

Examples of the solvent that can be used when the monomer composition is copolymerized by using the solution polymerization method include, but are not particularly limited to, the above-exemplified organic solvents and water. 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 coating composition (b), when a cross-linking agent composed of a polyisocyanate compound or a modified product thereof is added to the copolymer, among the above-exemplified organic solvents, aliphatic alcohols and alkylene glycol monoalkyl are included. Solvents which are active towards isocyanate groups, such as ethers and water, are not preferred.

When the monomer composition is copolymerized, a polymerization initiator can be used. Examples of the above-mentioned polymerization initiator include, for example, 2,2′-azobis (2-methylbutyronitrile), t-butylperoxy-2-ethylhexanoate, 2,2′-azobisisobutyronitrile, Examples thereof include usual 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 room temperature to 200 ° C., more preferably 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, for the purpose of controlling the molecular weight, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, carbon tetrachloride or carbon tetrabromide or a polymerization regulator may be used. That is, the molecular weight of the obtained copolymer is the reaction time, the reaction temperature, or the composition of the monomer composition to be used, the type of the polymerization initiator, and the like, and if necessary, a chain transfer agent or a polymerization regulator. It can be adjusted by 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 added to the coating composition (b) is not particularly limited as long as it is a compound having two or more functional groups capable of reacting with a hydroxyl group in one molecule.
Further, the crosslinking agent may be used alone, or two or more kinds 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-mentioned cross-linking agent, a two-part cross-linking type room temperature-curing type which cures 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 above-mentioned cross-linking agent, a one-pack cross-linking type coating composition can be suitably obtained. In addition, in the following description, for convenience of description, when it is necessary to distinguish the coating composition (b) by a crosslinking agent, a coating composition using a polyisocyanate compound or a modified product thereof as a crosslinking agent is used. Composition (b1)
The coating composition using the aminoplast resin or the blocked polyisocyanate compound as a crosslinking agent is referred to as a coating composition (b2).

The polyisocyanate compound or its modified product 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, metaxylylene diisocyanate, 4,4′-methylene bis. (Cyclohexyl isocyanate), and adduct polyisocyanate compounds such as trimethylolpropane adducts, burettes, and isocyanurates which are derivatives of these diisocyanates. The amount of the polyisocyanate compound or its modified product relative to the copolymer in the coating composition (b1) is not particularly limited.

Examples of the above aminoplast resins include aminoplast resins such as methyl etherified melamine resin, butyl etherified melamine resin, butyl etherified benzoguanamine resin, butyl etherified cyclohexyl benzoguanamine resin, and water-solubilized products thereof. It is not particularly limited. These aminoplast resins may be used alone,
Further, two or more kinds may be appropriately mixed and used. The compounding amount of the aminoplast resin or its water-solubilized product with respect to the copolymer in the coating composition (b2) 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, metaxylylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate. ), And a trimethylolpropane adduct which is a derivative of these diisocyanates,
Adduct polyisocyanate compounds such as burettes and isocyanurates, that is, the polyisocyanate compounds or their modified isocyanate groups are blocked polyisocyanates obtained by blocking compounds such as ε-caprolactam, phenol, cresol, oxime and alcohol. A compound etc. are mentioned. These block polyisocyanate compounds may be used alone, or two or more kinds may be appropriately mixed and used. Further, the compounding amount of the block polyisocyanate compound with respect to the copolymer in the coating composition (b2) is not particularly limited.

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

Examples of the above-mentioned pigment include the pigments exemplified above. Only one kind of these various additives may be used, or two or more kinds thereof may be appropriately mixed and used. Moreover, the amount of these additives used is not particularly limited. The coating composition (b) can be used as a colored coating by dispersing various pigments by a known pigment dispersion method, and has excellent dispersibility of pigments such as carbon black. Also,
It is also excellent in color mixing stability in composite pigment systems. The method of blending the copolymer, crosslinking agent, and various additives is not particularly limited. Further, the coating composition (b2)
In the above, the copolymer may be added in the form of a solution, a dispersion liquid, or a powder, and a crosslinking agent or the like may be added. Is preferred.

As described above, the coating composition (b) is a monomer composition containing the ultraviolet absorbing monomer (1), a cycloalkyl group-containing monomer, and a hydroxyl group-containing monomer. And a cross-linking agent. The coating composition (b) has a transparency, a luster, a longevity, a mechanical strength,
It has excellent acid resistance, solvent resistance, etc., and also has excellent ultraviolet absorption ability in the wavelength range of 300 nm to 400 nm, and almost no coloring due to the ultraviolet absorbing monomer (1) occurs, and for a long period of time. It is possible to form a coating film having excellent long-term weather resistance such as gloss retention in outdoor use and discoloration resistance. Then, the coating composition (b1) is prepared by blending the above copolymer with a crosslinking agent composed of a polyisocyanate compound or a modified product thereof. 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 prepared by blending the above copolymer with a crosslinking agent composed of an aminoplast resin or a block polyisocyanate compound. Therefore, a one-component cross-linking type coating composition can be obtained.

As described above, the coating composition used for forming the copolymer layer, that is, the coating composition (a).
(B) and a UV-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 adopted. That is, the method for forming the copolymer layer is, for example, a coating method such as brush coating, spray coating, or roll coater coating; once a film formed by copolymerizing a coating composition is formed, this film is used as a substrate. A method of laminating the base material with a film to form a copolymer layer by sticking or thermocompression bonding to the above can be adopted.

Next, the base material used in the ultraviolet absorbent processed product according to the present invention will be described. Examples of the base material according to the present invention include ABS (acrylonitrile-butadiene-styrene) resin, FRP (fiber reinforced plastic), PET (polyethylene terephthalate), polystyrene, PP (polypropylene), PC (polycarbonate), acrylic resin, Examples include various plastics such as vinyl chloride resin and polyester resin; various metals such as steel plates; glass; wood such as cypress and plywood, but are not particularly limited. Moreover, the shape and size of the base material are not particularly limited.

The adhesion between the coating film composed of the coating composition and the base material is good, and therefore, the base material is protected from ultraviolet rays by forming a copolymer layer on the surface of the base material. You can 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 or the like (described later) may be laminated between the base material and the copolymer layer.

Then, for example, when the base material is FRP, by forming a copolymer layer, the glass fiber or calcium carbonate in the FRP can be used even when the ultraviolet absorbing processed product is used for a long period of time. The particles (filler) and the like are not exposed on the surface of the processed product, and the weather resistance and solvent resistance are improved. Therefore, the ultraviolet-absorbing processed product can withstand long-term use and is suitable for a wide range of applications such as containers such as tanks and containers, and various building materials.

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

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

First, a method for producing an ultraviolet-absorbing processed product by applying the coating composition will be described. As shown in FIG. 1, first, an adhesive is applied to the surface of the base material 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, or a wood board 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 base material 1
The material of the cosmetic layer 3 is not particularly limited, and conventionally known materials can be used. Further, the above-mentioned adhesive may be appropriately selected according to the materials of the base material 1 and the decorative layer 3, and is not particularly limited.

Then, the 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 formed by baking at a relatively low temperature.
To form As a result, an ultraviolet absorbent processed product is manufactured. The above-mentioned coating composition may have an optimum composition depending on the material of the decorative layer 3, the use of the ultraviolet absorbing processed product, and the like. 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, the use of the ultraviolet absorbing processed product, and the like.

However, in the case of forming the copolymer layer 4 on the surface of the base material 1, when 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 preferably applied. The above-mentioned primer may be uniformly applied to the substrate so that the film thickness thereof will be 1 to 50 microns. As a method of applying the primer, for example, a general method such as brush coating, spray coating, roll coater coating or the like can be adopted. The base material made of polypropylene may be manufactured by a conventionally known molding method such as an extrusion molding method, a hollow molding method, an injection molding method, or a compression molding method.

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

As a result, a copolymer layer is formed on the surface of the base material 1 to manufacture an ultraviolet absorbing processed product. The above-mentioned coating composition may have an optimum composition depending on the meltability of the film 5, the material of the substrate 1, the use of the ultraviolet absorbing processed product, and the like. The method for molding the film 5 is not particularly limited.

Next, after forming the coating composition into a film,
A method for producing a UV-absorbing processed product by thermocompression bonding will be described. First, the coating composition is extrusion-molded under a predetermined condition using a T-die method or the like to obtain a film having a predetermined thickness. Next, as shown in FIG. 3, an adhesive is applied to the surface of the base material 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, a wood board, etc. 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
The material is not particularly limited, and conventionally known materials can be used. Further, the above-mentioned 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.
The material and forming method of the protective layer 6 are not particularly limited. Further, as a specific example of the unsaturated polyester resin, Epolak P-5 manufactured by Nippon Shokubai Co., Ltd.
A composition obtained by adding 1% of methyl ethyl ketone peroxide (polymerization initiator) to 12Y is mentioned, but it is not particularly limited.

Subsequently, the film 5 is placed on the surface of the protective layer 6, and the film 5 is bonded to the protective layer 6 by thermocompression bonding at a predetermined temperature and pressure. As a result, the copolymer layer is formed, and the ultraviolet absorbent processed product is manufactured. The coating composition may have an optimum composition depending on 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 molding 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, the use of the ultraviolet absorbing processed product, and the like. 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 the copolymer layer using a mold will be described. As shown in FIG. 4A, first, the mold release agent 11 is applied to the molding surface of the mold 10 such as a mold. In addition, release agent 1
The type 1 is not particularly limited, and conventionally known release agents can be used.

Next, as shown in FIG. 6B, after applying the coating composition to the molding surface, the mold 10 is heated to a predetermined temperature, for example, 40 ° C. to 60 ° C. The composition for use is heat-cured to form the copolymer layer 7. The coating composition may have an optimum composition according to the materials of the gel coat layer 8 and the base material 9 described below, the use of the ultraviolet absorbing processed product, and the like.

Then, as shown in FIG. 7C, after coating the copolymer layer 7 with, for example, an unsaturated polyester resin, the mold 10 is heated to a predetermined temperature to give the unsaturated resin. The polyester resin is heat-cured to form the gel coat layer 8. That is, the gel coat layer 8 is laminated on the copolymer layer 7. The material and 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 lined and laminated. As a specific example of the resin composition, Epolak G-1 manufactured by Nippon Shokubai Co., Ltd.
A resin composition obtained by impregnating glass fiber (chopped strand mat FEM-380-M-WN; manufactured by Fuji Fiber Glass Co., Ltd.) with a laminating resin obtained by adding 1% of methyl ethyl ketone peroxide to 12 is mentioned. It is not particularly limited. That is, the base material 9 is not particularly limited as long as it is made of a material that can be heat-cured.

Then, as shown in FIG. 10D, the mold 10 is heated to heat and cure the resin composition to mold the base material 9 and the surface of the base material 9. The above-mentioned copolymer layer 7 is transferred via the gel coat layer 8. After that, by removing the mold, an ultraviolet-absorbing processed product as shown in FIG. The formation of the gel coat layer 8 may be omitted depending on the material of the base material 9 and the application 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 at the time of heat molding and so-called foam fogging are reduced, and mold releasability and dimensional stability are improved.

As described above, the UV absorbing processed product according to the present invention is obtained by copolymerizing the monomer composition containing the UV absorbing monomer (1) and the cycloalkyl group-containing monomer. And a copolymer layer of Further, the processed product having an ultraviolet absorbing property according to the present invention is configured such that the monomer composition further contains an ultraviolet stable monomer (3) and / or an ultraviolet stable monomer (4).

The above-mentioned copolymer layer is obtained by copolymerizing a monomer composition containing an ultraviolet absorbing monomer (1) having a benzotriazole skeleton and a cycloalkyl group-containing monomer. Therefore, it has ultraviolet absorption ability and excellent long-term weather resistance, and also has good adhesion and adhesiveness to the base material, as well as the effect of protecting the base and the effect of preventing yellowing. It has excellent solvent properties. Therefore, the ultraviolet absorbent processed product of the present invention has an ultraviolet absorbing ability, is excellent in long-term weather resistance, and is also excellent in gloss, water resistance, solvent resistance and the like. Here, the “benzotriazole-based skeleton” refers to a structure in which a phenol ring is bonded to the 2-position nitrogen atom of the benzotriazole ring.

Further, as described above, in the method for producing an ultraviolet absorbent processed product according to the present invention, the copolymer layer formed by copolymerizing the above monomer composition is formed on the molding surface of the mold. After that, a base material to be a processed product is molded with the above mold, and the copolymer layer is transferred to the base material side. This makes it possible to easily produce an ultraviolet-absorbing processed product having the above-mentioned performance and having a copolymer layer having a smooth surface.

Examples of the ultraviolet absorbent processed products according to the present invention include plastic molded products such as tanks and containers, home electric appliances, steel products, large-scale structures, automobile interior and exterior parts, building materials, woodwork products, glass products and the like. However, it is not particularly limited.

[0136]

According to the above constitution, an ultraviolet absorbent processed product having an ultraviolet absorbing ability, a long-term weather resistance and a copolymer layer having excellent gloss, water resistance, solvent resistance and the like is provided. be able to. Further, according to the above method, it is possible to easily manufacture an ultraviolet absorbing processed product having the above-mentioned performance and having a copolymer layer having a smooth surface.

[0137]

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 addition, "part" in an Example shows "weight part" and "%" shows "weight%."

[Example 1] To a four-necked flask equipped with a thermometer, a gas blowing 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. Then, this solution was heated to 90 ° C. with stirring under a nitrogen gas stream.

On the other hand, in the above dropping funnel, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole (hereinafter referred to as benzotriazole) as an ultraviolet absorbing monomer (1) was added. (A)) 2.5
Part, cyclohexyl methacrylate as a cycloalkyl group-containing monomer (hereinafter referred to as CHMA) 20.0 parts, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine as an ultraviolet stable monomer (3) (Hereinafter referred to as piperidine (C)) 1.2 parts, methacrylic acid as an acid functional group-containing monomer 0.3 part, hydroxyethyl acrylate as a hydroxyl group-containing monomer 6.0 parts, butyl acrylate 10.0 as another monomer Composition (50 parts) consisting of 10 parts and methyl methacrylate (4.5 parts), toluene (4.5 parts) and xylene (2.2 parts), and 2,2'-azobis (2-methylbutyronitrile) as a polymerization initiator
A mixture consisting of 0.8 parts was added.

Next, while the solution in the flask was stirred at 90 ° C., the above mixture was added dropwise to the solution over 3 hours.
After completion of dropping, while stirring the reaction solution under a nitrogen gas stream,
Hold at 90 ° C. for 5 hours. Then, after the completion of the polymerization reaction, the reaction liquid 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 acrylic polyol solution had a nonvolatile content of 50%, a hydroxyl value of 29 mgKOH / g, an acid value of 2.0 mgKOH / g, and a viscosity measured by a Gardner-type foam viscometer of Z2 (viscosity standard liquid symbol). Met. In addition, the weight average molecular weight (M
w) was 11,000. The composition of the monomer composition, and
Table 1 is a summary of various measurement results of the acrylic polyol solution.
Shown in

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

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

After taking out the mold, at room temperature, a general-purpose unsaturated polyester resin for laminating (Epolak G-773PTMY; Japan Co., Ltd.) on the gel coat layer is used as a base material, that is, an FRP molded body. A catalyst and glass fiber (CM455FA; Asahi Fiber Co., Ltd.) were lined and laminated (3 plies). To the above laminating resin, 1% of methyl ethyl ketone peroxide as a polymerization initiator was added.

Then, by heating the die in a heating furnace, the lamination resin is heat-cured to form an FRP as a base material, and the above-mentioned co-weight is applied to the surface of the FRP molded body. The coalescence layer was transferred. After that, the mold was removed to obtain an FRP molded body as an ultraviolet absorbing processed product. The surface of the obtained FRP molded product, that is, the surface of the copolymer layer was smooth.

Next, a fluorescent UV condensation test (QUV test), which is a weathering test, is carried out using the above FRP molded body,
The yellowing degree (Δb value) was measured. The measurement is JIS K 5
It carried out based on 400-1979. As a measuring device, manufactured by Toyo Seiki Co., Ltd .; Yubucon (UVCON) U
C-1 type was used. As a measurement condition, a cycle of irradiation 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 product having no copolymer layer formed on the surface thereof, that is, an FRP which is a conventional processed product.
When the degree of yellowing of the molded product was measured in the same manner, QUV
The yellowing degree after 20 hours was 20.

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

Example 2 A 4-necked flask equipped with a thermometer, a gas blowing tube, a dropping funnel, a reflux condenser and a 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), 20.0 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 dropping funnel. Monomer composition consisting of parts (47
Parts) and 4.5 parts toluene and 2.1 parts xylene, 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, 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 to the solution at once, and the rest (80%) was added dropwise over 3 hours. After completion of the dropping, the reaction solution was maintained at 90 ° C. for 5 hours while stirring under a nitrogen gas stream. Then, after the completion of the polymerization reaction, the reaction liquid was cooled. As a result, an acrylic polyol solution was obtained. The acrylic polyol solution has a nonvolatile content of 50%, a hydroxyl value of 27 mgKOH / g, and an acid value of 2.0 mgKO.
The viscosity was 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. The composition of the monomer composition and various measurement results of the acrylic polyol solution are summarized in Table 1.

Next, the same operation as in Example 1 was carried out to prepare a coating composition (coating composition (b1)) which was to be a copolymer layer, using the above acrylic polyol solution. This coating material was extruded using the T-die method under predetermined conditions to obtain a film having a thickness of 20 μm. The extrusion moldability of the above paint was extremely good.

Subsequently, this film was thermocompression-bonded to one side of the PC sheet extruded under predetermined conditions, that is, the PC sheet immediately after being discharged from the extruder. As a result, a PC plate as an ultraviolet-absorbing processed product was obtained in which the above-mentioned film as the copolymer layer was laminated on the surface of the PC sheet as the 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 found to be a conventional PC film coated with a conventional resin film.
It was found that it has extremely excellent weather resistance as compared with the plate. Further, the PC board according to the present invention hardly caused discoloration and deterioration of gloss even when used for a long period of time. Furthermore, the PC board according to the present invention had impact resistance equivalent to that of a PC board having no copolymer layer formed on the surface thereof, that is, a PC sheet.

Example 3 In place of 50 parts of the monomer composition of Example 1, 2.5 parts of benzotriazole (A) and C were used.
A monomer composition comprising 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
The same reaction and operation as in Example 1 were carried out except that (part) was used to obtain an acrylic polyol solution. The acrylic polyol solution has a nonvolatile content of 50% and a hydroxyl value of 29%.
It was mgKOH / g, the acid value was 2.0 mgKOH / g, and the viscosity measured by a Gardner foam viscometer was Z2 (viscosity standard liquid symbol). The weight average molecular weight (Mw) of the acrylic polyol was 11,000. The composition of the monomer composition and various measurement results of the acrylic polyol solution are summarized in Table 1.

Next, the same operation as in Example 1 was carried out to prepare a coating material (coating composition (b1)) to be a copolymer layer, using the above acrylic polyol solution. Next, an ultraviolet absorbing processed product was prepared using the above coating material. That is, first, a PP plate (manufactured by Japan Test Panel Co., Ltd.) as a base material was coated with a primer (Super Clone 82
2; manufactured by Nippon Paper Industries Co., Ltd.) was sprayed to a film thickness of 5 μm, and then the primer was dried at 60 ° C. for 30 minutes. Next, the above-mentioned paint is applied on the primer layer to a film thickness of 20.
After spray coating so that the thickness becomes μm, the paint is applied at 80 ° C.
Dry for 60 minutes. As a result, a PP plate as an ultraviolet-absorbing processed product was obtained in which the primer layer and the copolymer layer (top coat) were laminated on the PP plate surface. Above P
The adhesion between the P 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 the present invention was found to have a conventional resin coating (for example, polyurethane coating, acrylic coating) generally used. It was found that it has extremely excellent weather resistance as compared with a PP plate coated and coated with a resin-based paint or an epoxy resin-based paint. Further, the PP plate according to the present invention hardly caused discoloration and deterioration of gloss even when used for a long period of time. Further, the PP plate according to the present invention had impact resistance equivalent to that of the PP plate having no copolymer layer formed on the surface.

[0157]

[Table 1]

[Example 4] Internal volume equipped with a thermometer, a gas blowing tube, a dropping funnel, a reflux condenser and a stirrer
In a 0.5 L separable flask, 70.0 parts of deionized water, 1.5 parts of nonipol 200 (trade name; polyoxyethylene nonylphenyl ether manufactured by Sanyo Kasei Co., Ltd.) as an emulsifier (surfactant) and Newpol PE-
68 (trade name; manufactured by Sanyo Kasei Co., Ltd., polyoxyethylene glycol-polyoxypropylene glycol-
0.3 parts of polyoxyethylene glycol / triblock copolymer) was charged. Then, this solution was heated to 65 ° C. with stirring under a nitrogen gas stream.

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.
Part, methyl methacrylate 14.0 parts, n-butyl methacrylate 25.0 parts and 2-ethylhexyl acrylate 10.0 parts (100 parts), and the above nonipol 2
00 (3.0 parts) and New Pole PE-68 (0.8 parts)
A preemulsion mixture consisting of and was added to 25.0 parts of deionized water.

Next, the solution in the separable flask was heated to 65 ° C.
The above pre-emulsion mixture was added dropwise to the solution over 2 hours with stirring. Before the dropping operation is completed, 6.0 parts of a 5.0% ammonium persulfate aqueous solution and 5 parts of a redox initiator are added to the above solution.
A 3.0% aqueous solution of sodium hydrogen sulfite was divided and added every 10 minutes.

After completion of dropping, the reaction solution was aged at 65 ° C. for 1 hour while stirring under a nitrogen gas stream. After completion of the polymerization reaction, the reaction solution is cooled, and then 25% ammonia water is added.
0.5 part was added to neutralize. As a result, 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 a copolymer layer was prepared using the above aqueous dispersion. That is, the above aqueous dispersion 1
To 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 part, CS-12 (product name: manufactured by Chisso Co., Ltd.) 10.0 which is a film forming aid
Parts and 5% Adecanol UH- which is a viscosity modifier
420 (trade name; manufactured by Asahi Denka Kogyo Co., Ltd.) 1.0 part of the mixture is mixed to form a coating material (176.3
Parts) were prepared.

Then, an ultraviolet-absorbing processed product was prepared using the above coating composition (coating composition (a)). That is, first, an acrylic resin (Aroset 5210; manufactured by Nippon Shokubai Co., Ltd.), which is a primer, is applied to a high impact (HI) polystyrene plate (H8652; manufactured by Asahi Chemical Industry Co., Ltd.) as a substrate so that the film thickness becomes 3 μm. After spray coating, the acrylic resin was dried at 60 ° C. for 10 minutes. Next, the above-mentioned paint is applied on the acrylic resin layer to form a film having a thickness of 10 μm.
Then, the coating material was dried at 60 ° C. for 30 minutes. As a result, a polystyrene plate as an ultraviolet-absorbing processed product was obtained 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 carried out and a weather resistance test was carried out. As a result, the polystyrene plate according to the present invention was found to be a polystyrene plate obtained by applying a general-purpose acrylic emulsion under the same conditions and methods as above. It was found that it has extremely excellent weather resistance as compared with. Further, the polystyrene plate according to the present invention hardly caused discoloration and deterioration of gloss even when used for a long period of time.

Example 5 To a four-necked flask equipped with a thermometer, a gas blowing tube, a dropping funnel, a reflux condenser and a stirrer was charged 100.0 parts of toluene. Then, this toluene was heated to 80 ° C. while stirring under a nitrogen gas stream.

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

Next, the above mixture was added dropwise to the solution in the flask while stirring at 80 ° C. for 2 hours.
After completion of dropping, while stirring the reaction solution under a nitrogen gas stream,
Hold at 80 ° C for 6 hours. Then, after the completion of the polymerization reaction, the reaction liquid 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 is 18,0
It was 00, and the glass transition temperature (Tg) converted by the predetermined method was 55 ° C. Subsequently, the obtained copolymer solution was diluted by adding thinner to a predetermined viscosity to obtain a coating material (ultraviolet absorbing lacquer composition) to be a copolymer layer.

Next, an ultraviolet absorbing processed product was prepared using the above coating material. That is, first, a hinoki material as a base material was brush-coated with the above coating so that the film thickness after drying was 25 μm, and then the coating was dried at room temperature for 7 days. As a result, a cypress 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 carried out and a weather resistance test was carried out. As a result, the hinoki material according to the present invention was found to be a hinoki material prepared by applying a general-purpose acrylic paint under the same conditions and methods as described above. It was found that it has extremely excellent weather resistance as compared with. Further, the cypress material according to the present invention hardly caused discoloration and deterioration of gloss even when used for a long period of time.

Example 6 First, the same reaction and operation as in Example 1 were carried out to obtain a coating material to be a copolymer layer.
Next, this coating material was extrusion-molded under a predetermined condition using a T-die method to obtain a film having a thickness of 20 μm.
The extrusion moldability of the above paint was extremely good.

Subsequently, on this film, a solution type copolyester adhesive (Vylon 50AS; manufactured by Toyobo Co., Ltd.) and an isocyanate crosslinking agent (Coronate HL;
Nippon Polyurethane Industry Co., Ltd.) and weight ratio 100: 3
A mixed solution prepared by mixing the above mixture was applied so as to have a film thickness of 8 μm, and then the mixed solution was dried at 60 ° C. to 80 ° C. to remove the solvent. Thereby, a film having an adhesive layer on the surface was obtained.

This film was attached to a PET plate (manufactured by Japan Test Panel Co., Ltd.) as a substrate and left at 80 ° C. for 30 minutes. As a result, a PET plate as an ultraviolet-absorbing processed product was obtained in which the above-mentioned film as a copolymer layer was attached to 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 carried out to carry out a weather resistance test. As a result, the PET plate according to the present invention was compared with a PET plate having no copolymer layer adhered to its surface. It was found to have extremely excellent weather resistance.
Further, the PET plate according to the present invention hardly caused discoloration and fading even when used for a long period of time.

[0174]

As described above, the ultraviolet absorbing processed product of the present invention comprises the ultraviolet absorbing monomer represented by the general formula (1) and the unsaturated monomer represented by the general formula (2). It is a structure having a copolymer layer formed by copolymerizing a monomer composition containing a monomer. Further, the ultraviolet absorbing processed product of the present invention,
As described above, the monomer composition further contains the UV stable monomer represented by the general formula (3) and / or the UV stable monomer represented by the general formula (4). It is a composition.

As a result, it is possible to provide an ultraviolet-absorbing processed product having a copolymer layer having an ultraviolet-absorbing ability, long-term weather resistance and gloss, water resistance and solvent resistance. Produce an effect.

As described above, the method for producing an ultraviolet-absorbing processed product of the present invention comprises the steps of forming a copolymer layer formed by copolymerizing the above-mentioned monomer composition on the molding surface of the mold. A method of molding a base material to be a processed product with the above mold and transferring the copolymer layer to the base material side.

As a result, 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.

[Brief description of drawings]

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

FIG. 2 is a cross-sectional view showing another example of the method for producing an 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, in which (a) is
It is a sectional view showing the state where a mold release agent was applied to a mold, (b)
Is a cross-sectional view showing a state in which a copolymer layer is formed,
(C) is sectional drawing which shows the state which laminated | stacked the gel coat layer, (d) is sectional drawing which shows the state which laminated | stacked the base material, (e) is sectional drawing which shows an ultraviolet absorption processed product. Is.

[Explanation 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 Model 11 Release Agent

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor ▲ Yoshi ▼ Masaya Ta No.5 Nishimitabicho, Suita City, Osaka Prefecture Nippon Catalyst Co., Ltd. No. 5-8 within Nippon Shokubai Co., Ltd.

Claims (3)

[Claims] 1. A compound of the general formula (1) (In the formula, 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 hydrogen. Represents an atom or a methyl group, and 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). A monomer and a general formula (2): (In the formula, 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). An ultraviolet-absorbing processed product having a copolymer layer obtained by copolymerizing a monomer composition containing the same. 2. The above monomer composition has the general formula (3): (Wherein, R ⁶ represents a hydrogen atom or a cyano group, R ^7,
R ⁸ independently represents a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, and R ⁹ is a hydrogen atom or 1 to 18 carbon atoms.
Of the formula (4), wherein Y is an oxygen atom or an imino group) and / or a UV 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). The ultraviolet absorbent processed product according to claim 1. 3. A base material to be a processed product in the mold after forming a copolymer layer on the molding surface of the mold by copolymerizing the monomer composition according to claim 1 or 2. And a step of transferring the copolymer layer to the base material side while molding the above.