JPH093396A - Coating composition and preparation thereof - Google Patents

Abstract

PURPOSE: To form a coating which has an ultraviolet absorption capability and possesses excellent long-term weather resistance, water-resistance, gloss, sharpness and other properties by emulsion-polymerizing a monomer compsn. comprising a particular ultraviolet-absorbing monomer (A) and a particular unsatd. monomer (B). CONSTITUTION: A monomer compsn. comprising 0.1 to 30wt % component (A) represented by the formula I (R<1> represent H or a 1-8 C hydrocarbon radical; R<2> represents a 1-6C alkylene; R<3> represent H or methyl; and X represents H, a halogen, a 1-8C hydrocarbon radical, a 1-4C alkoxy, cyano, or nitro) and 2 to 95wt.% component (B) represented by the formula II (R<10> represents H or a 1-2C hydrocarbon radical; and Z represents an optionally substd. cycloalkyl) is emulsion-polymerized using a water-soluble or water-dispersible, alkylterminal polymer having an acid value of 200mg KOH/g or more and/or its salt, the polymer being prepd. by polymerizing a monomer component contg. an unsatd. carboxylic acid (e.g. acrylic acid) in the presence of a 6-18C alkylmercaptan. The reaction temp. is pref. 0 to 100 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention has an ultraviolet absorbing ability,
The present invention relates to a coating composition capable of forming a coating film excellent in long-term weather resistance, water resistance, gloss, sharpness and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, when an ultraviolet absorber is added to a polymerization composition for use, deterioration of performance due to bleed-out of the ultraviolet absorber from the polymerization composition during processing or use thereof, and , Toxicity to the ecosystem has become a problem. Therefore, in order to improve the above problems, a method of using an ultraviolet absorber having a polymerizable skeleton and homopolymerizing it or copolymerizing it with a polymerizable monomer is used. As such a method, for example, 2,4-
A method has been reported in which an ester of dihydroxybenzophenone and acrylic acid (Japanese Patent Publication No. Sho 36-6771) is copolymerized with a polymerizable monomer.

However, the acrylic acid ester of a benzophenone derivative as an ultraviolet absorbing monomer has a relatively short maximum absorption wavelength, and therefore its accumulated energy is relatively large in the ultraviolet region of the sun rays on the ground. Insufficient to absorb in the wavelength range (320 nm to 400 nm). Therefore, various benzotriazole-based UV absorbers have been proposed which have a high UV absorption ability in the long wavelength region, a longer maximum absorption wavelength, and are free from elution from the polymerization composition and bleeding out. Then, for example, JP-A-6-172742 and JP-A-5-255447 disclose a benzotriazole-based ultraviolet absorber.

[0004]

However, 2- [2'-hydroxy-5 '-(β-methacryloyloxyethoxy)-, which is disclosed in the above-mentioned Japanese Patent Laid-Open No. 6-172742, is disclosed.
The ultraviolet absorber using 3'-t-butylphenyl] -4-t-butyl-2H-benzotriazole has a drawback that it is colored when it is continuously irradiated with ultraviolet rays for a long period of time. Further, the ultraviolet absorbing composition disclosed in the above-mentioned JP-A-5-255447, when used as a coating composition, is inferior in long-term weather resistance of a coating film comprising the ultraviolet absorbing composition. There is a problem.

That is, the above-mentioned conventional ultraviolet absorber has a problem that it is inferior in ultraviolet absorbing ability and long-term weather resistance when used as a coating composition. Therefore, there is a demand for a coating composition capable of forming a coating film having excellent ultraviolet absorption ability and long-term weather resistance.

The present invention has been made in view of the above-mentioned conventional problems, and an object thereof is to be particularly excellent in ultraviolet absorbing ability in a wavelength range of 300 nm to 400 nm, and to be long-term weather resistance, water resistance, and It is intended to provide a coating composition capable of forming a coating film excellent in gloss and image clarity, and a method for producing the same.

[0007]

[Means for Solving the Problems] The inventors of the present application have made earnest studies on a coating composition and a method for producing the same in order to achieve the above-mentioned object. As a result, an ultraviolet-absorbing monomer having a specific structure was identified. A coating composition obtained by emulsion-polymerizing a monomer composition containing an unsaturated monomer having a structure of 300,
It was found that a coating film with excellent UV absorption in the wavelength range of nm to 400 nm and excellent long-term weather resistance, water resistance, gloss, and image clarity can be formed, and a specific emulsifier is used. It was found that a coating composition having the above-mentioned properties can be easily produced by emulsion-polymerizing the above-mentioned monomer composition using the above-mentioned substances, and the present invention has been completed.

That is, in order to solve the above problems, the coating composition 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 is obtained by emulsion polymerization of a monomer composition containing an unsaturated monomer represented by It has a feature.

In order to solve the above problems, the coating composition of the invention of claim 2 is the same as the coating composition of claim 1, 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.

In order to solve the above-mentioned problems, the method for producing a coating composition according to the third aspect of the present invention has 6 carbon atoms.
Acid value 200mgKOH, which is obtained by polymerizing monomer component containing unsaturated carboxylic acid in the presence of ~ 18 alkyl mercaptan
characterized in that the monomer composition according to claim 1 or 2 is emulsion-polymerized by using a water-soluble or water-dispersible polymer having a terminal alkyl group and / or a salt thereof having an amount of / g or more as an emulsifier. I am trying.

In order to solve the above-mentioned problems, the method for producing a coating composition according to the fourth aspect of the present invention provides a method for producing the coating composition.
The method for producing a coating composition described above is characterized in that the monomer composition further contains a functional group-containing monomer containing a functional group having reactivity with a carboxyl group.

The present invention will be described in detail below. The coating composition according to the present invention is an emulsion-type coating composition, which comprises an ultraviolet absorbing monomer represented by the general formula (1) and an unsaturated monomer represented by the general formula (2). It is formed by emulsion polymerization of a monomer composition containing a monomer. 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, or may also contain a monomer containing a functional group having reactivity with a carboxyl group, and may further contain a monomer other than the above-mentioned 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 and 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, 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 above 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, other monomers optionally contained in the monomer composition (hereinafter referred to as other monomers) May be a compound that does not impair various physical properties required for a coating composition obtained by emulsion polymerization of the monomer composition.

Specific examples of the other monomer include hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate (for example, manufactured by Daicel Chemical Industries Ltd .; trade name Praxel F
M), a hydroxyl group-containing monomer such as mono (meth) acrylate of a polyester diol obtained from phthalic acid and propylene glycol; (meth) acrylic acid, crotonic acid,
Carboxyl group-containing monomers such as itaconic acid, maleic acid and maleic anhydride; sulfonic acid group-containing monomers such as vinyl sulfonic acid, styrene sulfonic acid and sulfoethyl (meth) acrylate; 2- (meth) acryloyloxyethyl acid Phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3-chloropropyl acid phosphate, 2-
Acidic functional group-containing monomers such as methacryloyloxyethyl phenylphosphoric acid and other acidic phosphate-based monomers; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate , (Butyl) (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and the like (meth) acrylic acid alkyl ester; Epoxy group-containing monomers such as glycidyl (meth) acrylate; nitrogen-containing monomers such as (meth) acrylamide, N, N'-dimethylaminoethyl (meth) acrylate, vinyl pyridine, vinyl imidazole; vinyl chloride, vinylidene chloride Halogen-containing unit such as Polymers: aromatic monomers such as styrene, α-methylstyrene, vinyltoluene; vinyl esters such as vinyl acetate; vinyl ethers; polymerizable cyan compounds such as (meth) acrylonitrile;
There is no particular limitation. As the other monomer, only one kind may be used as necessary, or two or more kinds may be appropriately mixed and used.

The content of each of the above-mentioned monomers in the monomer composition is not particularly limited, but the content of the ultraviolet absorbing monomer (1) is within the range of 0.1% by weight to 30% by weight. Preferably, it is more preferably in the range of 1% by weight to 20% by weight, and 2
Particularly preferably, it is within the range of 15% by weight to 15% by weight. 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, and particularly preferably in the range of 10% by weight to 75% by weight. preferable.
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, it is possible to impart ultraviolet absorbing ability to the coating film comprising the coating composition. Further, it is possible to improve dispersibility of an acidic pigment such as carbon black in a coating composition and color mixing stability when a composite pigment is used. Further, by setting the content of the cycloalkyl group-containing monomer within the above range, the coating film made of the coating composition is provided with long-term weather resistance, water resistance, gloss, image clarity, and the like. be able to. 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 resulting coating composition, that is, the coating film has an insufficient ultraviolet absorbing ability. Is not preferable. Further, when the content is more than 30% by weight, the appearance of the coating film made of the coating composition, for example, gloss and image clarity are poor, and the performance such as solvent resistance and chemical resistance is deteriorated. Is not preferred. 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, the weather resistance of the coating film when the resulting coating composition is used as an emulsion type coating material It is not preferable because the performance such as gloss, gloss and hardness is inferior. On the other hand, if the content is more than 95% by weight, the flexibility of the coating film made of the coating composition becomes poor, and cracks are likely to occur in the coating film over time, which is not preferable.

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 can be maintained for a long period of time. The ultraviolet stable monomers (3) and (4) are used within a range that does not impair the physical properties of the resulting coating composition. Also,
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 composed of the coating composition is lowered. May occur. If the total amount is more than 15% by weight, the coating film made of the coating composition may have inferior performance such as water resistance, gloss and image clarity.

The above-mentioned UV absorbing monomer (1), cycloalkyl group-containing monomer, UV 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 a coating composition according to the present invention, 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 surfactant. All conventionally known surfactants such as surfactants, amphoteric surfactants and polymer surfactants 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.

Further, in the method for producing a coating composition according to the present invention, a monomer component containing an unsaturated carboxylic acid is polymerized in the presence of an alkyl mercaptan having 6 to 18 carbon atoms as an emulsifier. It is more preferable to use a water-soluble or water-dispersible polymer having an terminal alkyl group (hereinafter referred to as a terminal alkyl group-containing polymer) having an acid value of 200 mgKOH / g or more 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 which is excellent in initial drying property and further excellent in performance such as long-term weather resistance, water resistance, gloss and sharpness. It is possible to produce an emulsion capable of forming a coating composition, that is, a coating composition.

The above-mentioned terminal alkyl group-containing polymer has an acid content in order to satisfy the polymerization stability during emulsion polymerization and the performance such as water resistance, solvent resistance and strength of the coating film comprising the coating composition. It must have a valency of 200 mgKOH / g or more and be water-soluble or water-dispersible. When the acid value of the terminal alkyl group-containing polymer is less than 200 mgKOH / g, sufficient emulsifying ability cannot be obtained, so that the polymerization stability during emulsion polymerization becomes poor and aggregates are generated. Moreover, the storage stability of the obtained coating composition 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 4000. 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.

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 the unsaturated carboxylic acid in the above-mentioned monomer component may be used within a range such that the resulting terminal alkyl group-containing polymer does not have an acid value of 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. Moreover, the storage stability of the obtained coating composition 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 7,000.
It can be adjusted within the range of, and the surface-active ability can be imparted to the terminal alkyl group-containing polymer.

The amount of the 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
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 obtained coating composition 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 above-mentioned functional group-containing monomer is not particularly limited as long as it is a monomer having 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 initial drying property, water resistance, solvent resistance, strength, etc. of the coating film made of the coating composition are inferior, which is not preferable. If the content is more than 40% by weight, the polymerization stability during emulsion polymerization becomes poor. Moreover, the storage stability of the obtained coating composition 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 a coating composition, but known additives for the polymer composition such as film-forming aids, pigments and fillers can be used. Further, a toner, a wetting agent, an antistatic agent, a defoaming agent, a viscosity adjusting agent and the like can be blended if 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 according to the present invention is an emulsion type coating composition and comprises a monomer containing the ultraviolet absorbing monomer (1) and a cycloalkyl group-containing monomer. The composition is obtained by emulsion polymerization of the body composition.

The coating composition of the present invention is obtained by emulsion-polymerizing a monomer composition containing an ultraviolet absorbing monomer (1) having a benzotriazole skeleton and a cycloalkyl group-containing monomer. Therefore, it has an excellent UV absorption capacity in the wavelength range of 300 nm to 400 nm, and has long-term weather resistance, water resistance, gloss, image clarity, solvent resistance, chemical resistance, discoloration resistance, and crack resistance. It is possible to form a coating film having excellent blister resistance and the like. Further, it is excellent in workability when applying the coating composition. 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.

The method for producing a coating composition according to the present invention comprises polymerizing a monomer component containing an unsaturated carboxylic acid in the presence of an alkyl mercaptan having 6 to 18 carbon atoms.
Water-soluble or water-dispersible with an acid value of 200 mgKOH / g or more,
It is a method of emulsion-polymerizing the above-mentioned monomer composition using a polymer having a terminal alkyl group and / or a salt thereof as an emulsifier. By the above method, a coating composition capable of forming a coating film having further excellent performance can be easily produced.

The article to which the above-mentioned coating composition can be applied is not particularly limited. Examples of the object to be coated include various plastics such as ABS (acrylonitrile-butadiene-styrene) resin, FRP (fiber reinforced plastic), PET (polyethylene terephthalate), polystyrene, polypropylene, polycarbonate, acrylic resin; various metals; glass. Etc. By coating the coating composition of the present invention on the surface of the article to be coated to form a coating film, the article can be protected from ultraviolet rays. That is, the coating composition of the present invention is for plastic moldings, home appliances,
It can be widely used as an ultraviolet absorbing coating agent for steel products, large structures, automobiles, building materials, woodworking, etc.

[0070]

[Advantage] According to the above-mentioned constitution, the ultraviolet absorbing ability is particularly excellent in the wavelength range of 300 nm to 400 nm, and the long-term weather resistance, water resistance, gloss, sharpness, solvent resistance, chemical resistance, Color fastness,
It is possible to provide a coating composition capable of forming a coating film having excellent crack resistance and blister resistance. Further, according to the above method, it is possible to easily produce a coating composition capable of forming a coating film having further excellent performance.

[0071]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these. In the Examples and Comparative Examples, “parts” means “parts by weight”, and “%” means “% by weight”.
Is shown.

[Example 1] 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, in the above dropping funnel, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole (hereinafter referred to as benzotriazole) as the ultraviolet absorbing monomer (1) was added. (A)) 5.0
Parts, cyclohexyl methacrylate (hereinafter referred to as CHMA) as a cycloalkyl group-containing monomer 45.0 parts, acrylic acid as another monomer 1.0 part, methyl methacrylate 14.0 parts, n-butyl methacrylate 25.0 parts and
Monomer composition consisting of 10.0 parts of 2-ethylhexyl acrylate (100 parts) and the above nonipol 200 (3.0 parts)
And Newpol PE-68 (0.8 parts) with deionized water
25.0 parts of pre-emulsion mixture was added. The composition of the monomer composition is summarized in Table 1.

Next, the solution in the separable flask is 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. Thus, an emulsion polymer solution as a coating composition, 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 was prepared using the above aqueous dispersion. That is, 150.0 parts of the above aqueous dispersion was mixed with deionized water.
15.0 parts, antifoaming agent Nopco 8034 (trade name; manufactured by San Nopco Ltd.) 0.3 parts, film forming aid CS-12
By mixing 10.0 parts (trade name; manufactured by Chisso Corporation) and 1.0 part of 5% Adecanol UH-420 (product name; manufactured by Asahi Denka Kogyo Co., Ltd.), which is a viscosity modifier, the paint according to the present invention ( 176.3 parts) were prepared.

On the other hand, aroset 5 is used as the base paint.
252 (trade name; manufactured by Nippon Shokubai Co., Ltd., vinyl acetate resin) 100.0 parts, titanium oxide as an inorganic pigment (trade name Typark R-820; manufactured by Ishihara Sangyo Co., Ltd.) 50.0 parts, and solvent toluene 50.0 A vinyl acetate-based solvent-based white paint (200.0 parts) was prepared by mixing with 10 parts.

Then, by applying the prepared solvent-based white paint to a flexible board made of cement or the like,
The paint was applied to the surface of the board so that the dry film thickness was about 20 μm. Next, the paint according to the present invention was applied to the coated surface so that the dry film thickness was about 25 μm. Then, this flexible board was dried for 7 days under the conditions of a temperature of 23 ° C. and a humidity of 65% to prepare a test piece for a fluorescent UV condensation test (QUV test).

Then, using this test piece, the 60 ° gloss value, gloss retention, discoloration resistance (ΔE) and crack resistance were measured. The measurement was performed based on JIS K 5400-1979. As a measuring device, Yubucon (UVCON) UC-1 type manufactured by Toyo Seiki Seisakusho Co., Ltd. was used. As the measurement conditions, irradiation 70 ° C x 4 hours and wetting 50
The cycle was repeated by setting one set at 4 ° C. for 4 hours, and the above various physical properties were measured after 1000 hours of QUV.
The crack resistance was evaluated by visual observation in four grades (excellent, good, normal, and poor). The initial 60 ° gloss value is 94.
Met.

As a result, the gloss retention was 88%, the discoloration resistance (ΔE) was <1, and the crack resistance was good. The results of these measurements are summarized in Table 2.

Example 2 First, a terminal alkyl group-containing polymer according to the present invention was prepared. That is, a separable flask equipped with a thermometer, a gas blowing tube, a dropping funnel, a reflux condenser and a stirrer was charged with 180 parts of isopropyl alcohol as a solvent, and heated to 81 ° C. while stirring under a nitrogen gas stream. And refluxed for 10 minutes.

On the other hand, in the above dropping funnel, 174 parts of acrylic acid as an unsaturated carboxylic acid (monomer component), 36 parts of n-dodecyl mercaptan as an alkyl mercaptan,
Then, a mixture of 0.42 parts of 2,2′-azobisisobutyronitrile as a polymerization initiator was added.

Next, the solvent in the separable flask was heated to 81 ° C.
The above mixture was added dropwise to the solvent with stirring for 1 hour to carry out a polymerization reaction. After completion of the dropping, the reaction solution was agitated under a nitrogen gas stream and aged for 1 hour while refluxing. Then, after the completion of the polymerization reaction, the reaction solution was cooled to obtain a reaction solution containing a polymer containing a terminal alkyl group.

The solid content of this reaction solution, that is, the content of the terminal alkyl group-containing polymer was 53.9%. The terminal alkyl group-containing polymer has a structure represented by the following general formula, an acid value of 645 mgKOH / g, and a number average molecular weight (M
n) 1200 white powdery substance.

[0085]

Embedded image

Next, a coating composition was prepared using the reaction liquid containing the above-mentioned terminal alkyl group-containing polymer. That is, in a separable flask equipped with a thermometer, a gas blowing tube, a dropping funnel, a reflux condenser and a stirrer, 70.0 parts of pure water and a reaction solution containing the above-mentioned terminal alkyl group-containing polymer 1.4.
And 0.5 part of 25% ammonia water was added to neutralize the mixture to obtain an emulsifier. Then, the emulsifier was gently heated to 65 ° C. with stirring under a nitrogen gas stream.

On the other hand, 5 parts of benzotriazole (A), 40 parts of CHMA, and 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine (as a UV stable monomer (3) were added to the dropping funnel. Hereinafter referred to as piperidine (C))
2.5 parts, acrylic acid as other monomer 1 part, methyl methacrylate 14 parts, n-butyl methacrylate 22.5
Part, 10.0 parts of 2-ethylhexyl acrylate and 5 parts of glycidyl methacrylate (100 parts)
Part) and a reaction liquid containing the terminal alkyl group-containing polymer 4.2.
Parts neutralized with 1.8 parts of 25% ammonia water (6 parts)
Part) and 24.5 parts of pure water were added to the pre-emulsion mixture. The composition of the monomer composition is summarized in Table 1.

Next, the emulsifier in the separable flask was washed with 65
While stirring at 0 ° C, 10% of the above pre-emulsion mixture was added dropwise to the emulsifier. After this dropping operation was completed, 4.0 parts of a 5% aqueous solution of 2,2′-azobis (2-aminodipropane) dihydrochloride as a polymerization initiator was added to the solution in the separable flask. After the addition, the solution was stirred under a nitrogen gas stream at 65 ° C for 10 minutes.

Then, while stirring the above solution, 3 parts of the rest (90%) of the above pre-emulsion mixture were added to the solution.
It dripped over time. During the dropping operation, the reaction temperature was maintained at 65 ° C to 70 ° C.

After the completion of dropping, the reaction solution was aged at 65 ° C to 70 ° C for 1 hour with stirring under a nitrogen gas stream. Then, after the completion of the polymerization reaction, the reaction liquid was cooled. Thus, an emulsion polymer solution as a coating composition, that is, an aqueous dispersion was obtained. This aqueous dispersion has a nonvolatile content of 50% and a viscosity of 20.
It was 00 cps.

Then, the same operation as in Example 1 was carried out to prepare a coating material. Moreover, the same operation as in Example 1 was performed using the obtained coating material to prepare a test piece. Then, using this test piece, 60 ° gloss value, gloss retention rate, color fastness (Δ
E) and crack resistance were measured. The results of these measurements are summarized in Table 2.

Example 3 In place of 100 parts of the monomer composition in Example 2, 15.0 parts of benzotriazole (A),
CHMA 20.0 parts, acrylic acid 1.0 parts, methyl methacrylate 20.0 parts, n-butyl methacrylate 21.0 parts, 2-ethylhexyl acrylate 19.0 parts and glycidyl methacrylate 4.0 parts except that a monomer composition (100 parts) was used, The same reaction and operation as in Example 2 were carried out to obtain an aqueous dispersion as a coating composition. The nonvolatile content of this aqueous dispersion was 50% and the viscosity was 1200 cps.

Next, the same operation as in Example 1 is performed to 60 °
The gloss value, gloss retention, discoloration resistance (ΔE), and crack resistance were measured. The results of these measurements are summarized in Table 2.

Comparative Example 1 Instead of 100 parts of the monomer composition in Example 2, 30.0 parts of CHMA and 1.0 part of acrylic acid were used.
Parts, methyl methacrylate 30.0 parts, n-butyl methacrylate 20.0 parts, 2-ethylhexyl acrylate 15.0 parts and glycidyl methacrylate 4.0 parts, except that a comparative monomer composition (100 parts) was used. The reaction and operation were carried out to obtain an aqueous dispersion as a coating composition for comparison. The nonvolatile content of this aqueous dispersion was 50% and the viscosity was 1700 cps.

Then, the same operation as in Example 1 is carried out to obtain 60 °
The gloss value, gloss retention, discoloration resistance (ΔE), and crack resistance were measured. The results of these measurements are summarized in Table 2.

Comparative Example 2 In place of 100 parts of the monomer composition in Example 2, 10.0 parts of benzotriazole (A),
Except for using a comparative monomer composition (100 parts) consisting of 1.0 part of acrylic acid, 40.0 parts of methyl methacrylate, 26.0 parts of n-butyl methacrylate, 19.0 parts of 2-ethylhexyl acrylate and 4.0 parts of glycidyl methacrylate,
The same reaction and operation as in Example 2 were carried out to obtain an aqueous dispersion as a coating composition for comparison. The nonvolatile content of this aqueous dispersion was 50% and the viscosity was 1000 cps.

Then, the same operation as in Example 1 is carried out at 60 °
The gloss value, gloss retention, discoloration resistance (ΔE), and crack resistance were measured. The results of these measurements are summarized in Table 2.

Comparative Example 3 2- [2′-hydroxy-5 ′-(β-methacryloyloxyethoxy) -3′-t-butylphenyl] was used instead of 100 parts of the monomer composition in Example 2. -Four
-t-Butyl-2H-benzotriazole (hereinafter referred to as benzotriazole (B)) 5.0 parts, CHMA 20.0 parts, acrylic acid 1.0 part, methyl methacrylate 30.0 parts, n-butyl methacrylate 16.0 parts, 2-ethylhexyl acrylate
The same reaction and operation as in Example 2 were carried out except that a comparative monomer composition (100 parts) consisting of 24.0 parts and 4.0 parts of glycidyl methacrylate was used, and an aqueous dispersion was prepared as a coating composition for comparison. A liquid was obtained. The nonvolatile content of this aqueous dispersion was 50% and the viscosity was 1400 cps.

Next, the same operation as in Example 1 is performed to 60 °
The gloss value, gloss retention, discoloration resistance (ΔE), and crack resistance were measured. The results of these measurements are summarized in Table 2.

[0100]

[Table 1]

[0101]

[Table 2]

As is clear from the results shown in Table 2,
A coating film comprising the coating composition of the present invention has a 60 ° gloss value after QUV 1000 hours, a gloss retention rate, and a color change resistance (Δ
Both E) and crack resistance are excellent. Thereby, the coating composition of the present invention is particularly excellent in the ultraviolet absorbing ability in the wavelength region of 300 nm to 400 nm, and long-term weather resistance,
It can be seen that a coating film excellent in gloss, discoloration resistance, crack resistance and the like can be formed.

[0103]

As described above, the coating composition 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 composition obtained by emulsion-polymerizing a monomer composition containing a monomer.

As a result, the ultraviolet absorbing ability in the wavelength range of 300 nm to 400 nm is particularly excellent, and the long-term weather resistance, water resistance, gloss, sharpness, solvent resistance, chemical resistance, discoloration resistance, and It is possible to provide a coating composition capable of forming a coating film having excellent crack resistance, blister resistance and the like.

As described above, the method for producing the coating composition of the present invention comprises polymerizing a monomer component containing an unsaturated carboxylic acid in the presence of an alkylmercaptan having 6 to 18 carbon atoms. This is a method of emulsion-polymerizing the above monomer composition using a water-soluble or water-dispersible polymer having an acid value of 200 mgKOH / g or more and having a terminal alkyl group and / or a salt thereof as an emulsifier.

As a result, it is possible to easily produce a coating composition capable of forming a coating film having more excellent performance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naka ▲ Saki ▼ Mitsuo 5-8 Nishiomitabicho, Suita City, Osaka Prefecture Nippon Shokubai Co., Ltd. (72) Inventor Masaya Uchida 5-8 Nishiomitabicho, Suita City, Osaka Prefecture No. Japan Co., Ltd.

Claims (4)

[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). A coating composition obtained by emulsion-polymerizing 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 coating composition according to claim 1. 3. A water-soluble or water-dispersible terminal alkyl group having an acid value of 200 mgKOH / g or more, which is obtained by polymerizing a monomer component containing an unsaturated carboxylic acid in the presence of an alkyl mercaptan having 6 to 18 carbon atoms. A method for producing a coating composition, which comprises subjecting the monomer composition according to claim 1 or 2 to emulsion polymerization using a polymer having a group and / or a salt thereof as an emulsifier. 4. The coating composition according to claim 3, wherein the monomer composition further contains a functional group-containing monomer containing a functional group having reactivity with a carboxyl group. Manufacturing method.