JP2003160753A - Coating resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating resin composition excellent in coating properties such as hardness, solvent resistance and weatherability without affecting the environment and human bodies which may avoid lifting on repair or the like. <P>SOLUTION: In the composition containing an acrylic polyol, alicyclic and/or aliphatic hydrocarbon-based solvent, the polyol is obtained by copolymerizing a monomer component containing a cycloalkyl structure-containing unsaturated monomer (a) of 5 pts.wt. or more and a hydroxyl group-containing unsaturated monomer (b) of 2-40 pts.wt. in a total monomer of 100 pts.wt., it has a hydroxyl group value expressed in terms of the solid content (x) of 0 mg KOH/g<x<200 mg KOH/g and a number average molecular weight (Mn) of (-0.05x+5)×1,000≤Mn≤(-0.25x+50)×1,000 and dissolves in the alicyclic and/or aliphatic hydrocarbon-based solvent. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coating resin composition containing an acrylic polyol as a main component.

[0002]

BACKGROUND OF THE INVENTION Acrylic polyols are useful in various applications such as building exterior applications because of their excellent coating film performance.
Usually, it is used as a paint by dissolving it in a polar solvent in consideration of its solubility. However, such a coating material may cause lifting if the existing coating film or the undercoating film is poor in solvent resistance, for example, when overcoating on the existing coating film or the undercoating film at the time of repair or the like. It was known to cause problems. Therefore, in order to prevent lifting during repairs and the like, paints in which an acrylic polyol is dissolved in a non-polar organic solvent containing a hydrocarbon solvent have been conventionally used.

However, when an aromatic hydrocarbon solvent is used as the hydrocarbon solvent, it is necessary to increase the content of the aromatic hydrocarbon solvent, which may be odorous or toxic, to some extent. It was not completely satisfactory from the viewpoint of existing environmental problems and effects on the human body. On the other hand, when an alicyclic hydrocarbon solvent or an aliphatic hydrocarbon solvent is used as the hydrocarbon solvent, odor and toxicity do not matter, but considering the solubility of the acrylic polyol, the hydroxyl value of the acrylic polyol is considered. Since the molecular weight and the molecular weight cannot be set high, there is a problem that the coating film performance such as hardness, solvent resistance and weather resistance is impaired.

On the other hand, in recent years, non-aqueous dispersion paints have also been studied, but since it is necessary to use a polymer that dissolves in a solvent as a dispersing resin for dispersing particles, the above problems can be avoided. You will not get it.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is excellent in coating film performance such as hardness, solvent resistance, and weather resistance, and has no effect on the environment or human body. An object of the present invention is to provide a resin composition for coatings, which can avoid lifting during repair and the like.

[0006]

Means for Solving the Problems The present inventor has conducted extensive studies to solve the above problems. As a result, an acrylic polyol obtained by copolymerizing a monomer component containing a specific amount of a cycloalkyl structure-containing unsaturated monomer (a) and a hydroxyl group-containing unsaturated monomer (b), and Solubility in an alicyclic hydrocarbon-based solvent and / or an aliphatic hydrocarbon-based solvent if the acrylic polyol is such that the hydroxyl value (x) in terms of solid content and the number average molecular weight (Mn) satisfy a specific relationship. The present invention has been completed by discovering that it is possible to ensure the above-mentioned properties and, at the same time, it can exhibit excellent coating film performance and is effective in solving the above problems.

That is, the resin composition for coating material of the present invention is
Acrylic polyol, alicyclic hydrocarbon solvent and /
Alternatively, in the resin composition containing an aliphatic hydrocarbon solvent, the acrylic polyol is 10 monomers in total.
5 parts by weight or more of a cycloalkyl structure-containing unsaturated monomer (a) and a hydroxyl group-containing unsaturated monomer (b) 2 in 0 part by weight.
To 40 parts by weight, the hydroxyl value (x) in terms of solid content is in the range of 0 mgKOH / g <x <200 mgKOH / g, and the number average molecular weight (Mn ) Is (−0.05x + 5) × 1000 ≦ Mn ≦ (−0.25
x + 50) × 1000, and is soluble in the alicyclic hydrocarbon solvent and / or aliphatic hydrocarbon solvent.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition for coating material of the present invention copolymerizes a monomer component containing a cycloalkyl structure-containing unsaturated monomer (a) and a hydroxyl group-containing unsaturated monomer (b). It contains an acrylic polyol obtained by. Examples of the cycloalkyl structure-containing unsaturated monomer (a) include:
An unsaturated monomer represented by the following general formula (1) is preferable. The cycloalkyl structure-containing unsaturated monomer (a) may be used alone or in combination of two or more kinds.

[0009]

[Chemical 1]

(In the formula (1), R ¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ² is an ester group having a cycloalkyl structure having 3 to 36 carbon atoms which may have a substituent. In the general formula (1), the substituent in the cycloalkyl structure which may have a substituent of the ester group represented by R ² is not particularly limited, but may have, for example, 1 to 1 carbon atoms.
18 hydrocarbon groups and the like can be mentioned. The cycloalkyl structure in the cycloalkyl structure which may have a substituent of the ester group represented by R ² is not particularly limited, and examples thereof include a cyclobutyl structure, a cyclopentyl structure, a cyclohexyl structure, a cyclobutyl structure, and a cyclooctyl structure. Examples include a structure, a cyclononyl structure, a cyclodecyl structure, a cycloundecyl structure, a cyclododecyl structure, a cyclotridecyl structure, a cyclotetradecyl structure, a cyclopentadecyl structure, a cyclohexadecyl structure, a cycloheptadecyl structure, and a cyclooctadecyl structure.

Examples of the unsaturated monomer represented by the general formula (1) include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate and te.
rt-Butylcyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclododecyl (meth) acrylate, isobornyl methacrylate (for example, trade name "light ester IB-X" manufactured by Kyoeisha Chemical Co., Ltd.), isobornyl acrylate (For example, trade name "FA-544A" manufactured by Hitachi Chemical Co., Ltd., trade name "Light acrylate IB-XA" manufactured by Kyoeisha Chemical Co., Ltd.), dicyclopentanyl methacrylate (for example, trade name "FA
-513M "manufactured by Hitachi Chemical Co., Ltd.), dicyclopentanyl acrylate (for example, trade name" FA-513A "manufactured by Hitachi Chemical Co., Ltd.), 4-methylol cyclohexylmethyl acrylate (trade name" CHDMMA "Nippon Kasei) Etc.), 4-methylcyclohexylmethyl (meth) acrylate, cyclohexylmethyl (meth) acrylate and the like.

The ratio of the cycloalkyl structure-containing unsaturated monomer (a) in the above monomer components is 10 in total.
It is important that the amount is 5 parts by weight or more in 0 parts by weight. Preferably 20 to 80 parts by weight, more preferably 20 to 6
It is preferably 0 parts by weight. When the cycloalkyl structure-containing unsaturated monomer (a) is less than 5 parts by weight, the hardness of the coating film,
Performances such as luster, durability, and weather resistance will be insufficient, and the solubility of the resulting acrylic polyol in a solvent will be reduced. The hydroxyl group-containing unsaturated monomer (b) is not particularly limited, but examples thereof include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate (trade name “Placcel FM” Daicel Chemical Industry Co., Ltd.), a polyester diol mono (meta) consisting of phthalic acid and propylene glycol
Examples thereof include (meth) acrylic monomers having a hydroxyl group such as acrylate. The hydroxyl group-containing unsaturated monomer (b) may be used alone or in combination of two or more kinds.

The proportion of the hydroxyl group-containing unsaturated monomer (b) in the monomer component is 100 parts by weight of the total amount of the monomers,
It is important to be 2 to 40 parts by weight. Preferably,
It is preferably 4 to 35 parts by weight. When the amount of the hydroxyl group-containing unsaturated monomer (b) is less than 2 parts by weight, the hydroxyl groups contained in the resulting acrylic polyol are small, so that the crosslinking density is low and the desired coating performance cannot be obtained. On the other hand, if the amount exceeds 40 parts by weight, it becomes difficult to secure the solubility of the obtained acrylic polyol in a solvent, or the water resistance of the coating film decreases. In the present invention, the monomer having both a cycloalkyl structure and a hydroxyl group is the monomer (a) and the monomer (b).
In this case, the amount of the monomer having both the cycloalkyl structure and the hydroxyl group is considered as the amount of each of the monomer (a) and the monomer (b). And That is, the weight of the monomer having both the cycloalkyl structure and the hydroxyl group is counted as the weight of the monomer (a) in the monomer component, and at the same time, the weight of the monomer in the monomer component is the same. It will also be counted as the weight of the monomer (b).

In addition to the monomers (a) and (b), the monomer component for obtaining the acrylic polyol is an ultraviolet stable unsaturated monomer (c) and / or an ultraviolet absorbing unsaturated compound. It is preferable that the monomer (d) is also included. In addition,
The ultraviolet stable unsaturated monomer (c) and / or the ultraviolet absorbing unsaturated monomer (d) may be used alone or in combination of two or more kinds. Examples of the UV-stable unsaturated monomer (c) are polymerizable with a piperidinyl group having a sterically hindered nitrogen atom, such as an unsaturated monomer represented by the following general formula (2). Preferable are monomers having at least one unsaturated group in the molecule.

[0015]

[Chemical 2]

(In the formula (2), R ³ represents a hydrogen atom or a cyano group, R ⁴ and R ⁵ are each independently a hydrogen atom,
Represents a methyl group or an ethyl group, R ⁶ represents a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, and Y represents an imino group or an oxygen atom) The ultraviolet stable unsaturated monomer (c) As a specific example of, for example, 4- (meth) acryloyloxy-2,
2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-2,
2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6, 6-tetramethylpiperidine, 4-
Crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-
Tetramethylpiperidine, 1- (meth) acryloyl-
4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4
-Cyano-4- (meth) acryloylamino-2,2,
6,6-Tetramethylpiperidine, 1-crotonoyl-
4-crotonoyloxy-2,2,6,6-tetramethylpiperidine etc. are mentioned.

Specific examples of the ultraviolet absorbing unsaturated monomer (d) include 2- [2'-hydroxy-
5 '-(meth) acryloyloxyethylphenyl]-
2H-benzotriazole, 2- [2'-hydroxy-
5 '-(meth) acryloyloxypropylphenyl]
-2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyhexylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tret-butyl-5'-( (Meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2 −
[2'-hydroxy-5'-tert-butyl-3'-
(Meth) acryloyloxyethylphenyl] -2H-
Benzotriazole, 2- [2'-hydroxy-5'-
(Meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl] -5-methoxy-2H-benzotriazole, 2-
[2′-Hydroxy-5 ′-(meth) acryloyloxyethylphenyl] -5-cyano-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl] -5-tert -Butyl-2H-benzotriazole, 2- [2'-hydroxy-5 '-(β-methacryloyloxyethoxy)-
3'-tert-Butylphenyl] -4-tert-butyl-2H-benzotriazole and other benzotriazole compounds; 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloyl) (Oxy) propoxybenzophenone, 2-hydroxy-4- (2-methacryloxy)
Benzophenone compounds such as ethoxybenzophenone and 2-hydroxy-4-vinyloxycarbonylmethoxybenzophenone; and the like.

As the ultraviolet absorbing unsaturated monomer (d), a benzotriazole type unsaturated monomer represented by the following general formula (3) is particularly preferable.

[0019]

[Chemical 3]

(In the formula (3), R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ⁸ represents 1 to 6 carbon atoms.
Represents a linear or branched alkylene group, and R ⁹ is
Represents a hydrogen atom or a methyl group, Z 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) The proportion of the UV stable unsaturated monomer (c) and the proportion of the UV absorbing unsaturated monomer (d) in the total are not particularly limited, but the total amount of the monomers is 10
It is preferably 0.1 to 20 parts by weight in 0 parts by weight. When the UV stable unsaturated monomer (c) or the UV absorbing unsaturated monomer (d) is less than 0.1 part by weight in 100 parts by weight of the total monomers, the weather resistance of the resulting coating film is If it exceeds 20 parts by weight, it tends to be insufficient.
The appearance of the coating film may be impaired and the solubility of the acrylic polyol in the solvent may decrease.

The monomer components for obtaining the acrylic polyol include the monomers (a), (b), (c),
In addition to (d), it may further contain other polymerizable monomer (e) copolymerizable with them. The other copolymerizable polymerizable monomer (e) is not particularly limited, and specific examples thereof include those described in (1) to (10) below. In addition, these may use only 1 type and may use 2 or more types together. (1) (meth) acrylic acid esters: methyl (meth)
Acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) Acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl methacrylate (trade name "AAEM" yeast Ltd., etc.) and the like.

(2) Unsaturated monomers having an acidic functional group: (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, carboxyl group-terminated caprolactone modified acrylate, carboxyl group-terminated caprolactone modified methacrylate ( Product name "Plaxel FMA series" (manufactured by Daicel Chemical Industries, Ltd.) and other polymerizable unsaturated monomers having a carboxyl group; sulfoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) Acidic phosphoric acid ester-based polymerizable unsaturated monomers such as acryloyloxypropyl acid phosphate;

(3) Vinyl esters: vinyl acetate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, octyl acid. Vinyl, monochlorovinyl acetate, vinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl cinnamate, etc. (4) Polymerizable unsaturated monomer having a silicon atom: vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, trimethylsiloxyethyl. Methacrylate etc.

(5) Halogen atom-containing polymerizable unsaturated monomer: trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadodecafluorodecyl (meth) acrylate , Β- (perfluorooctyl) ethyl (meth) acrylate, hexafluoropropyl methacrylate, tribromophenol 3
EO-added methacrylate, perfluorooctylethyl (meth) acrylate, etc. (6) Polymerizable unsaturated monomer having a nitrogen atom: (meth)
Acrylamide, N, N-dimethylaminopropyl acrylamide, N-isopropyl acrylamide, ter
t-butylacrylamide, methylenebis (meth) acrylamide, N-methoxymethylacrylamide, N-
Ethoxymethyl acrylamide, N-butoxymethyl acrylamide, N-methylol (meth) acrylamide, N, N'-dimethylaminoethyl (meth) acrylate, N, N'-diethylaminoethyl (meth) acrylate, N-methyl-N-vinyl Formamide, methacryloyloxyethyltrimethylammonium chloride, dimethylaminoethyl methacrylate sulfate, morpholine EO addition methacrylate, N-vinylmethyl carbemate, N, N'-methylvinylacetamide, imide (meth) acrylate, dimethylaminoethyl (meth) acrylate Quaternary compounds, diacetone acrylamide, etc.

(7) Polyfunctional polymerizable unsaturated monomer: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol diacrylate, polyethylene glycol # 200 di (meth) acrylate, polyethylene glycol # 40
0 di (meth) acrylate, polyethylene glycol #
600 di (meth) acrylate, polyethylene glycol # 1000 diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 -Nonanediol diacrylate, neopentyl glycol di (meth) acrylate, polypropylene glycol # 400 di (meth) acrylate, EO-modified trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tris. Acryloyloxyethyl phosphate, glycerin dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane diacrylate, trime Trimethylolpropane tri (meth) acrylate. The polyethylene glycol # 200 di (meth) acrylate, polyethylene glycol # 400 di (meth) acrylate, polyethylene glycol # 600 di (meth) acrylate, polyethylene glycol # 1000 diacrylate, polypropylene glycol # 400 di (meth) acrylate. Is
Polyethylene glycol with a degree of polymerization of 200,
Polyethylene glycol with degree of polymerization of 400, degree of polymerization of 6
It is an ester of (meth) acrylic acid with polyethylene glycol of 00, polyethylene glycol having a degree of polymerization of 1000, or polypropylene glycol having a degree of polymerization of 400.

(8) Vinyl ethers: vinyl methyl ether, vinyl ethyl ether, vinyl isopropyl ether, vinyl-n-propyl ether, vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-
n-amyl ether, vinyl isoamyl ether, vinyl-2-ethylhexyl ether, vinyl-n-octadecyl ether, cyanomethyl vinyl ether, 2,2
-Dimethylaminoethyl vinyl ether, 2-chloroethyl vinyl ether, β-difluoromethyl vinyl ether, divinyl ether, divinyl acetal and the like. (9) Polymerizable unsaturated monomer having isocyanate group:
2-methacryloyloxyethylisocyanate (trade name "Karenzu MOI" manufactured by Showa Denko, etc.), metacroyl isocyanate (trade name "MAI" manufactured by Nippon Paint Co., Ltd.)
etc. (10) Vinyl chloride, vinylidene chloride, macromer compound (trade name “AA-6” manufactured by Toagosei Chemical Industry Co., Ltd.) and the like.

The proportion of the other polymerizable monomer (e) in the monomer component is 9 in 100 parts by weight of the total amount of the monomers.
There is no particular limitation as long as it is 5 parts by weight or less, and it may be appropriately set as needed. The polymerization method for obtaining the acrylic polyol by polymerizing the monomer components is not particularly limited, and for example, conventionally known polymerization methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization can be used. You can use it. Examples of the solvent that can be used in the polymerization include an alicyclic hydrocarbon solvent described below; an aliphatic hydrocarbon solvent described below; an aromatic hydrocarbon solvent such as toluene and xylene; ethyl acetate, acetic acid. Ester solvents such as n-propyl, n-butyl acetate, isobutyl acetate, n-amyl acetate, ethylene glycol ethyl ether acetate (cellosolve acetate), propylene glycol monomethyl ether acetate (trade name "ARCOSOLVE PMA" manufactured by Kuraray Co., Ltd.); Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, propylene glycol Glycol monomethyl ether (trade name "PGM" manufactured by Kuraray Co., Ltd.), propylene glycol monoethyl ether (trade name "PE" manufactured by Kuraray Co., Ltd.), propylene glycol tert-butyl ether (trade name "PTB" manufactured by Kuraray Co., Ltd.) , 3-methyl-3-methoxybutanol (trade name "Solfit"
Kuraray Co., Ltd.), dipropylene glycol monomethyl ether (trade name “D-PGM” manufactured by Kuraray Co., Ltd.) and other alcohol solvents; ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene Glycol monobutyl ether (butyl cellosolve), diethylene glycol monoethyl ether (ethyl carbitol),
Ether solvent such as diethylene glycol monobutyl ether (butyl carbitol); tetrahydrofuran,
Solvents such as N, N-dimethylformamide, dimethylacetamide, dioxane, chloroform and the like can be used alone or in combination, but are not limited thereto. Among these solvents,
Alicyclic hydrocarbon-based solvents and aliphatic hydrocarbon-based solvents are preferable, and the amount of alicyclic hydrocarbon-based solvent and / or aliphatic hydrocarbon-based solvent used is 80% by weight or more of the total amount of all solvents used. , And more preferably 90% by weight or more. The total amount of all the solvents used is not particularly limited and may be appropriately set depending on the polymerization reaction.

In the above polymerization, a polymerization initiator can be used if necessary. The polymerization initiator is not particularly limited, and includes, for example, 2,2′-azobis- (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis. Azo initiators such as (2,4-dimethylvaleronitrile); benzoyl peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, t
Ordinary radical initiators such as peroxide initiators such as ert-butylperoxy-2-ethylhexanoate; and the like can be used alone or in combination. The amount of the polymerization initiator used is not particularly limited, but is preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the total amount of the monomer components, and is preferably 0. 1
More preferably, it is from 10 to 10 parts by weight.

In the above polymerization, a chain transfer agent can be used if necessary. The chain transfer agent is not particularly limited, for example, n-butyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, cetyl mercaptan, stearyl mercaptan, thioglycolic acid, Mercaptans such as thioglycerol, ethylene thioglycol, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, mercaptoglycerin, mercaptosuccinic acid and mercaptopropionic acid; halogen compounds such as carbon tetrachloride, chloroform, trichlorobromoethane, bromoform; Disulfides; secondary alcohols; isopropyl alcohol, dioxane, tetrahydrofuran, isopropyl benzene, α-methyl styrene dimer, , 4
Diphenyl-4-methyl-1-pentene; and the like can be used alone or in combination. The amount of the chain transfer agent used is not particularly limited, but is 0.1-10 with respect to 100 parts by weight of the total amount of the monomer components.
It is preferable to use parts by weight.

The polymerization conditions for the above-mentioned polymerization are not particularly limited and may be appropriately selected. Specifically, the polymerization temperature is room temperature to 200 ° C., preferably 40 to 1
A range of 40 ° C is preferable. The polymerization time may be appropriately selected depending on the progress of the reaction. In addition, in the polymerization, other known additives such as a photopolymerization catalyst may be added, if necessary, in addition to those described above. In the present invention, the acrylic polyol has a hydroxyl value (x) in terms of solid content in the range of 0 mgKOH / g <x <200 mgKOH / g, and the number average molecular weight (Mn) thereof is (−0.05x + 5) × 1000 ≦ Mn ≦ (−0.25
It is important that the range is x + 50) × 1000. Since the solid-state-converted hydroxyl value (x) and the number average molecular weight (Mn) of the acrylic polyol are in the above ranges, the acrylic polyol is soluble in an alicyclic hydrocarbon solvent and / or an aliphatic hydrocarbon solvent. It can be an acrylic polyol. When the hydroxyl value (x) is 200 mgKOH / g or more, the solubility of the acrylic polyol in the solvent cannot be secured.
If the number average molecular weight (Mn) of the acrylic polyol is smaller than the above range, the coating performance such as weather resistance becomes poor, while if it is larger than the above range, the solubility of the acrylic polyol in the solvent cannot be secured. . In addition,
The hydroxyl value (x) may be a theoretical calculated value calculated from the raw materials used in the production or a measured value by the acetylation method.

The coating resin composition of the present invention contains an alicyclic hydrocarbon solvent and / or an aliphatic hydrocarbon solvent. This makes it possible to avoid lifting during repairs and the like without affecting the environment or the human body. The alicyclic hydrocarbon solvent and / or the aliphatic hydrocarbon solvent are not particularly limited,
Examples of the alicyclic hydrocarbon-based solvent include cyclohexane, methylcyclohexane, dimethylcyclohexane,
Ethylcyclohexane, hydrogenated product of C9 high boiling aromatic hydrocarbon solvent (“Ricasolve 900” manufactured by Shin Nippon Rika Co., Ltd.), hydrogenated product of C10 high boiling aromatic hydrocarbon solvent (“Naphthol 150” Maruzen Petroleum) (Chemical Co., Ltd.)
Examples of the aliphatic hydrocarbon solvent include n-heptane and the like, and commercially available products include trade name "Rose" manufactured by Ciel Co., Netherlands, trade name "Isopar E or G" US Exon. Chemicals, product name "naphtha 5 or 6" Exxon Chemical Co., USA, product name "IP Solvent 1620" Idemitsu Petrochemical Co., Ltd., product name "Whitesol" Kyodo Petrochemical Co., Ltd. Is mentioned. These solvents may be used alone or in combination of two or more.

In the resin composition for coating material of the present invention, the acrylic polyol, the alicyclic hydrocarbon solvent and /
Alternatively, the ratio with the aliphatic hydrocarbon solvent may be appropriately set according to the application and is not particularly limited, but for example, acrylic polyol / alicyclic hydrocarbon solvent and / or aliphatic hydrocarbon solvent = 7. It is preferably / 3 to 2/8 (weight ratio). The coating resin composition of the present invention may also contain a solvent other than the alicyclic hydrocarbon-based solvent and the aliphatic hydrocarbon-based solvent. Examples of the other solvent include the solvents described above as the solvent that can be used in the polymerization for obtaining the acrylic polyol. However, when it also contains other solvent, the content of the alicyclic hydrocarbon-based solvent and / or the aliphatic hydrocarbon-based solvent is 80% by weight or more of the total amount of all the solvents, more preferably 90% by weight. It is desirable to set it to be at least%.

From the viewpoint of durability, water resistance and solvent resistance, it is preferable that the coating resin composition of the present invention further contains a (block) polyisocyanate compound as a curing agent. The (block) polyisocyanate compound is not particularly limited as long as it has two or more isocyanate groups in one molecule,
For example, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,
6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate Isocyanates; adducts, burettes, isocyanurates of the above compounds; blocking compounds (alcohols such as ethanol, oximes such as acetoxime, ε-
Block polyisocyanates blocked with lactams such as caprolactam). In addition, these may use only 1 type and may use 2 or more types together.

When the (block) polyisocyanate compound is also contained, the ratio is such that the isocyanate group is 0. 1 with respect to 1 equivalent of the hydroxyl group in the acrylic polyol.
6 to 1.5 equivalents are preferable, and 0.
It is more preferable that the amount is 8 to 1.2 equivalents.
When the (block) polyisocyanate compound is also contained, the coating resin composition of the present invention further contains a curing catalyst for the purpose of accelerating the urethanization reaction between the hydroxyl group in the acrylic polyol and the isocyanate group. Preferably. The curing catalyst is not particularly limited, and examples thereof include dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, di-n-butyltin dichloride, stannas octoate, tetra-n-.
Organotin catalysts such as butyl-1,3-diacetoxy-distannoxane; phosphoric acid or phosphoric acid ester compounds such as phosphoric acid, monomethyl phosphate, monoethyl phosphate, dibutyl phosphate; p-toluene sulfonic acid,
Methanesulfonic acid, dodecylbenzenesulfonic acid, p-
Organic sulfonic acid catalysts such as methyl toluene sulfonate;
Sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium-ter
Basic catalysts such as t-butoxide, sodium hydroxide and potassium hydroxide; amine catalysts such as ammonia, triethylamine and tripropylamine; and the like. In addition, these may use only 1 type and may use 2 or more types together. Further, when these curing catalysts are contained, the ratio is not particularly limited and may be appropriately set within a range that does not impair the effects of the present invention.

If desired, the coating resin composition of the present invention may contain a polymer compound other than the acrylic polyol. For example, polystyrene, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyurethane, polymethyl methacrylate, polycarbonate, polyester, polyamide, polybutadiene, polyvinyl alcohol resin, ABS (acrylonitrile-butadiene-styrene) resin, acetate resin, acrylic resin , Fluororesins, epoxy resins, chlorinated polypropylene, alkyd resins, silicone resins, vinyl acetate resins, styrene-butadiene resins, polyester-modified acrylic resins and other modified resins, cellulose derivatives,
Vinyl chloride organosol, organosilicate condensate,
A melamine resin, a polyisocyanate compound and the like can be appropriately blended within a range that does not impair the effects of the present invention.

The coating resin composition of the present invention may optionally contain various additives within a range that does not impair the effects of the present invention. Specific examples thereof include those shown in (1) to (4) below. In addition, as for various additives, only 1 type may be used and 2 or more types may be used together. (1) Pigments: heavy calcium carbonate, light calcium carbonate, cold water stone, kaolin, clay, porcelain clay, China gray, diatomaceous earth, hydrous fine powder silicic acid, talc, barium sulfate, precipitated barium sulfate, barium carbonate, silica powder, wow Extender pigments such as rustonite; Metal powder pigments such as aluminum powder, copper powder, stainless steel powder, nickel powder; rutile titanium oxide, anatase acid value titanium, antimony trioxide zinc white, lithobon, lead white, zinc white, Carbon black, run black, graphite, iron black, copper / chromium black, copper / iron / manganese black, cobalt / iron / chromium black, molybdate orange, red iron oxide, yellow lead, yellow iron oxide, loess, titanium yellow , Titanium / antimony / chrome yellow, chrome green, chrome oxide green, cobalt / titanium / d Inorganic pigments such as kel / zinc green, cobalt / aluminum / chromium green, cobalt green, ultramarine blue, navy blue, cobalt blue, cobalt / aluminum / chrome blue, cobalt violet, manganese violet; permanent red 4R, dinitroaniline orange, brilliant Carmine FB, Permanent Red F5RK, Pyrazolone Red, Benzimidazolone Orange, Permanent Red 2B, Lake Red, Bordeaux 10B, Bon Maroon Medium, Bon Maroon Light, First Yellow-G, First Yellow-10G, First Yellow-5GX, First Yellow. -FGL, Benzimidazolone Yellow-H
3G, benzimidazolone yellow-H4G, permanent yellow-HR, condensed azo pigments, azo pigments such as isoindolinone yellow and isoindoline yellow pigments; anthraquinone pigments such as anthraquinone red, anthrapyrimidine yellow and flavandron yellow; Thioindigo-based pigments such as thioindigo bold; perylene-based pigments such as perylene red perylene scarlet and perylene maroon; quinacridone pigments such as quinacridone red, quinacridone magenta, dichloroquinacrylon magenta, quinacridone maroon quinacrylon scaret, quinacdrine violet; Diketopyrrolopyrrole pigments such as diketopyrrolopyrrole red; Azomethine type copper complex yellow, Nitroso type nickel complex yellow, Nickel azo yellow Metal complex pigments such as quinophthalone yellow pigments such as quinophthalone yellow; phthalocyanine pigments such as chlorinated phthalocyanine green, chlorochlorinated phthalocyanine green, copper phthalocyanine blue, phthalocyanine blue, metal-free phthalocyanine blue and indanthrene blue; Dioxazine-based pigments such as oxazine violet; zinc dust, lead suboxide, red lead,
Anticorrosion pigments such as zinc chromate, calcium leadate, strontium chromate, lead cyanamide, basic lead chromate, basic lead sulfate, phosphates, molybdates, phosphomolybdates and MIO; fluorescent pigments; Glass beads; litharge; pearlescent pigment; muscovite; aluminum silicate; etc.

(2) Thickener: organic bentonite type, ultrafine silica type, surface-treated calcium carbonate type, amide wax type, hydrogenated castor oil wax type, penzylidene sorbitol type, various metal soaps, polyethylene oxide type, Polymerized vegetable oil type, sulfuric acid ester type anionic surfactant, polyether / ester type surfactant, polycarboxylic acid amine salt, etc. (3) Dispersant and wetting agent: high molecular weight unsaturated polycarboxylic acid, polyether / polyester carboxylate salt, high molecular weight polyester acid polyamine salt, high molecular weight polycarboxylic acid salt, phosphoric acid ester, high molecular weight polyester acid amide Amine salts, long-chain polyamide phosphates, aliphatic polyamides, salts of long-chain polyaminoamides and high-molecular polyester acids, phosphoric acid ester salts, high-molecular polyether salts, etc.

(4) Defoaming agent: silicone type, oxyalkylene type, Bronic type, mineral type and the like. The coating resin composition of the present invention can be applied to various base materials. As the base material, for example, glass, slate, concrete,
Inorganic base materials such as mortar; aluminum, iron, zinc,
Metal base materials such as tin, copper, titanium, stainless steel, tin plate, galvanized metal, metal whose surface is plated with zinc, tin or chromium, and metal whose surface is treated with chromic acid or phosphoric acid; polyethylene, polyvinyl chloride, ABS (Acrylonitrile-butadiene-styrene) resin, FRP (fiber reinforced plastic), polycarbonate, polymethylmethacrylate,
Examples thereof include plastic substrates such as polystyrene, polypropylene, polyester, acrylic resins, epoxy resins, and nylon resins; wood such as cypress, cedar, pine, and plywood; organic substrates such as paper;

The coating method for coating the resin composition for coating of the present invention is not particularly limited, and examples thereof include dip coating, brush / roll brush coating, spray coating, roll coating, spin coating, bar coating, Conventionally known methods such as flow coating, electrostatic coating, die coating, film laminating and gel coating may be used. The coating resin composition of the present invention includes, for example, plastic molded products, solar cells / polymer batteries, home appliances, steel products, large-scale structures, automobiles, buildings, building materials, woodworking, ink binders, guard fences, and displays. It can be preferably used for applications such as machines, instruments, and glass products.

[0040]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the following, "parts" means "parts by weight" unless otherwise specified.
"%" Indicates "% by weight". The physical properties of the acrylic polyols and resin compositions obtained in the examples and comparative examples were measured as follows. The solid hydroxyl value and the solid acid value of the acrylic polyol are shown by theoretical calculation values calculated from the raw materials at the time of production. [Nonvolatile content of resin composition] Approximately 1 g of the resin composition was weighed and dried with a hot-air dryer at 200 ° C for 15 minutes to determine the residual amount of dry matter as the nonvolatile content, and the ratio with respect to the weight before drying was% by weight. Indicated.

[Viscosity of Resin Composition] The viscosity was measured at 25 ° C. using a Gardner-Holt viscometer according to the Gardner viscosity measuring method. [Number average molecular weight and weight average molecular weight of acrylic polyol] Gel permeation chromatography (HL
C-8020 type) and TKgel G-50 as a column
00HXL (manufactured by Tosoh Corporation) and TSKgel G
MHXL-L (manufactured by Tosoh Corp.) was used in series and measured in terms of polystyrene. [Glass Transition Point (Tg) of Acrylic Polyol] The temperature (K) theoretically calculated by the following Fox equation was converted to (° C.). 1 / Tg = Σ (Wi / Tgi) (where Wi represents the mass distribution of the monomer i, and Tgi represents the Tg of the homopolymer of the monomer i.) (Example 1) Thermometer, gas blowing pipe, dropping In a four-necked flask equipped with a funnel, a reflux condenser and a stirrer, an alicyclic hydrocarbon solvent (“Ricasolve 9
00 ", manufactured by Shin Nippon Rika Co., Ltd .; hydrogenated product of C9 high boiling aromatic hydrocarbon solvent) was charged, and the temperature was raised to 100 ° C with stirring under a nitrogen stream.

On the other hand, in the dropping funnel, methacrylic acid (M
MA) 0.8 part, hydroxyethyl methacrylate (H
EMA) 2.3 parts, styrene (St) 20 parts, cyclohexyl methacrylate (CHMA) 52 parts, 2-ethylhexyl acrylate (2EHA) 23.9 parts, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine. A mixture of 100 parts of a monomer component consisting of 1 part of (HALS), 8 parts of the above-mentioned “Ricasolve 900” and 1 part of tert-butylperoxy-2-ethylhexanoate as a polymerization initiator was charged. While stirring the solvent in the flask at 100 ° C., the mixture in the dropping funnel was dropped into the flask over 3 hours. After completion of the dropping, the reaction solution was heated to 105 ° C. with stirring under a nitrogen stream. After that, te is added as an additional polymerization initiator every 30 minutes.
After adding 0.2 parts of rt-butylperoxy-2-ethylhexanoate three times, the mixture was aged for 2 hours to obtain an acrylic polyol. After the completion of the reaction, 22.2 parts of the above-mentioned "Ricasolve 900" was added as a diluent solvent and diluted to obtain a resin composition of the present invention. The physical properties of the resulting acrylic polyol and resin composition are shown in Table 1.

(Examples 2 to 9 and Comparative Examples 1 to 6) Type and amount of solvent initially charged in flask, type and amount of each component of monomer component and solvent in dropping funnel, polymerization in dropping funnel Except that the amount of the initiator, the amount of the additional polymerization initiator, the type and amount of the diluting solvent, and the temperature inside the flask (dripping temperature) at the time of dropping the mixture in the dropping funnel are changed as shown in Tables 1 to 3, respectively. In the same manner as in Example 1, a resin composition of the present invention was obtained. Physical properties of the obtained acrylic polyol and resin composition are shown in Tables 1 to 3.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

In Tables 1 to 3, the following abbreviations are used. MMA: methacrylic acid HEMA: hydroxyethyl methacrylate St: styrene CHMA: cyclohexyl methacrylate 2EHA: 2-ethylhexyl acrylate t-BMA: t-butyl methacrylate i-BMA: isobutyl methacrylate LMA: lauryl methacrylate HALS: 4-methacryloyloxy-2,2 , 6, 6
-Tetramethylpiperidine UVA: 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole Ricasolve: Alicyclic hydrocarbon solvent ("Ricasolve 90
0 ”manufactured by Shin Nippon Rika Co., Ltd .; hydrogenated product of C9 high-boiling aromatic hydrocarbon solvent) Naphthol: alicyclic hydrocarbon solvent (“ Naphthol 15
0 ”Maruzen Petrochemical Co., Ltd .; C10 high boiling aromatic hydrocarbon solvent hydrogenated product) Next, test pieces were prepared using the resin compositions obtained in the above Examples and Comparative Examples. The following evaluation was performed. The results are shown in Table 4.

[Preparation of Specimen] Titanium acid value (“Taipaque CR-95” manufactured by Ishihara Sangyo Co., Ltd.) was added to the resin composition so that the pigment concentration in the non-volatile content was 40% by weight, and the mixture was sand milled. After being uniformly dispersed, a curing agent (“Duranate TSA-100” manufactured by Asahi Kasei Co., Ltd.) was mixed in an amount such that isocyanate groups / hydroxyl groups in the resin composition = 1/1 (equivalent ratio), and further mixed with air. It was diluted with the above-mentioned "Ricasolve 900" until it became a sprayable viscosity to obtain a paint. Then, the coating material was applied to a zinc phosphate-treated steel sheet (manufactured by Nippon Test Panel Co., Ltd.) having a thickness of 0.8 mm to obtain a dry film thickness of 20 to 3
After applying by air spray to 0 μm, 80
A test piece was prepared by drying at 30 ° C. for 30 minutes. The test pieces were subjected to the following evaluations after 2 days had passed after the production.

[Appearance (Glossiness)] JIS-K-540
07.6 according to the photometer (Nippon Denshoku "VZ-200
0 ") was used to measure the glossiness at an incident angle of 60 degrees of the light source. [Hardness] A pencil scratching test was performed according to JIS-K-5400 8.4.1, and the pencil hardness when scratched was defined as the hardness. [Adhesion] A test was performed by a cross-cut tape method according to JIS-K-5400 8.5.2, and evaluated as follows. ◎: No peeling, ○: Less than 5% of peeling area, △: Peeling area 5
% Or more and less than 20%, x: Peeling area 20% or more [solvent resistance] The condition of the coating film when the surface of the test piece was rubbed 50 times with absorbent cotton impregnated with methyl ethyl ketone was visually observed. evaluated. ⊚: No change, ◯: Gloss is recognized, X: Dissolved and disappeared coating film [accelerated weather resistance] Sunshine weather meter (“WEL-SUN-HC-B” manufactured by Suga Test Instruments: black panel temperature 63 ° C., 2 Acceleration test was conducted by using (rainfall for 18 minutes every hour), and the time when the gloss retention rate was 80% or less was measured.

[0050]

[Table 4]

[0051]

EFFECT OF THE INVENTION The coating composition of the present invention has excellent coating properties such as hardness, solvent resistance and weather resistance, and avoids lifting during repairs without affecting the environment or human body. It is possible.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor ▲ Yoshi ▼ Masaya Ta             5-8 Nishiomitabicho, Suita City, Osaka Prefecture             Within Nippon Shokubai F-term (reference) 4J038 CG001 CH071 CH121 CH201                       DG191 DG261 DG262 DG301                       DG302 GA03 GA08 KA06                       MA14 NA03 NA04 NA11 PB12

Claims (3)

[Claims] 1. A resin composition comprising an acrylic polyol and an alicyclic hydrocarbon solvent and / or an aliphatic hydrocarbon solvent, wherein the acrylic polyol is contained in 100 parts by weight of a total amount of monomers, It is obtained by copolymerizing a monomer component containing 5 parts by weight or more of a cycloalkyl structure-containing unsaturated monomer (a) and 2 to 40 parts by weight of a hydroxyl group-containing unsaturated monomer (b), and is a solid. The hydroxyl value in terms of minutes (x) is in the range of 0 mgKOH / g <x <200 mgKOH / g, and the number average molecular weight (Mn) is (−0.05x + 5) × 1000 ≦ Mn ≦ (−0.25
x + 50) × 1000, which is soluble in the alicyclic hydrocarbon-based solvent and / or the aliphatic hydrocarbon-based solvent. 2. The coating resin according to claim 1, wherein the monomer component also contains an ultraviolet stable unsaturated monomer (c) and / or an ultraviolet absorbing unsaturated monomer (d). Composition. 3. The resin composition for coating according to claim 1, which further contains a (block) polyisocyanate compound as a curing agent.