JPH11315225A - Novel resin composition for powder coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in weathering resistance by using as the essential component a vinyl polymer obtained by copolymerizing a silyl-containing vinyl monomer with an acid-anhydride-group-containing vinyl monomer and other vinyl monomers, having silyl groups as crosslinking groups, and having a specified glass transition temperature and a specified number- average molecular weight. SOLUTION: This composition essentially consists of a vinyl copolymer obtained by copolymerizing 1-30 pts.wt. vinyl monomer represented by the formula [e.g. 3-(meth)acryloxypropyltrimethoxysilane] with 1-30 pts.wt. acid-anhydride- group-containing vinyl monomer (e.g. maleic anhydride) and 40-98 pts.wt. other vinyl monomers containing 1-20 pts.wt. hydroxyl-containing vinyl monomer [e.g. 2-hydroxyethyl (meth)acrylate or the like]. This copolymer has silyl groups represented by the formula as crosslinking groups and has a glass transition temperature of 40-100 deg.C and a number-average molecular weight of 2,000-20,000. In the formula, R<1> is a 1-10C alkyl, a 6-10C alkyl, or a 7-10C aralkyl; X is H, a halogen, hydroxyl, or the like; and (a) is an integer of 0-2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin composition for powder coatings. More specifically, for example, relates to a resin composition for powder coatings suitably used for automotive parts, industrial machinery, steel furniture, building interior and exterior, home appliances and the like, and more specifically, excellent water resistance, appearance, heat The present invention relates to a resin composition for powder coatings which exhibits curability, impact resistance, and the like, and exhibits extremely excellent weather resistance.

[0002]

2. Description of the Related Art Conventionally, for painting automotive parts, industrial machines, steel furniture, interior and exterior of buildings, home electric appliances, etc., acid-
A paint mainly containing an ester resin or an epoxy resin by epoxy crosslinking is used. However, although the paint is relatively inexpensive, there is a problem that the weather resistance is extremely reduced when used outdoors.

As a paint having excellent weather resistance outdoors, there is a paint using a fluorine resin. However, in this case, the cost jumps greatly and is not practical.

[0004] In addition, since the influence on the global environment is regarded as important, solvent-based paints are being shunned by the generation of a large amount of volatile components, and it is necessary to replace solvent-based paints with powder paints.

[0005] Polyester resins, which are often used in powder coatings, have a good balance of coating film properties, but have insufficient weather resistance. On the other hand, an acrylic resin is used to improve weather resistance, but a physical property balance as high as that of a polyester resin cannot be obtained. Acrylic resins tend to be harder and more brittle than polyester resins, and their mechanical properties and the like are inferior to polyester resins.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide an ester resin or an epoxy resin by the above-mentioned acid-epoxy crosslinking which has been frequently used. Overcoming the shortcomings of resin, not only has excellent weather resistance, but also clears environmental issues,
It is another object of the present invention to provide a powder coating having a new crosslinking type, which can be manufactured at low cost. By using the method of the present invention, it is possible to obtain a coating film having mechanical properties that cannot be realized by a conventional acrylic resin.

[0007]

SUMMARY OF THE INVENTION The present invention provides a novel resin composition having the following constitution, thereby achieving the above object. 1) 1 to 30 parts by weight of a vinyl monomer (a) containing a silyl group represented by the following general formula (1), 1 to 30 parts by weight of a vinyl monomer (b) containing an acid anhydride group Parts, and a vinyl copolymer (A) obtained by copolymerizing 98 to 40 parts by weight of a copolymerizable vinyl monomer (c) other than the components (a) and (b). As the component, the component (A) has a silyl group represented by the following general formula (1) as a main crosslinkable group, and has a glass transition temperature of 40 to 100 ° C and a number average molecular weight of 2000 to 20,000. Characteristic resin compositions for powder coatings.

[0008]

Embedded image (Wherein, R1 is an alkyl group having 1 to 10 carbon atoms, 6 carbon atoms)
At least one group selected from the group consisting of an aryl group having 10 to 10 and an aralkyl group having 7 to 10 carbon atoms,
In the case of a plurality, they may be the same or different. X is a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, a phenoxy group, a thioalkoxy group, an acyloxy group, an aminoxy group, a ketoximate group, an amino group,
It is at least one group selected from the group consisting of an amide group and an alkenyloxy group, and when there are a plurality of groups, they may be the same or different. a is an integer of 0 to 2. 2) A crosslinkable and curable polymer other than the component (A) is included, and the component (A) is at least 20% by weight and less than 100% by weight of the total of the component (A) and the polymer. The resin composition for a powder coating according to claim 1, wherein 3) The resin composition for a powder coating according to claim 1 or 2, wherein X in the general formula (1) is an alkoxy group. 4) The component (a) comprises 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane and 3- (meth) The resin composition for powder coating according to any one of claims 1 to 3, wherein the resin composition is at least one selected from the group consisting of acryloxypropylmethyldiethoxysilane. 5) The powder according to any one of claims 1 to 4, wherein the component (b) is at least one selected from the group consisting of maleic anhydride, itaconic anhydride and citraconic anhydride. Resin composition for body paint. 6) Among 98 to 40 parts by weight of the other copolymerizable vinyl monomer of the component (c), 1 to 20 parts by weight of a hydroxyl-containing vinyl monomer (d) is contained. The resin composition for a powder coating according to any one of claims 1 to 5. 7) The hydroxyl group-containing vinyl monomer of the component (c) is 2-hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) Acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, hydroxystyrene,
Group consisting of 2-hydroxy-3-phenoxypropyl acrylate, a vinyl monomer having a group represented by the following general formula (2), and a vinyl monomer having a group represented by the following general formula (3) The resin composition for a powder coating according to any one of claims 1 to 6, wherein the resin composition is at least one member selected from the group consisting of: -O ｛CO (CH2) 5O｝ m-H (2) (where m is an integer of 1 to 50) -O −C (R2) (CH2) 2O｝ n-H (3) (Formula Wherein R2 is hydrogen or a methyl group, and n is an integer of 2 to 100.) 8) 30 to 200 parts by weight of the hydroxyl group-containing acrylic resin (B) based on 100 parts by weight of the component (A). The resin composition for a powder coating according to any one of claims 1 to 7, wherein: 9) The powder-based coating material according to any one of claims 1 to 8, wherein the hydroxyl group-containing resin as the component (B) contains a silyl group represented by the general formula (1). Resin composition. 10) The component (B) is a silyl group-containing vinyl monomer (a) represented by the following general formula (1): 1 to 50 parts by weight, and (d) a hydroxyl group-containing vinyl monomer. 1 to 30 parts by weight, (e) a polymer obtained by copolymerizing 98 to 20 parts by weight of another vinyl monomer copolymerizable with the component (a) and the component (d). The resin composition for powder coating according to any one of claims 1 to 9. 11) The compound (C) having 2 or more hydroxyl groups in one molecule is contained in 2 to 60 parts by weight per 100 parts by weight of the component (A). The resin composition for powder coating according to the above. 12) at least one compound selected from the group consisting of the general formulas (4) to (6) and polyester resins having hydroxyl groups at both ends, wherein the compound having two or more hydroxyl groups in one molecule of the component (C) is 12. The method according to claim 1, wherein
The resin composition for powder coating according to any one of the above.

[0009]

Embedded image (In the formula, R3 is a straight-chain or branched alkylene group having 6 to 30 carbon atoms.)

[0010]

Embedded image (In the formula, R4 is a linear or branched alkylene group having 2 to 30 carbon atoms, m is an integer of 1 to 50, and n is an integer of 0 to 50.)

[0011]

Embedded image (In the formula, R5 is hydrogen or a methyl group, and n is an integer of 2 to 100.) 13) In the resin composition for powder coating, the component (A) 1
0.001 to 1 part by weight of the curing catalyst (D)
The resin composition for a powder coating according to any one of claims 1 to 12, comprising 0 part by weight. 14) The component (D) is at least one selected from the group consisting of an organic acidic compound, a mixture or a reaction product of the organic acidic compound and a nitrogen-containing compound, and an organometallic compound, or a mixture of two or more types. Claims 1 to
14. The resin composition for a powder coating according to any one of 13). 15) The component (D) is at least one selected from the group consisting of an organic sulfonic acid and a mixture of an organic sulfonic acid and a nitrogen-containing compound, or a mixture of two or more thereof. 15. The resin composition for a powder coating according to any one of 14. 16) The component (D) is at least one selected from the group consisting of an organic tin compound, an organic titanium compound, an organic aluminum compound, and an organic zirconium compound, or 2
A mixture of at least one species.
The resin composition for powder coating according to any one of the above. 17) The resin composition for powder coating according to any one of claims 1 to 16, wherein the resin composition for powder coating is baked and cured at 150 to 250 ° C. The component (A) is a component (a) that is a vinyl monomer containing a silyl group represented by the general formula (1), and a component (b) is a vinyl monomer that contains an acid anhydride group. And (c) a copolymerizable vinyl monomer other than the component (a) and the component (b).

The component (a) is not particularly limited as long as it has a silyl group represented by the general formula (1).
2 = CHSi (OCH3) 3, CH2 = CHSi (CH
3) (OCH3) 2, CH2 = C (CH3) Si (OC
H3) 3, CH2 = C (CH3) Si (CH3) (OC
H3) 2, CH2 = CHSi (OC2H5) 3, CH2
= CHSi (OC3H7) 3, CH2 = CHSi (OC
4H9) 3, CH2 = CHSi (OC6H13) 3, C
H2 = CHSi (OC8H17) 3, CH2 = CHSi
(OC10H21) 3, CH2 = CHSi (OC12H
25) 3, CH2 = CHSi (OCH2CH2OCH)
3) 3, CH2 = CHCOO (CH2) 3Si (OCH
3) 3, CH2 = CHCOO (CH2) 3Si (CH
3) (OCH3) 2, CH2 = C (CH3) COO (C
H2) 3Si (OCH3) 3, CH2 = C (CH3) C
OO (CH2) 3Si (CH3) (OCH3) 2, CH
2 = CHCOO (CH2) 3Si (OC2H5) 3, C
H2 = CHCOO (CH2) 3Si (CH3) (OC2
H5) 2, CH2 = C (CH3) COO (CH2) 3S
i (OC2H5) 3, CH2 = C (CH3) COO (C
H2) 3Si (CH3) (OC2H5) 2, CH2 = C
HCOO (CH2) 3Si (OCH2CH2OCH3)
3, CH2 = CHCOO (CH2) 3Si (CH3)
(OCH2CH2OCH3) 2, CH2 = C (CH3)
COO (CH2) 3Si (OCH2CH2OCH3)
3, CH2 = C (CH3) COO (CH2) 3Si (C
H3) (OCH2CH2OCH3) 2, CH2 = C (C
H3) COO (CH2) 2O (CH2) 3Si (OCH
3) 3, CH2 = C (CH3) COO (CH2) 2O
(CH2) 3Si (CH3) (OCH3) 2, CH2 =
C (CH3) COO (CH2) 11Si (OCH3)
3, CH2 = C (CH3) COO (CH2) 11Si
(CH3) (OCH3) 2, CH2 = CHCH2OCO
(O-C6H4) COO (CH2) 3Si (OCH3)
3 (where o-C6H4 is an orthophenylene group), CH2 = CHCH2OCO (o-C6H4) CO
O (CH2) 3Si (CH3) (OCH3) 2, CH2
= CH (CH2) 4Si (OCH3) 3, CH2 = CH
(CH2) 8Si (OCH3) 3, CH2 = CHO (C
H2) 3Si (OCH3) 3, CH2 = CHCH2O
(CH2) 3Si (OCH3) 3, CH2 = CHCH2
OCO (CH2) 10Si (OCH3) 3, CH2 = C
H (p-C6H4) Si (OCH3) 3, CH2 = CH
(P-C6H4) Si (CH3) (OCH3) 2 (where p-C6H4 is a paraphenylene group), CH2
= C (CH3) (p-C6H4) Si (OCH3) 3,
CH2 = C (CH3) (p-C6H4) Si (CH3)
Alkoxysilyl group-containing monomers such as (OCH3) 2;
CH2 = CHCOO (CH2) 3Si (CH3) Cl
2, CH2 = CHCOO (CH2) 3SiCl3, CH
2 = C (CH3) COO (CH2) 3Si (CH3) 2
Cl, CH2 = C (CH3) COO (CH2) 3Si
(CH3) Cl2, CH2 = C (CH3) COO (CH
2) Halosilyl group-containing monomer such as 3SiCl3; CH
2 = C (CH3) COO (CH2) 3Si (OH) 3,
CH2 = C (CH3) COO (CH2) 3Si (CH
3) Silanol group-containing monomers such as (OH) 2; CH2
= C (CH3) COO (CH2) 3Si (OCOCH
3) acetoxysilyl group-containing monomers such as 3; Among these, an alkoxysilyl group-containing monomer is particularly preferable in terms of cost, stability, reactivity, and the like. For example, 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltrimethoxysilane are preferable. One selected from the group consisting of ethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane and 3- (meth) acryloxypropylmethyldiethoxysilane,
Or a mixture of two or more of these. Here, “(meth) acryloxy” means “methacryloxy or acryloxy”. Note that the term “(meta)” used in the following also means the same notation.

The component (a) is composed of the component (A) 100
1 to 30 parts by weight per part by weight is copolymerized. Preferably 2
It is preferable to copolymerize 25 parts by weight, more preferably 3 to 22 parts by weight. When the amount of the component (a) is less than 1 part by weight, the curing properties of the resin composition for powder coating and the weather resistance of the coating film are poor, and when it exceeds 30 parts by weight, the storage stability of the resin is increased. Decrease.

The component (b), that is, the vinyl monomer containing an acid anhydride group, is one having both an acid anhydride group and a polymerizable carbon-carbon double bond in one molecule. There is no particular limitation, and examples thereof include one selected from the group consisting of maleic anhydride, itaconic anhydride, citraconic anhydride, and the like, or a mixture of two or more thereof. The component (b) is copolymerized in an amount of 1 to 30 parts by weight based on 100 parts by weight of the component (A). The copolymer is preferably copolymerized in an amount of preferably 2 to 25 parts by weight, more preferably 3 to 20 parts by weight. When the amount of the component (b) is less than 1 part by weight, the mechanical properties of the coating film of the resin composition for powder coating are inferior. When the amount exceeds 30 parts by weight, the storage stability of the composition is reduced. The smoothness of the coating film decreases.

The component (c), which is a copolymerizable vinyl monomer other than the components (a) and (b), includes:
There is no particular limitation, for example, vinyl monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, and cyclohexyl (meth) acrylate; Aromatic hydrocarbon vinyl monomers such as styrene, α-methylstyrene, chlorostyrene, 4-hydroxystyrene, and vinyltoluene; acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, fumaric acid, and citraconic acid Acid having a polymerizable carbon-carbon double bond such as α, β-ethylenically unsaturated carboxylic acid, styrene sulfonic acid, vinyl sulfonic acid and the like;
Or salts thereof (alkali metal salts, ammonium salts, amine salts, etc.); half esters of an acid anhydride such as maleic anhydride with a linear or branched alcohol having 1 to 20 carbon atoms; dimethylaminoethyl (meth) Acrylate,
(Meth) acrylates having an amino group such as dimethylaminopropyl (meth) acrylate and diethylaminoethyl (meth) acrylate; glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate,
Glycidyl group-containing vinyl monomers such as allyl glycidyl ether; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3
Hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as -hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; (meth) acrylamide, α- Ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N,
N-dimethylacrylamide, N-methylacrylamide, acryloylmorpholine or their hydrochloric acid,
Acetate; vinyl ester and allyl ester compounds such as vinyl acetate, vinyl propionate, and diallyl phthalate;
Vinyl monomers containing a nitrile group such as (meth) acrylonitrile; vinyl compounds containing a phosphoric ester group or vinyl compounds such as a (meth) acrylate containing a urethane bond or a siloxane bond; AS-6, AN-6, AA −
6, methacryloyl group-containing macromonomers such as AB-6 and AK-5 (all manufactured by Toa Gosei Chemical Co., Ltd.); vinyl methyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, N-vinylimidazole, etc. Other vinyl monomers and the like can be mentioned. Of these 98 to 40 parts by weight of the component (c), it is preferable to contain 1 to 20 parts by weight of a hydroxyl group-containing monomer (d). More preferably, 2 to 15 parts by weight, and still more preferably, 3 to 10 parts by weight is copolymerized.

The vinyl monomer (d) having a hydroxyl group contains a hydroxyl group and contains the above (a) and (b)
There is no particular limitation as long as it can be copolymerized with the components. For example, 2-hydroxyethyl (meth) acrylate, 2
-Hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) A) hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as acrylates; 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, hydroxystyrene, 2-hydroxy-3-phenoxypropyl acrylate, the above-mentioned general formula Examples of the vinyl monomer having a group represented by (2) (that is, a polycaprolactone chain) include, for example, CH2 = CHOCO (CH
2) 5OH, CH2 = CHO ｛CO (CH2) 5O｝ 4
H, CH2 = CHCH2OCO (CH2) 5OH, CH
2 = CHCH2O ｛CO (CH2) 5O｝ 4H, CH2
= CHCOO (CH2) 2OCO (CH2) 5OH, C
H2 = CHCOO (CH2) 2O ｛CO (CH2) 5
O｝ 2H, CH2 ＝ CHCOO (CH2) 2O ｛CO
(CH2) 5O｝ 3H, CH2 = CHCOO (CH2)
2O ｛CO (CH2) 5O｝ 4H, CH2 = CHCOO
(CH2) 2O ｛CO (CH2) 5O｝ 5H, CH2 =
CHCOO (CH2) 2O ｛CO (CH2) 5O｝ 10
H, CH2 = CHCOO (CH2) 2O ｛CO (CH
2) 5O｝ 20H, CH2 = CHCOO (CH2) 2O
{CO (CH2) 5O} 30H, CH2 = C (CH3)
COO (CH2) 2OCO (CH2) 5OH, CH2 =
C (CH3) COO (CH2) 2O ｛CO (CH2) 5
O｝ 2H, CH2 = C (CH3) COO (CH2) 2O
{CO (CH2) 5O} 3H, CH2 = C (CH3) C
OO (CH2) 2O ｛CO (CH2) 5O｝ 4H, CH
2 = C (CH3) COO (CH2) 2O ｛CO (CH
2) 5O｝ 10H, CH2 ＝ C (CH3) COO (CH
2) 2O ｛CO (CH2) 5O｝ 20H, CH2 = C
(CH3) COO (CH2) 2O ｛CO (CH2) 5
O @ 30H, PlacelFA-1, Plac
celFA-4, PlacelFM-1, Placc
e-caprolactone-modified hydroxyethyl (meth) acrylates such as elFM-4 (all manufactured by Daicel Chemical Industries, Ltd.); vinyl-based having a group represented by the general formula (3) (that is, a polyalkylene oxide chain) As the monomer, for example, CH2 = CHO (CH2CH2O) 5
H, CH2 = CHO (CH2CH2O) 10H, CH2
= CHO ｛CH2 (CH3) CH2O｝ 10H, CH2
= CHCH2O (CH2CH2O) 5H, CH2 = CH
CH2O (CH2CH2O) 10H, CH2 = CHCH
2O ｛CH2 (CH3) CH2O｝ 10H, CH2 ＝ C
HCOO (CH2CH2O) 5H, CH2 = CHCOO
(CH2CH2O) 10H, CH2 = CHCOO (CH
2CH2O) 20H, CH2 = CHCOO (CH2CH)
2O) 30H, CH2 = CHCOO (CH2CH2O)
50H, CH2 = CHCOO ｛CH2 (CH3) CH2
O｝ 10H, CH2 = CHCOO ｛CH2 (CH3) C
H2O｝ 20H, CH2 ＝ C (CH3) COO (CH2
CH2O) 2H, CH2 = C (CH3) COO (CH2
CH2O) 3H, CH2 = C (CH3) COO (CH2
CH2O) 5H, CH2 = C (CH3) COO (CH2
CH2O) 7H, CH2 = C (CH3) COO (CH2
CH2O) 10H, CH2 = C (CH3) COO (CH
2CH2O) 15H, CH2 = C (CH3) COO (C
H2CH2O) 20H, CH2 = C (CH3) COO
(CH2CH2O) 30H, CH2 = C (CH3) CO
O (CH2CH2O) 50H, CH2 = C (CH3) C
OO ｛CH2 (CH3) CH2O｝ 3H, CH2 ＝ C
(CH3) COO ｛CH2 (CH3) CH2O｝ 5H,
CH2 = C (CH3) COO ｛CH2 (CH3) CH2
O｝ 7H, CH2 ＝ C (CH3) COO ｛CH2 (CH
3) CH2O @ 10H, CH2 = C (CH3) COO
Polyalkylene glycol monomethacrylates such as {CH2 (CH3) CH2O} 20H, Blemmer PP series, Blemmer PE series, etc., Blemmer P
Polyethylene glycol polypropylene glycol monomethacrylates such as EP series, Blemmer AP
Glycol acrylates such as -400 and Blemmer AE-350, Blemmer NKH-5
And alkylene oxide-modified (meth) acrylates such as 050 (glycerol monomethacrylate) (both manufactured by NOF Corporation).

The component (d) is copolymerized in an amount of 1 to 20 parts by weight based on 100 parts by weight of the component (A). Preferably 2 to 1
It is preferable to copolymerize 5 parts by weight, more preferably 3 to 10 parts by weight. When the amount of the component (d) is less than 1 part by weight, the resin composition for powder coating has poor smoothness and impact resistance. When the amount exceeds 20 parts by weight, the storage stability of the resin is poor.
The blocking resistance decreases.

The copolymer (A) has a silyl group represented by the general formula (1) as a crosslinkable group. The silyl group is a main crosslinkable group having a function of crosslinking between molecules, and the component (A) can have an acid anhydride group of the component (b) as another crosslinkable group. If desired
For example, it may have another crosslinkable group such as an epoxy group. It is preferable that the number of the silyl groups is 50% or more of all the crosslinkable groups present in the component (A).
%, More preferably at least 80%. The silyl group is preferably present in one molecule of the component (A) at least one, more preferably 2 to 10. The acid anhydride group is represented by the following formula (A):
Preferably, at least one, and more preferably, two to eight are present in the molecule. As the method for producing the component (A), known polymerization methods such as bulk polymerization, suspension polymerization, and solution polymerization can be used. Particularly, from the viewpoint of ease of synthesis, radical initiators such as peroxides and azo compounds are used. Solution polymerization using is preferred.

The polymerization solvent used in the solution polymerization includes hydrocarbons (toluene, xylene, n-hexane, cyclohexane, etc.), acetates (ethyl acetate, butyl acetate, etc.), alcohols (methanol, ethanol, etc.).
Non-reactive solvents such as isopropanol, n-butanol, ethers (ethyl cellosolve, butyl cellosolve, cellosolve acetate, etc.), ketones (methyl ethyl ketone, ethyl acetoacetate, acetylacetone, diacetone alcohol, methyl isobutyl ketone, acetone, etc.) If so, there is no particular limitation.

Examples of the initiator used in the solution polymerization include organic peroxides such as benzoyl peroxide and tert-butyl peroxide, 2,2'-azobisisobutyronitrile,
2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (2-methylbutyronitrile) and the like There is no particular limitation as long as it is a radical initiator such as an azo compound.

In the above solution polymerization, if necessary, n
-Dodecyl mercaptan, t-dodecyl mercaptan,
n-octyl mercaptan, n-octadecyl mercap
Tan, 3-mercaptopropyltrimethoxysilane, 3
-Mercaptopropyltriethoxysilane, 3-merca
Ptopropylmethyldimethoxysilane, 3-mercapto
Propylmethyldiethoxysilane, (H_ThreeCO)_ThreeSi-
SS-Si (OCH _Three)_Three, (H_ThreeCO)_ThreeSi-S₆−
Si (OCH_Three)_ThreeAdjust the molecular weight using a chain transfer agent such as
Can be knotted. In particular, an alkoxysilyl group
Chain transfer agent, such as 3-mercaptopropion
With the use of rutrimethoxysilane, silyl group-containing acrylic
Introducing an alkoxysilyl group at the end of the copolymer
Can be.

In the above solution polymerization, a predetermined amount of the above-mentioned monomers, initiator, chain transfer agent and the like are added to a polymerization solvent, polymerization is carried out, and the solvent is removed under reduced pressure. A) The component is obtained.

The number average molecular weight of the component (A) is from 2000 to 2000.
20000 is preferable, and 3000 to 10 is more preferable.
000. When the molecular weight is less than 2,000, it is difficult for the coating film to exhibit sufficient mechanical properties, and when it exceeds 20,000, there is a problem that the coating film has poor smoothness. Further, the glass transition temperature of the component (A) is preferably from 40 to 100 ° C, more preferably from 5 to 100 ° C.
0-80 ° C. When the temperature is lower than 40 ° C., the storage stability of the powder coating material is poor. On the other hand, when the temperature is higher than 100 ° C., the smoothness of the coating film is poor. The hydroxyl group-containing acrylic resin (B) is obtained by copolymerizing a hydroxyl group-containing vinyl monomer (d) with another copolymerizable vinyl monomer other than the component (d). Manufactured by Further, the component (a) which is a vinyl monomer containing a silyl group represented by the general formula (1) can be copolymerized. Component (d) is 1 in 100 parts by weight of component (B).
３０30 parts by weight are copolymerized. The copolymer is preferably copolymerized in an amount of preferably 2 to 25 parts by weight, more preferably 3 to 20 parts by weight. When the amount of the component (d) is less than 1 part by weight, the smoothness and impact resistance of the resin composition for powder coating are poor, and when it exceeds 30 parts by weight, the storage stability of the resin is reduced. . Component (a) is 1 to 5 in 100 parts by weight of component (B).
0 parts by weight are copolymerized. The copolymer is preferably copolymerized in an amount of preferably 3 to 40 parts by weight, more preferably 5 to 30 parts by weight.
When the amount of the component (a) is less than 1 part by weight, the curing properties of the resin composition for powder coating and the weather resistance of the coating film are poor. When the amount exceeds 50 parts by weight, the storage stability of the resin is reduced. , The smoothness is reduced. The method for producing the component (B) includes:
Known polymerization methods such as bulk polymerization, suspension polymerization, and solution polymerization can be used, but solution polymerization using a radical initiator such as a peroxide or an azo compound is particularly preferable because of ease of synthesis. The number average molecular weight of the component (B) is 2,000.
~ 20,000, more preferably 3,000-1
0000. When the molecular weight is less than 2,000, it is difficult for the coating film to exhibit sufficient mechanical properties, and when it exceeds 20,000, there is a problem that the coating film has poor smoothness. Further, the glass transition temperature of the component (B) is preferably from 40 to 100 ° C, more preferably from 5 to 100 ° C.
0-80 ° C. When the temperature is lower than 40 ° C., the storage stability of the powder coating material is poor. On the other hand, when the temperature is higher than 100 ° C., the smoothness of the coating film is poor. The component (B) includes:
It is used in an amount of 30 to 200 parts by weight, preferably 40 to 180 parts by weight, and more preferably 50 to 150 parts by weight, based on 100 parts by weight of the component (A).

The ratio of the number of acid anhydride groups to the number of hydroxyl groups in the component (A), the component (B) and the component (C) described below is preferably 1: 3 to 3: 1. 1: 2-2:
A range of 1 is preferred.

The copolymer of component (A) forms a siloxane bond by the action of moisture and is a crosslinkable and curable copolymer. The copolymer of component (B) also forms a siloxane bond by the action of moisture. And a crosslinkable and curable copolymer. The components (A) and (B) can be crosslinked by a half esterification reaction between an acid anhydride group and a hydroxyl group. In the present invention, only the components (A) and (B) may be used as a crosslinkable and curable copolymer. Further, another crosslink-curable copolymer, for example, an epoxy resin or a polyester resin may be used in combination. When another cross-linkable curable copolymer is used in combination, the component (A) is a cross-linkable curable copolymer of 2
It is preferable to use 0% by weight or more, preferably 30% by weight,
50% by weight is more preferable, and 80% by weight or more is particularly preferable. The component (C) is not particularly limited as long as it is a compound containing at least two hydroxyl groups in one molecule, but from the viewpoint of the performance of the obtained coating film, the compounds represented by the general formulas (4) to (6) And one or a mixture of two or more selected from the group consisting of polyester resins containing hydroxyl groups at both ends. As the compound represented by the general formula (4), for example, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-
Dodecanediol, 1,18-stearyldiol and the like. Examples of the compound represented by the general formula (5) include HO [CO (CH ₂ ) ₅ O] ₅ H and HO [CO
(CH ₂ ) ₈ O] ₅ H, HO [CO (CH ₂ ) ₁₀ O] ₅ H, HO
[CO (CH ₂ ) ₁₅ O] ₅ H, HO [CO (CH ₂ ) ₂₀ O]
₅ H, HO [CO (CH ₂ ) ₃₀ O] ₅ H, HO [CO (C
H ₂ ) ₄₀ O] ₅ H. Examples of the compound represented by the general formula (6) include HO (C ₂ H ₄ O) ₇ H,
HO (C ₂ H ₄ O) ₁₀ H, HO (C ₂ H ₄ O) ₁₂ H, HO
(C ₂ H ₄ O) ₂₀ H, HO (C ₂ H ₄ O) ₃₀ H, HO (C _{2
H 4 O) 40 H, HO} [CH (CH3) CH 2 O] 10 H, HO
_{[CH (CH3) CH 2 O} ] 20 H, HO [CH (CH3) C
H ₂ O] ₃₀ H. As the component (C), any of a liquid and a solid at room temperature can be used. However, it is preferable to use a solid at room temperature from the viewpoint of preventing a decrease in powder characteristics and storage stability. The component (C) includes:
It is used in an amount of 2 to 60 parts by weight, preferably 3 to 50 parts by weight, and more preferably 4 to 40 parts by weight, based on 100 parts by weight of the component (A). The hydroxyl group in the component (C) reacts with the acid anhydride group in the component (A) by heating to act as a crosslinking agent. Therefore, only the components (A) and (C) exhibit sufficient curability. The component (A), the component (B) and the component (C) are characterized in that a reaction between an acid anhydride and a hydroxyl group occurs between the component (A) and the component (B) and between the component (A) and the component (C). An acid is formed, which
Since it serves as a catalyst for the hydrolysis / condensation reaction of the silyl group represented by the general formula (1), crosslinking of the silyl group and crosslinking of the acid anhydride-hydroxyl group are formed. If necessary, the curing catalyst (D) Can be used.

As the component (D), a curing catalyst capable of accelerating the hydrolysis reaction of the silyl group represented by the general formula (1) in the component (A) and the component (B) and promptly causing a condensation reaction. If it can be used without particular limitation, organic sulfonic acid,
Examples thereof include a mixture or a reaction product of an organic sulfonic acid and a nitrogen-containing compound, phosphoric acid or phosphoric acid esters, and an organic metal compound.

Specific examples of the component (D) include, for example, dodecylbenzenesulfonic acid, p-toluenesulfonic acid,
Organic sulfonic acid compounds such as 1-naphthalenesulfonic acid and 2-naphthalenesulfonic acid; the organic sulfonic acid compounds and nitrogen-containing compounds (for example, 1-amino-2-propanol, monoethanolamine, diethanolamine,
2- (methylamino) ethanol, 2-dimethylethanolamine, 2-amino-2-methyl-1-propanol, diisopropanolamine, 3-aminopropanol, 2-methylamino-2-methylpropanol, morpholine, oxazolidine, , 4-dimethyloxazolidine, 3,4,4-trimethyloxazolidine, etc.) or a reaction product thereof; phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monododecyl phosphate, dimethyl phosphate, diethyl phosphate ,
Phosphoric acid or phosphoric acid ester such as dibutyl phosphate, dioctyl phosphate, didodecyl phosphate; propylene oxide, butylene oxide, cyclohexene oxide, glycidyl methacrylate, glycidol, acrylic glycidyl ether, 3-glycidoxypropyltrimethoxysilane, 3-glycide Epoxy compounds such as xypropyltriethoxysilane, 3-glycidoxypropyltrimethyldimethoxysilane, Cardura E manufactured by Yuka Shell Epoxy, Epicoat 828 and Epicoat 1001 manufactured by Yuka Shell Epoxy, and phosphoric acid and / or phosphoric acid. Or an addition reaction product with a monophosphate; hexylamine, di-2-ethylhexylamine, N, N-dimethyldodecylamine, DABC
Amines such as O, DBU, morpholine and diisopropanolamine; reactants of these amines with acidic phosphate esters; alkaline compounds such as sodium hydroxide and potassium hydroxide; benzyltriethylammonium chloride or bromide, tetrabutylammonium Quaternary ammonium salts such as chloride or bromide, and phosphonium salts; divalent tin compounds such as tin octylate and tin stearate, dibutyltin dioctoate,
Dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin bistriethoxysilicate, dibutyltin distearate, dibutyltin compounds such as dibutyltin malate, dioctyltin diversate, dioctyltin dilaurate, dioctyltin distearate, dioctyltin malate Organic titanate compounds such as tetramethoxytitanium and tetrastearyloxytitanium; organic aluminum compounds such as aluminum isopropoxide and aluminum acetylacetonate; zirconia stearate and zirconium tetraacetylacetate Organic zirconium compounds such as nates.

Of these, organic titanate compounds and organic zirconium compounds are preferred from the viewpoint of curability during baking.

These curing catalysts may be used alone or in combination. These curing catalysts are used in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the component (A).
It is preferably 0.1 parts by weight, more preferably 0.1 to 10 parts by weight. 10
If the amount is more than the weight part, there arises a problem that the storage stability is lacking and the appearance of the coating film is deteriorated. The resin composition for powder coatings, if necessary, polyester, epoxy, acrylic and other resins, titanium dioxide, carbon black, iron oxide, inorganic pigments such as chromium oxide and phthalocyanine-based, quinacodrine-based organic pigments, Additives such as a coloring aid, a spreading agent, an antifoaming agent, an ultraviolet absorber, an antistatic agent and an antiblocking agent can be added. The mixing ratio of these additives can be appropriately selected according to the required characteristics,
It is also possible to use a mixture.

The powder coating is prepared by using a melt kneader such as a heating roll or a kneader, cooling, and then pulverizing. Or, in the solution after polymerization of the vinyl copolymer,
A method in which a curing catalyst, a pigment, an additive, and the like are added and mixed, followed by spray drying can also be used.

The powder coating obtained in this manner is applied to a substrate by a known method such as electrostatic coating or fluid immersion coating. The thickness of the coating film can be appropriately selected as needed, and is usually 20 to 200 μm, preferably 40 to 150 μm.
μm is good. When the thickness is less than 20 μm, the coating film tends to be uneven, and when the thickness is more than 200 μm, there is a problem that the coating film tends to have irregularities.

The obtained coated product is usually at 150 to 250 ° C.
By baking at a temperature of about 5 minutes to 1 hour, it can be sufficiently cured, and a cured product (coating film) having excellent physical properties such as weather resistance and acid resistance can be formed. Fifteen
If the temperature is lower than 0 ° C or shorter than 5 minutes, the coating film is not sufficiently cured, and if the temperature is higher than 250 ° C or longer than 1 hour, workability deteriorates and costs such as utility costs increase. Problem arises.

The composition of the present invention is used, for example, for building interiors and exteriors such as aluminum siding and fences, road materials such as guardrails, and home appliances such as air conditioners and refrigerators.

[0034]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In addition, the part shown below shall show a weight part unless there is particular notice. The analytical values, characteristic values, and performance of the coating film in the examples were measured or evaluated by the following methods. Analytical values (1) Number average molecular weight of polymer Measured by gel permeation chromatography (GPC). Using a Waters 600 GPC system, chloroform was used as the mobile phase and the flow rate was 1 m.
L / min. The column temperature was measured at 40 ° C. The number average molecular weight was calculated using polystyrene as a standard sample. (2) Glass transition temperature Differential scanning calorimeter (DSC, Shimadzu Corporation DSC-
50 type) under a nitrogen atmosphere at a heating rate of 5 ° C./mi.
n and determined. Characteristic value and performance of coating film (1) Appearance Appearance and smoothness were visually evaluated. ：: extremely good, ：: good, Δ: gloss, ×: poor (2) Weather resistance The appearance of the coating film after 3000 hours of irradiation with a sunshine weather meter was visually evaluated. ◎: extremely good, ○: slightly glossy, Δ: glossy,
×: cracking and peeling (3) Acid resistance The coating film appearance after immersing the coating film in a 5% aqueous sulfuric acid solution at room temperature for 24 hours was visually evaluated. ◎: extremely good, ○: slightly glossy, Δ: glossy,
×: cracking, peeling (4) Curability 1 g of the baked composition was wrapped in a 200-mesh stainless steel wire gauze, immersed in acetone for 24 hours, and the weight change of the composition was examined. 1
00%. ◎: 90% or more, ：: 90 to 80%, Δ: 80 to 70
%, ×: 70% or less (5) Adhesion The adhesion was evaluated by a grid tape method according to JIS K5400. ◎: No missing portion, ○: Within 5% of missing portion, Δ: 5% of missing portion
１５15%, ×: 15% or more of defective part (6) Storage stability The change in gel fraction before and after storage was examined as a measure of the progress of gelation of powder coatings stored at 40 ° C. for one month. ◎: no change, ：: change in gel fraction within 5%, Δ: 5%
Gel fraction change of １５15%, ×: Gel fraction change of 15% or more Resin Production Examples 1 to 23 50 parts of toluene was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel. After charging and raising the temperature to 110 ° C. while introducing nitrogen gas, the copolymer components shown in Tables 1 and 2 were dropped at a constant rate over 5 hours by a dropping funnel. After the addition of the mixture was completed, a mixture of 0.5 part of 2,2′-azobisisobutyronitrile and 10 parts of toluene was added dropwise at a constant speed over 1 hour. After completion of the dropwise addition, the mixture was further heated at 110 ° C. for 1 hour and then cooled. The solvent was distilled off from the resin solution under reduced pressure to obtain solid resins (α-1) to (α-23).

[0035]

[Table 1]

[0036]

[Table 2] (In the table, TSMA is 3-methacryloxypropyltrimethoxysilane, TESMA is 3-methacryloxypropyltriethoxysilane, MMA is methyl methacrylate, BA is butyl acrylate, MAn is maleic anhydride, and ST is styrene. , HEMA represents 2-hydroxyethyl methacrylate, and AIBN represents 2,2′-azobisisobutyronitrile.) Comparative Resin Production Examples 1 to 5 The copolymer components shown in Table 3 were used in the same manner as in the resin production examples. By the method, solid-state resins (β-1) to (β-5) were obtained.

[0037]

[Table 3] (In the table, TSMA is 3-methacryloxypropyltrimethoxysilane, MMA is methyl methacrylate, B
A is butyl acrylate, GMA is glycidyl methacrylate, ST is styrene, HEMA is 2-hydroxyethyl methacrylate, AA is acrylic acid, A
IBN represents 2,2'-azobisisobutyronitrile. Examples 1 to 30 Using resin (α-1) to (α-23), according to the formulations in Tables 4 to 6, all components were dry-rendered (Henschel (trade name, manufactured by Mitsui Chemicals, Inc.) After mixing uniformly for 1 minute using a mixer, the mixture is melt-kneaded using an extrusion kneader (BUSS Co. Kneader PR-46, manufactured by BUSS) at a temperature of 100 to 110 ° C., cooled, and then jet-milled ( Finely pulverized using Seishin Enterprise Co., Ltd., trade name Single Track Jet Mill STJ200) to obtain powder coatings (γ-1) to (γ-3) having an average particle size of 30 μm.
0) was prepared. The obtained powder coating material was coated on a 0.8 mm-thick zinc phosphate treated steel sheet so as to have a thickness of 50 to 60 μm by an electrostatic coating machine (manufactured by Nippon Wagner Spray Tech Co., Ltd., trade name: Airmatic Spray Co., Ltd.). Gun PEM-
C1) was applied and baked at 220 ° C. for 15 minutes to form a coating film. The results of evaluating the performance of the obtained coating films are shown in Tables 4 to 6.

[0038]

[Table 4]

[0039]

[Table 5]

[0040]

[Table 6] (In the table, TST is tetrastearyloxytitanium, P
CL220 is a hydroxyl-terminated polycaprolactone oligomer manufactured by Daicel Chemical Industries, Ltd., ER-7400 is a hydroxyl-terminated polyester resin manufactured by Nippon Ester Co., Ltd., TiO ₂ is titanium oxide CR-90 manufactured by Ishihara Sangyo Co., Ltd., and Acronal 4F is The leveling agent manufactured by BASF is shown. Comparative Examples 1 to 5 According to Table 7, the powder coatings (γ-31) to (γ-35) were produced in the same manner as in the production examples. Further, coating was performed in the same manner as in the production example, and the results of evaluating the performance of the obtained coating film are shown in Table 7.

[0041]

[Table 7] In the table, TST is tetrastearyloxytitanium, Coronate 2513 is a blocked isocyanate manufactured by Nippon Polyurethane Co., Ltd., TGIC is triglycidyl isocyanurate, and TiO ₂ is titanium oxide C manufactured by Ishihara Sangyo Co., Ltd.
R-90 and Acronal 4F indicate a leveling agent manufactured by BASF. )

[0042]

According to the present invention, excellent weather resistance, acid resistance,
It is possible to provide a powder coating having a new cross-linking form, which has appearance and adhesion, clears environmental problems, and can be manufactured at low cost.

Claims (17)

[Claims] 1. A silyl group-containing vinyl monomer (a) represented by the following general formula (1): 1 to 30 parts by weight, and an acid anhydride group-containing vinyl monomer (b) 1 To 30 parts by weight, and a vinyl copolymer (A) obtained by copolymerizing 98 to 40 parts by weight of a copolymerizable vinyl monomer (c) other than the component (a) and the component (b). ) As an essential component, and the component (A) has a silyl group represented by the following general formula (1) as a main crosslinkable group, and has a glass transition temperature of 40 to 100.
A resin composition for powder coatings having a number average molecular weight of 2,000 to 20,000 at ℃. Embedded image (Wherein, R1 is an alkyl group having 1 to 10 carbon atoms, 6 carbon atoms)
At least one group selected from the group consisting of an aryl group having 10 to 10 and an aralkyl group having 7 to 10 carbon atoms,
In the case of a plurality, they may be the same or different. X is a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, a phenoxy group, a thioalkoxy group, an acyloxy group, an aminoxy group, a ketoximate group, an amino group,
It is at least one group selected from the group consisting of an amide group and an alkenyloxy group, and when there are a plurality of groups, they may be the same or different. a is an integer of 0 to 2. ) 2. The composition contains a crosslinkable and curable polymer other than the component (A), and the component (A) accounts for 20% by weight or more and less than 100% by weight of the total of the component (A) and the polymer. The resin composition for a powder coating according to claim 1, wherein: 3. The resin composition for a powder coating according to claim 1, wherein X in the general formula (1) is an alkoxy group. 4. The composition according to claim 1, wherein the component (a) is 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane and 3- (meth) acryloxypropylmethyldimethoxysilane.
The resin composition for a powder coating according to any one of claims 1 to 3, wherein the resin composition is at least one selected from the group consisting of (meth) acryloxypropylmethyldiethoxysilane. 5. The method according to claim 1, wherein the component (b) is at least one selected from the group consisting of maleic anhydride, itaconic anhydride and citraconic anhydride.
5. The resin composition for a powder coating according to any one of 4. 6. The method of claim 1, wherein the other copolymerizable vinyl monomer of component (c) comprises 1 to 20 parts by weight of a hydroxyl-containing vinyl monomer (d) out of 98 to 40 parts by weight. The resin composition for a powder coating according to any one of claims 1 to 5, which is characterized in that: 7. The hydroxyl group-containing vinyl monomer of component (c) is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
-Hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, hydroxystyrene, 2-hydroxy-3-phenoxypropyl acrylate, a vinyl monomer having a group represented by the following formula (2), and a compound represented by the following formula (3) The resin composition for a powder coating according to any one of claims 1 to 6, wherein the resin composition is at least one selected from the group consisting of vinyl monomers having a group. -O ｛CO (CH2) 5O｝ m-H (2) (where m is an integer of 1 to 50) -O −C (R2) (CH2) 2O｝ n-H (3) (Formula In the formula, R2 is hydrogen or a methyl group, and n is an integer of 2 to 100.) 8. The method according to claim 1, wherein the acrylic resin (B) having a hydroxyl group is contained in an amount of 30 to 200 parts by weight based on 100 parts by weight of the component (A). A resin composition for powder coatings. 9. The powder according to claim 1, wherein the hydroxyl group-containing resin as the component (B) contains a silyl group represented by the general formula (1). Resin composition for body paint. (10) The component (B) is a vinyl monomer having a silyl group represented by the following general formula (1):
50 parts by weight, (d) a vinyl monomer containing a hydroxyl group 1
(E) a polymer obtained by copolymerizing 98 to 20 parts by weight of another vinyl monomer copolymerizable with the component (a) and the component (d). Claim 1
10. The resin composition for a powder coating according to any one of items 9 to 9. 11. 1 part by weight of component (A)
Compound (C) 2 containing two or more hydroxyl groups in the molecule
The resin composition for powder coating according to any one of claims 1 to 10, comprising 60 parts by weight. 12. The compound having two or more hydroxyl groups in one molecule of component (C) is selected from the group consisting of general formulas (4) to (6) and polyester resins having hydroxyl groups at both ends. The resin composition for powder coating according to any one of claims 1 to 11, wherein the resin composition is at least one kind. Embedded image (In the formula, R3 is a linear or branched alkylene group having 6 to 30 carbon atoms.) (In the formula, R4 is a linear or branched alkylene group having 2 to 30 carbon atoms, m is an integer of 1 to 50, and n is an integer of 0 to 50.) (In the formula, R5 is hydrogen or a methyl group, and n is an integer of 2 to 100.) 13. The resin composition for a powder coating material comprises 0.001 to 10 parts by weight of a curing catalyst (D) based on 100 parts by weight of the component (A). 13. The resin composition for a powder coating according to any one of 1 to 12. 14. The component (D) is at least one selected from the group consisting of an organic acidic compound, a mixture or reaction product of the organic acidic compound and a nitrogen-containing compound, and a mixture of two or more organic metal compounds. The resin composition for a powder coating according to any one of claims 1 to 13, wherein: 15. The method according to claim 15, wherein the component (D) is at least one kind or a mixture of two or more kinds selected from the group consisting of an organic sulfonic acid and a mixture of an organic sulfonic acid and a nitrogen-containing compound. Item 15. The resin composition for powder coatings according to any one of Items 1 to 14. 16. The method according to claim 16, wherein the component (D) is at least one selected from the group consisting of an organic tin compound, an organic titanium compound, an organic aluminum compound, and an organic zirconium compound.
The resin composition for powder coating according to any one of claims 1 to 15, wherein the resin composition is a mixture of two or more kinds. 17. The method according to claim 17, wherein the resin composition for powder coating is 150 to 2 parts.
The composition is baked and cured at 50 ° C.
16. The resin composition for a powder coating according to any one of the above items 16.