JP2001279132A - Resin composition for thermosetting coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for a thermosetting coating which is low-viscous though an organic solvent is not used and therefore excellent in workability, suffers from no deterioration in lubricity of a coating film even when subjected to a warm-water treatment such as a retort treatment, or the like, and exhibits environmental adaptability. SOLUTION: This resin composition for a thermosetting coating comprises as essential components (A) a polyester-based resin bearing at least one radically polymerizable unsaturated group at a molecular end and having a numberaverage mol.wt., per unsaturated group, of 500-20,000 and/or an acrylic resin bearing at least one radically polymerizable unsaturated group in a molecular side chain and having a number-average mol.wt., per unsaturated group, of 1,000-20,000, (B) a polyfunctional (meth)acrylate having a number-average mol.wt., per (meth)acryloyl group, of 85-300 and (C) an organopolysiloxane bearing a radically polymerizable unsaturated group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition for a thermosetting coating. More specifically, the present invention relates to a resin composition for a thermosetting coating material, which is suitable for a coating material for coating the outer surface of a metal can and has a lubricating coating film.

[0002]

2. Description of the Related Art Conventionally, paints used for metal cans are composed of various synthetic resin solutions, coloring agents, various auxiliaries, and the like. Particularly, overcoat paints impart lubricity to the surface of the paint film. It is important to be. If the surface of the coating film does not have lubricity, it may be damaged in the process of manufacturing metal cans, or when the cans filled with the contents flow through the filling line, contact cans between the cans or between the cans and the guideline, etc. May be clogged or scratched in the line. As a method for imparting lubricity to a coating film, a method of blending a modified silicone having an alkenyl group with a thermosetting resin such as an epoxy resin, a polyester resin and an acrylic resin (Japanese Patent Application Laid-Open No. Sho 63-295677).
And so on.

[Problems to be solved by the invention]

[0003] However, the conventional one has a problem that the lubricating property of the coating film is deteriorated by hot water treatment such as retort treatment due to detachment of the silicone copolymer from the coating film. An object of the present invention is to provide a resin composition for a thermosetting coating material in which lubricity of a coating film is not reduced even when a hot water treatment such as a retort treatment is performed.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to obtain a thermosetting paint capable of achieving the above object, and as a result, have reached the present invention. That is, the present invention has at least one radically polymerizable unsaturated group at a molecular terminal, and has a number average molecular weight of 500 to 20,000 per unsaturated group.
Having at least one polyester-based resin or / and a radically polymerizable unsaturated group in a molecular side chain;
Acrylic resin (A) having a number average molecular weight of 1,000 to 20,000 per unit, polyfunctional (meth) acrylate (B) having a number average molecular weight of 85 to 300 per (meth) acryloyl group, and Resin composition for thermosetting paint characterized by containing organopolysiloxane (C) having a radical polymerizable unsaturated group as an essential component; thermosetting paint containing the composition; curing the paint And a metal can formed by deep drawing a metal material having a coating layer obtained by curing the paint.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The resin (A) includes a polyester resin (A1), an acrylic resin (A2) and a combination thereof. (A1) and (A2) each have at least one radically polymerizable unsaturated group in the molecule,
~ 8, preferably 1-6, more preferably 1-3
It has one. In the method for introducing a radically polymerizable unsaturated group in (A), it is possible to introduce a radically polymerizable unsaturated group at any stage of production.
In advance, after producing a polyester-based resin or acrylic resin containing no radically polymerizable unsaturated group,
A method of introducing a radically polymerizable unsaturated group, a method of simultaneously introducing a radically polymerizable unsaturated group at the stage of polycondensing a polyester resin from its constituent monomers, and one or more radically polymerizable unsaturated groups in advance. A method of producing a polyester resin containing two or more radically polymerizable unsaturated groups by combining them after producing a polyester resin containing more than that, and the like.

In the present invention, the polyester resin (A)
In the case of the above production method, 1) is a polyester resin (a1) having at least one active hydrogen-containing group and a compound (e) having a functional group capable of reacting with the active hydrogen-containing group and a radical polymerizable unsaturated group. ).

The active hydrogen-containing group contained in (a1) includes a hydroxyl group and a carboxyl group. Examples of the functional group capable of reacting therewith include a carboxyl group, an ester-forming group [lower alkyl (1 to 4 carbon atoms) ester group, an acid anhydride group, an acid halide group, etc.] -Methylolamide group, N-alkoxyalkylamide group and the like], and a carboxyl group includes a hydroxyl group and an epoxy group.

A compound (a1) comprising (a1) and providing a carboxyl group as an active hydrogen-containing group to the (a1)
1) has 2 to 40 carbon atoms (preferably 2 to 10)
Aliphatic or alicyclic dicarboxylic acids [oxalic acid, succinic acid, malonic acid, adipic acid, glutaric acid, azelaic acid, sebacic acid, hexahydrophthalic acid, nadic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid Acid, dimer acid, etc.]; an aromatic dicarboxylic acid having 8 to 18 carbon atoms [phthalic acid, isophthalic acid, terephthalic acid, etc.]; 3 to 8 carbon atoms having 8 to 60 (preferably 8 to 18).
Tetravalent or higher aliphatic or alicyclic polycarboxylic acid [methylcyclohexentricarboxylic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, trimer acid, etc.]; trivalent to tetravalent or higher having 9 to 18 carbon atoms Aromatic polycarboxylic acids [trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, etc.]; their ester-forming derivatives [acid anhydrides, lower alkyl (C1-4) esters, acid halides, etc.]; And a combination of two or more of these. Of these, preferred are aliphatic dicarboxylic acids, aromatic dicarboxylic acids, tri- or higher-valent or higher aromatic polycarboxylic acids (anhydrides), and combinations of two or more of these. Dicarboxylic acids, aromatic divalent to tetravalent carboxylic acids and combinations thereof are particularly preferred, and aromatic polycarboxylic acids selected from adipic acid and / or sebacic acid and isophthalic acid, terephthalic acid and (trimellitic anhydride) are particularly preferred. Combined use with acid [mass ratio (20
To 50): (80 to 50)].

The compound (a12) which constitutes (a1) and imparts a hydroxyl group as an active hydrogen-containing group to (a1) includes, for example, aliphatic dihydric alcohols having 2 to 12 carbon atoms (ethylene glycol, propylene glycol) , 1,2
-, 1,3-, 2,3- or 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-
Pentanediol, 2-methyl-2,4-pentanediol, 2,2-diethyl-1,3-propanediol,
2-ethyl-1,3-hexanediol, 2,2,4-
Trimethyl-1,3-pentanediol, 2-butyl-
2-ethyl-1,3-propanediol, 1,9-nonanediol, 1,12-dodecanediol, etc.), an alicyclic dihydric alcohol having 6 to 15 carbon atoms [1,4-cyclohexylene glycol, 1, 4-cyclohexanedimethanol, 2,2-bis (4,4'-hydroxycyclohexyl) propane, 4,4'-dihydroxycyclohexylsulfone, 4,4'-dihydroxycyclohexylmethane, etc.], and aromatics having 8 to 15 carbon atoms Dihydric alcohols (such as xylylene glycol), (poly) oxyalkylene ethers of these dihydric alcohols (1 to 20 or more oxyalkylene units), dihydric phenols [monocyclic dihydric phenols (hydroquinone, Resorcinol, catechol, etc.), bisphenols (bisphenol A, bispheno) Diols such as polyoxyalkylene ethers (having 2 to 20 or more oxyalkylene units); aliphatic trihydric alcohols having 3 to 6 carbon atoms (glycerin, trimethylolethane, Methylol propane,
Triols such as 1,2,6-hexanetriol) and (poly) oxyalkylene ethers (the number of oxyalkylene units is 1 to 30 or more, preferably 1 to 20) of these trihydric alcohols; 1
Aliphatic tetrahydric alcohols such as pentaerythritol, diglycerin, methyl glucoside and the like;
Tetraols such as (poly) oxyalkylene ethers of a polyhydric alcohol (the number of oxyalkylene units is 1 to 40 or more, preferably 1 to 20); 5 to 12 or more aliphatic polyhydric compounds having 6 to 30 carbon atoms. Dihydric alcohol (dipentaerythritol, sorbitol, sucrose,
Polyols such as polyglycerin (degree of polymerization: 3 to 10) and (poly) oxyalkylene ethers (the number of oxyalkylene units per hydroxyl group is 1 to 20 or more) of these polyhydric alcohols; and two kinds thereof. A mixture of the above is mentioned. Of these, preferred are aliphatic dihydric alcohols, aliphatic trihydric alcohols, aliphatic tetrahydric alcohols, and combinations of two or more of these (particularly, combinations of dihydric alcohols with trihydric alcohols and / or tetrahydric alcohols). Is more preferable.
Neopentyl glycol, 2-butyl-2-ethyl-
A combination of a dihydric alcohol selected from 1,3-propanediol and 1,6-hexanediol, and trimethylolpropane and / or pentaerythritol. In the case of combined use, the mass ratio of the dihydric alcohol to the trihydric alcohol and / or the tetrahydric alcohol is (99.5: 0.
5) to (70:30), especially (98: 2) to (80: 2)
0) is preferred.

In the above and the following, (poly) oxyalkylene ether means oxyalkylene ether and / or polyoxyalkylene ether, and the oxyalkylene group constituting the same has 2 to 12 carbon atoms (preferably 2 to 12 carbon atoms). 4) oxyalkylene such as oxyethylene, oxypropylene, 1,2
-, 1,3-, 2,3- or 1,4-oxybutylene and a combination of two or more thereof (block and / or
Or random). Preferred are oxyethylene and / or oxypropylene. These can be produced by adding an alkylene oxide (hereinafter abbreviated as AO) to the polyhydric alcohol or the dihydric phenol. As AO, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-butylene oxide,
Tetrahydrofuran, styrene oxide, carbon number 8-1
2 α-olefin oxides and the like.

In the present invention, (a1) is usually (a1)
It is produced by polycondensing 1) and (a12). The active hydrogen-containing group is a carboxyl group (a1)
When obtaining (a1), the carboxyl group of (a11) and (a1)
The equivalent ratio of hydroxyl groups in (2) is usually (1.05: 1) to (1.
3: 1), preferably (1.07: 1) to (1.2:
1). When (a1) in which the active hydrogen-containing group is a hydroxyl group is obtained, the carboxyl group of (a11) and (a12)
The equivalent ratio of the hydroxyl group is usually (1: 1.05) to (1: 1.
3), preferably (1: 1.07) to (1: 1.2). In addition to the above (a11) and (a12), if necessary, a monocarboxylic acid and / or a monoalcohol (a1
One or more of 3) may be polycondensed. Examples of the monocarboxylic acids include aliphatic saturated monocarboxylic acids having 2 to 20 carbon atoms (acetic acid, propionic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, castor oil fatty acid, stearic acid, and the like). Can be Monoalcohols include aliphatic monoalcohols having 1 to 20 carbon atoms (methanol, ethanol, propanol,
-Butanol, 2-butanol, 1-octanol, 2
-Ethylhexanol, lauryl alcohol, etc.), and oxyalkylene ethers (the number of oxyalkylene units is 1 to 20) of these monoalcohols.
Of these, preferred are monocarboxylic acids, and more preferred are saturated monocarboxylic acids. The (a
The amount of (13) used is (a11), (a12) and (a1).
The amount is usually 10 equivalent% or less, preferably 0.5 to 5 equivalent%, based on the total number of equivalents of the carboxyl group and the hydroxyl group in 3).

Further, (a1) is obtained by adding (a1) to (a12).
It can also be produced by reacting the anhydride of 1) with AO. Furthermore, (a1) is (a11) or (a
12) or lactone (a1)
It can also be manufactured by adding 4). (A14) includes a lactone having 4 to 12 carbon atoms;
For example, γ-butyrolactone, ε-caprolactone, γ-
Valerolactone and mixtures of two or more of these. The number of moles of (a14) is preferably 2 to 1,
000.

When the active hydrogen-containing group (a1) is a hydroxyl group, the hydroxyl value is preferably from 2 to 120, more preferably from 3 to 100 mgKOH / g. When the active hydrogen-containing group in (a1) is a carboxyl group, the acid value is preferably from 2 to
140, more preferably 3 to 120 mgKOH / g.

The method for producing (a1) is not particularly limited.
It can be produced by a usual esterification method or transesterification method. The reaction temperature is usually 100 to 300 ° C. At the time of the reaction, a catalyst [for example, a mineral acid (sulfuric acid, hydrochloric acid, etc.), an organic acid (p-toluenesulfonic acid, etc.), a Lewis acid (boron fluoride etherate, etc.), an organic metal (dibutyltin dilaurate) for smooth reaction. , Tin octylate, lithium naphthenate, tetrabutoxytitanium, etc.),
An ion exchange resin (eg, an acidic ion exchange resin)], a dehydration auxiliary solvent [eg, an aromatic hydrocarbon (eg, toluene, xylene), or a ketone (eg, methyl ethyl ketone, methyl isobutyl ketone)] may be used.

The compound (e1) having a functional group capable of reacting with (a1) and a radical polymerizable unsaturated group includes, for example, a radical polymerizable unsaturated monomer capable of directly reacting with the hydroxyl group of (a1); Saturated monocarboxylic acids [unsaturated monocarboxylic acids [(meth) acrylic acid, crotonic acid, etc.]], alkyls of unsaturated monocarboxylic acids (C1 to C1)
5) Esters [methyl (meth) acrylate,
Ethyl (meth) acrylate, butyl (meth) acrylate], unsaturated dicarboxylic acids [maleic anhydride, fumaric acid, itaconic anhydride, etc.],
Monoalkyl (1 to 5 carbon atoms) esters of unsaturated dicarboxylic acids [monomethyl maleate, monoethyl maleate, monobutyl itaconate, etc.], lactones of unsaturated monocarboxylic acids (3 to 1 carbon atoms)
2) adducts (addition moles 1 to 10) [for example, (meth)
1-5 mol adduct of acrylic acid with ε-caprolactone]
Etc.), (meth) acrylates having a methylolated amide group; for example, methylolated (meth) acrylamides [[N-methylol (meth) acrylamide and the like], alkoxy (C1-4) alkyl (C1-4) (Meth) acrylamides [N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethylacrylamide, etc.] and the like. Examples of the radically polymerizable unsaturated monomer capable of reacting with the carboxyl group of (a1) include, for example, aliphatic dihydric alcohols having 2 to 12 carbon atoms such as hydroxyl group-containing (meth) acrylates (eg, ethylene glycol, propylene glycol, , 2-, 1,3- or 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-methyl-2 , 4-
Pentanediol, 1,9-nonanediol, 2,2-
Mono (meth) acrylates such as diethyl-1,3-propanediol), and (poly) oxyalkylene ethers of the above dihydric alcohols (having 1 to 1 oxyalkylene units).
20) mono (meth) acrylate [for example, polyoxyethylene (number of oxyethylene units 2 to 20) mono (meth) acrylate, polyoxypropylene (number of oxypropylene units 2 to 20) mono (meth) acrylate, etc.], Mono (meth) of a tri- or higher-valent or higher aliphatic polyhydric alcohol (for example, glycerin, trimethylolpropane, diglycerin, triglycerin, pentaerythritol, sorbitol, dipentaerythritol, etc.)
Acrylates, (poly) oxyalkylene ethers of the above-mentioned polyhydric alcohols (number of oxyalkylene units 1-2)
0) mono (meth) acrylates;
Polyfunctional (meth) acrylates, etc., which are at least one hydroxyl group of an octahydric or higher aliphatic polyhydric alcohol, and others are (meth) acrylated, etc.], epoxy group-containing monomers, for example, Glycidyl esters [eg, glycidyl (meth) acrylate, glycidyl crotonate, etc.] and glycidyl ethers [eg, (meth) allyl glycidyl ether, propenyl glycidyl ether, etc.] can be mentioned. Of these (e1)
Are preferably unsaturated carboxylic acids and hydroxyl group-containing radically polymerizable unsaturated monomers, and more preferably (meth) acrylic acid, (anhydride) maleic acid and aliphatic dihydric alcohols having 2 to 6 carbon atoms. Alternatively, it is a mono (meth) acrylate (having 1 to 20 oxyalkylene units) of the (poly) oxyalkylene ether (oxyethylene and / or oxypropylene).

The number average molecular weight of (A1) (based on GPC).
The same applies hereinafter) is usually 500 to 120,000, preferably 800 to 100,000, and more preferably 1,000.
~ 80,000. The number average molecular weight per radically polymerizable unsaturated group of (A1) is usually 500 to 20,
000, preferably 800 to 12,000, and more preferably 1,000 to 10,000. If the number average molecular weight per radically polymerizable unsaturated group is less than 500, the flexibility (processability) of the obtained coating film becomes insufficient,
If it exceeds 000, the viscosity of the paint becomes high, and the workability is reduced. The concentration of the radically polymerizable unsaturated group in (A1) can be measured by measuring the H ¹ -NMR of (A1), and from the measurement of the number average molecular weight by GPC, the radically polymerizable unsaturated group 1 The number average molecular weight per piece can be calculated.

The method for producing (A1) is not particularly limited, and examples thereof include the following method. Dehydration is carried out at an equivalent ratio of 1 equivalent or more (preferably 1.05 to 10 equivalents) of unsaturated monocarboxylic acid to 1 equivalent of active hydrogen of polyester resin (a1) having at least one active hydrogen-containing group (for example, hydroxyl group). Esterification reaction (reaction temperature 90 to 150
And normal pressure to 250 hPa), and if necessary, removing unreacted unsaturated carboxylic acids by washing with alkaline water or the like;
The transesterification reaction is carried out at an equivalent ratio of 1 equivalent or more (preferably 1.02 to 8 equivalents) of an alkyl (C1 to C4) ester of an unsaturated monocarboxylic acid to 1 equivalent of the active hydrogen of the above (a1). Reaction temperature 90 ~ 150 ℃, normal pressure ~ 200m
mHg) and, if necessary, removing by-produced alcohol and unreacted alkyl esters of unsaturated carboxylic acids by distillation or the like.

In the esterification reaction or transesterification reaction, the above-mentioned catalyst, dehydration auxiliary solvent and radical polymerization inhibitor (for example, hydroquinone, hydroquinone monomethyl ether, copper oleate, air, etc.) may be used.

In the case of the above-mentioned production method, (A1) is obtained by polycondensation using (e) simultaneously with the above (a11) and (a12). Specifically, it can be produced by the polyesterification method described above.

In the case of the above-mentioned production method, (A1) is a method in which a polyester resin containing a radically polymerizable unsaturated group at one end and an active hydrogen-containing group such as a hydroxyl group at the other end is produced in advance (for example, (meth) acrylic). Lactone-modified adducts of acids), and these are polyisocyanates [aromatic, aliphatic, alicyclic and araliphatic polyisocyanates having 2 to 18 carbon atoms (excluding carbon in the isocyanate group), for example, diphenylmethane- 2,4'- or 4,
4′-diisocyanate (MDI), 2,4- or 2,6-tolylene diisocyanate (TDI), carbodiimide-modified MDI, etc.], polyalkyl halide (1 to 4 carbon atoms) (eg, bromochloromethane, dichloromethane, etc.) And by reacting with a linking agent such as

In the present invention, the acrylic resin (A2)
Can be produced by reacting an acrylic resin (a2) having at least one active hydrogen-containing group with a compound (e2) having a functional group capable of reacting with the active hydrogen-containing group and a radical polymerizable unsaturated group. it can.

The active hydrogen-containing group contained in (a2) includes a hydroxyl group, a carboxyl group, an amino group (primary and secondary), an amide group and a monosubstituted amide group. Examples of the functional group capable of reacting therewith include a carboxyl group and an ester-forming group [lower alkyl (C1-4) S group, acid anhydride group, acid halide group, etc.] for the hydroxyl group. The carboxyl group includes a hydroxyl group, and the amino group includes a carboxyl group and an epoxy group.

The acrylic resin (a2) having at least one active hydrogen-containing group includes a monomer (a21) having an active hydrogen-containing group and a monomer (a22) having no active hydrogen-containing group. Polymers.

The above (a21) includes a carboxyl group-containing monomer; an unsaturated monocarboxylic acid [eg, (meth)
Acrylic acid, crotonic acid, etc.], unsaturated dicarboxylic acids [for example, (anhydrous) maleic acid, fumaric acid, (anhydride) itaconic acid, etc.], monoalkyl (1-5 carbon atoms) esters of unsaturated dicarboxylic acids [for example, Monomethyl maleate, monoethyl maleate, monobutyl itaconate, etc.), lactone (3-12 carbon atoms) adduct of unsaturated monocarboxylic acid (1-10 moles added) [eg, (meth) acrylic Ε-caprolactone of acid 1 to 5
A hydroxyl-containing monomer;
Mono (meth) acrylates of aliphatic dihydric alcohols (for example, those mentioned above) and (poly) of the above dihydric alcohols
Mono (meth) acrylate of oxyalkylene ether (number of oxyalkylene units 1 to 20) [for example, polyethylene glycol (degree of polymerization 2 to 20) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 2)
0) Mono (meth) acrylates and the like], aliphatic polyhydric alcohols having 3 to 12 or more valences (for example, those described above)
An amino group-containing monomer such as a mono (meth) acrylate of the above (poly) oxyalkylene ether (number of oxyalkylene units 1 to 20) mono (meth) acrylate of the above polyhydric alcohol; Examples of the acrylate include aminoalkyl (C2-8) (meth) acrylates [for example, aminoethyl (meth) acrylate, N- (2-aminoethyl) aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, and the like], As the secondary amino group-containing (meth) acrylate, monoalkyl (C1-6) aminoalkyl (C2-
8) Amide group-containing monomers such as (meth) acrylates [for example, monomethylaminoethyl (meth) acrylate and the like]; (meth) acrylamide, corresponding to the above-mentioned amino group-containing (meth) acrylate (ester bond is an amide bond) (Meth) acrylamide [eg, N- [3- (dimethylamino) propyl]
(Meth) acrylamide, etc.], N-alkyl (C1
6) (meth) acrylamide [for example, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, etc.], N
-Alkoxy (C1-6) alkyl (C2-8) (meth) acrylamide [for example, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, etc.] , N-methylol (meth) acrylamide,
Isobutoxymethylol (meth) acrylamide and the like. Preferred among these are unsaturated carboxylic acids, hydroxyl-containing monomers and combinations thereof,
More preferred are (meth) acrylic acid, maleic acid, aliphatic dihydric alcohols having 2 to 6 carbon atoms or (poly) oxyalkylene ethers thereof (oxyethylene and / or oxypropylene; the number of oxyalkylene units is from 1 to 20). Mol) mono (meth) acrylate and a combination of two or more thereof.

A monomer having no active hydrogen-containing group (a2
As 2), the (cyclo) alkyl group has 1 to 2 carbon atoms.
0 (cyclo) alkyl (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth)
Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Lauryl (meth) acrylate, etc.]; tertiary amino group-containing (meth) acrylate [dialkyl (C1-6) aminoalkyl (C2-8) (meth) acrylate,
For example, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, etc.];
N, N-dialkyl (C1-4) (meth) acrylamide [N, N-dimethyl (meth) acrylamide etc.]; N, N-dialkoxy (C1-4) alkyl (C2-8) (Meth) acrylamide [for example,
N, N-dimethoxymethyl (meth) acrylamide, etc.]; vinylformamide, vinylacetamide, etc .; aromatic ring-containing (meth) acrylate [eg, benzyl (meth) acrylate]; aromatic unsaturated hydrocarbon [styrene-based compound, eg, styrene] , Α-methylstyrene, ethylstyrene, dimethylstyrene, vinyltoluene, α
Glycidyl group-containing compound [for example, glycidyl (meth) acrylate, (meth)
Allyl glycidyl ether, etc.]; nitrile group-containing compounds [eg, (meth) acrylonitrile, etc.]; vinyl ester monomers [eg, vinyl acetate, vinyl propionate, etc.]; halogen-containing monomers [eg, vinyl chloride, vinyl fluoride, Vinylidene chloride, vinylidene fluoride, etc.]; olefinic monomers such as alkenes (2-8 carbon atoms) and alkadienes (4-10 carbon atoms), such as ethylene and propylene as alkenes and butadiene and isoprene as alkadienes. And combinations of two or more of these. Among them, preferred are at least one alkyl (meth) acrylate having an alkyl group having 1 to 10 (preferably 1 to 8) carbon atoms in view of imparting hardness and water resistance of the obtained coating film to a styrene-based resin. The compound is preferably used in combination with a compound, particularly preferably one or more selected from methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, and styrene and α-methyl. It is used in combination with one or more kinds selected from styrene and α-methylstyrene dimer.

The mass ratio of the alkyl (meth) acrylate (a22) to the styrene compound is usually (55-95) :( 45-95) from the viewpoint of the viscosity of the obtained paint and the gloss of the coating film.
5).

(A2) and (a21) and (a)
At least one of 22) is a (meth) acrylate monomer. The content of the (meth) acrylate-based monomer in (a2) is from 10 to 100% by mass, especially from 20 to 10% by mass.
0% by mass is preferred. The mass ratio of (a21) to (a22) is (2-4) in view of the hardness and workability of the obtained coating film.
0): (98-60), especially (5-30): (95-
70) is preferred.

The method for producing (a2) is not particularly limited.
It can be produced by a usual radical polymerization method (bulk polymerization, solution polymerization, emulsion polymerization, etc.). In the polymerization, a known radical polymerization initiator, chain transfer agent, organic solvent, or the like may be used. Examples of the polymerization initiator include azobisisobutyronitrile, azobisisovaleronitrile,
Azo compounds such as azobisisovaleric acid; organic peroxides such as benzoyl peroxide, t-butyl hydroperoxide, lauroyl peroxide, cumene hydroperoxide; potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, etc. And two or more of these inorganic peroxides. The amount of the polymerization initiator used is usually 0.1 to 5% by mass based on the total amount of the monomers.
It is. Examples of the chain transfer agent include mercaptans (butyl mercaptan, dodecyl mercaptan, etc.), α
-Methylstyrene dimer, chloroform and the like. The amount of the chain transfer agent is usually 5 to the total amount of the monomer.
% By mass or less, preferably 0.1 to 3% by mass. Examples of the organic solvent include alcohols (methanol, ethanol, n- or i-propanol, n-
-, Sec- or t-butanol, ethyl cellosolve, butyl cellosolve, ethyl carbitol, propylene glycol monoethyl ether, etc.), esters (ethyl acetate, butyl acetate, isoamyl acetate, cellosolve acetate, etc.); ethers (dioxane, etc.), Ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); aliphatic or alicyclic hydrocarbons (n-hexane, n-heptane, cyclohexane, etc.); aromatic hydrocarbons (toluene, xylene, trimethylbenzene, etc.) And mixtures of two or more of these. Of these, ketones and aromatic hydrocarbons are preferred. The organic solvent may be removed by a method such as distillation after polymerization.

As the compound (e2) having a radical polymerizable unsaturated group capable of reacting with active hydrogen of (a2), the same compounds as those described in (e1) can be used.

The method for producing (A2) is not particularly limited, and for example, the following method can be exemplified. For example, when the active hydrogen of (a2) is a hydroxyl group, 1 equivalent or more of (meth) acrylic acid (preferably 1.05 equivalent) is added to 1 equivalent of the hydroxyl group of (a2).
A dehydration esterification reaction (reaction temperature: 90 to 150 ° C., normal pressure: 250 hPa) at an equivalent ratio of 10 to 10 equivalents), and, if necessary, removing unreacted (meth) acrylic acid by washing with alkaline water; a1) equivalent of the hydroxyl group of (a), alkyl (C1-5) ester of (meth) acrylic acid
The transesterification reaction (reaction temperature 90-150 ° C, normal pressure-200 m
mHg) and, if necessary, removing by-produced alcohol and unreacted alkyl (meth) acrylate by distillation or the like.

In the above-mentioned esterification reaction or transesterification reaction, the above-mentioned catalyst, dehydration co-solvent, radical polymerization inhibitor and the like can be used in order to carry out the reaction smoothly.

The number average molecular weight of (A2) is usually 1,000
~ 200,000, preferably 2,000 ~ 100,0
00, more preferably 3,000 to 80,000. The number average molecular weight per radically polymerizable unsaturated group of (A2) is usually 1,000 to 20,000, preferably 3,000 to 15,000, and particularly preferably 8,000.
0 to 13,000. When the number average molecular weight per radically polymerizable unsaturated group is less than 1,000, the flexibility (workability) of the obtained coating film is reduced, and when it exceeds 20,000, the viscosity of the coating material is increased, and the workability is increased. Decrease.

When the resin (A) contains a carboxyl group, a part or the whole thereof may be neutralized with a volatile base or a nonvolatile base. Preferably it is a volatile base. Examples of the volatile base include ammonia; a primary, secondary or tertiary monoamine having 1 to 4 carbon atoms of alkyl [eg, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, dibutylamine, etc.]; alkanol ( 2 carbon atoms
4) amines [monoethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, diisopropanolamine, etc.]; cyclic amines [morpholine, N-ethylmorpholine, etc.] and a combination of two or more thereof. Among these volatile bases, preferred are alkanolamines from the viewpoints of odor of paint and water resistance of coating film, and particularly preferred are diethanolamine and N-methyldiethanolamine. In particular, when water is used as a diluent for the paint (for example, in an amount exceeding 15% by weight based on the total weight of (A) and (B)), at least a part of the carboxyl groups of (B) is neutralized with a base. It is desirable to have been. In this case, the degree of neutralization is at least 50 equivalent% of carboxyl groups, especially 80%.
The equivalent% or more is preferable. The neutralization is usually performed after the polymerization, but may be performed before or during the polymerization.

The polyfunctional (meth) acrylate (B) having a number average molecular weight of 85 to 300 per (meth) acryloyl group has 2 to 6 or more (meth) acryloyl groups in the polyfunctional (meth) acrylate (B). Specifically, carbon number 2
~ 12 aliphatic dihydric alcohols (ethylene glycol,
Propylene glycol, 1,2-, 1,3-, 2,3-
Or 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-
Methyl-2,4-pentanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2- Butyl-2-ethyl-1,3-propanediol, 1,9-nonanediol, 1,12-
Dodecanediol, 11,12-dodecanediol, etc.), an alicyclic dihydric alcohol having 6 to 15 carbon atoms [1,4
-Cyclohexylene glycol, 1,4-cyclohexanedimethanol, 2,2-bis (4,4'-hydroxycyclohexyl) propane, 4,4'-dihydroxycyclohexylsulfone, 4,4'-dihydroxycyclohexylmethane, hydrogenated bisphenol A etc.], aromatic dihydric alcohols having 8 to 15 carbon atoms (such as xylylene glycol), and (poly) oxyalkylene ethers of these dihydric alcohols (having 1 to 1 oxyalkylene units)
0), dihydric phenols having 6 to 30 carbon atoms (monocyclic dihydric phenols (hydroquinone, resorcinol, catechol, etc.), bisphenols (bisphenol A, bisphenol S, bisphenol, etc.), etc.) and these dihydric phenols Di (meth) acrylates of diols such as polyoxyalkylene ethers (having 2 to 9 oxyalkylene units); aliphatic trihydric alcohols having 3 to 6 carbon atoms (glycerin, trimethylolethane, trimethylolpropane, 2,6-hexanetriol, etc.) and polyoxyalkylene ethers of these trihydric alcohols (number of oxyalkylene units 1 to 15)
Di- or tri (meth) acrylates such as triols; aliphatic tetrahydric alcohols having 5 to 10 carbon atoms (pentaerythritol, diglycerin, methylglycoside, sorbitan, etc.) and (poly) oxyalkylenes of these tetrahydric alcohols Di-, tri- or tetra (meth) acrylates of tetraols such as ethers (number 1 to 20 of oxyalkylene units);
12 or more aliphatic polyhydric alcohols (eg, dipentaerythritol, sorbitol, sucrose, polyglycerin (degree of polymerization: 3 to 10)) and (poly) oxyalkylene ethers (number of oxyalkylene units) of these polyhydric alcohols Poly (2-12 functional) (meth) acrylates of polyols, such as 1-20 or more); and mixtures of two or more of these.
Of these, preferred are aliphatic dihydric alcohols and / or di (meth) oxy (alkyl) ethers (having 1 to 10 oxyalkylene units).
Acrylates, aliphatic trihydric alcohols and / or di- or tri (meth) acrylates of these (poly) oxyalkylene ethers (number of oxyalkylene units 1 to 15, preferably 1 to 10), aliphatic tetrahydric alcohols and / or Or di (tri) or tetra (meth) acrylates of these (poly) oxyalkylene ethers (number of oxyalkylene units of 1 to 20, preferably 1 to 10) and mixtures of two or more of these, and more preferred are , 2-butyl-2-ethyl-1,3-propanediol and / or a di (meth) acrylate of this (poly) oxyalkylene ether (1 to 10 oxyalkylene units), trimethylolpropane and / or Poly) oxyalkylene ether (oxyalkylene unit) Tri (meth) acrylate having 1 to 10), pentaerythritol, and / or a (poly) tri- or tetra (meth) acrylate and their combination oxyalkylene ether (C1-10 oxyalkylene units). The number average molecular weight per (meth) acryloyl group of (B) is usually 85 to 30.
0, preferably 90 to 250, particularly preferably 100 to 250
200. If the molecular weight per (meth) acryloyl group is less than 85, the flexibility of the obtained coating film is reduced, so that the processability such as deep drawing is reduced. If it exceeds 300, the hardness of the obtained coating film is reduced.

The method for producing (B) is not particularly limited, and examples thereof include the following method. Dehydration esterification reaction (reaction temperature 90-150 ° C, normal pressure-250 hPa) at an equivalent ratio of 1 equivalent or more of (meth) acrylic acid to 1 equivalent of hydroxyl group of polyhydric alcohols (preferably 1.03 to 5).
After that, if necessary, unreacted (meth) acrylic acid is removed by washing with alkaline water or the like; alkyl (meth) acrylic acid (1 to 4 carbon atoms) per equivalent of hydroxyl group of the above-mentioned polyhydric alcohols. After the ester exchange reaction (reaction temperature: 90 to 150 ° C., normal pressure to 250 hPa) at an equivalent ratio of 1 equivalent or more (preferably 1.05 to 5), the by-produced alcohol and unreacted ( A method of removing alkyl (meth) acrylate by distillation or the like.

In the above-mentioned esterification reaction or transesterification reaction, the above-mentioned catalyst, dehydration co-solvent, radical polymerization inhibitor and the like can be used in order to smoothly carry out the reaction.

The weight ratio of (A) :( B) in the composition of the present invention is preferably (5-80) :( 95-20),
More preferably, it is (10-65): (90-35). When the ratio of (A) is 5 or more, the flexibility of the obtained coating film is improved, so that workability such as deep drawing is improved. When the ratio is 80 or less, the viscosity of the coating material is reduced and workability is improved.
When (A1) and (A2) are used together as (A),
The mass ratio of (A1) :( A2) is preferably (1 to 9).
9): (99-1), more preferably (20-8)
0): (80 to 20).

The organopolysiloxane (C) having a radically polymerizable unsaturated group can react with the organopolysiloxane (c1) having at least one active hydrogen-containing group or epoxy group and the active hydrogen-containing group or epoxy group. Reaction with compound (e3) having a functional group and a radical polymerizable unsaturated group, or organopolysiloxane (c2) having a functional group capable of reacting with an active hydrogen-containing group
And a compound (e4) having an active hydrogen-containing group and a radical polymerizable unsaturated group.

As the (c1), the following general formulas (1) to (1)
The organopolysiloxane derivative represented by (4) is exemplified.

[0040]

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[0041]

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[0042]

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[0043]

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In the formula, R is the same or different and has 1 to 1 carbon atoms.
3, an alkyl group or a phenyl group, and R 'is a hydroxyl group, a carboxyl group, an amino group, an epoxy group, a mercapto group, and a hydroxy (poly) alkoxy group (oxyalkylene group having 2 to 4 carbon atoms, polymerization degree of 1 to 20 or more) ) Or a hydrocarbon group having 1 to 25 carbon atoms having these reactive groups. x is usually 3 to 10
0, preferably an integer of 5 to 70, y is usually an integer of 1 to 10, preferably 1 to 5, and particularly preferably 1. When x is less than 3, lubricity is hardly exhibited, and when x exceeds 100, compatibility with other resins is reduced.

In the general formulas (1) to (4), examples of R include a methyl group, an ethyl group, an n- or i-propyl group and a phenyl group, and preferred are a methyl group and a phenyl group. R ′ is a hydroxyalkyl (2 to 6 carbon atoms) group (for example, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, etc.); a carboxyalkyl (1 to 6 carbon atoms) group (for example, carboxyethyl group, carboxypropyl group, Carboxybutyl group and the like); aminoalkyl (C1-6) group (for example, aminoethyl group, aminopropyl group, aminobutyl group and the like);
Epoxyalkyl (C1-6) group (for example, 1,2-
Epoxybutyl group, 1,2-epoxypentyl group, 1,
2-epoxyhexyl group, etc.); mercaptoalkyl (C2-6) group (for example, mercaptoethyl group, mercaptopropyl group, mercaptobutyl group, etc.); hydroxymono or poly (polymerization degree 2-20 or more) alkoxy ( C2-C4 alkyl (C1-C6) group [hydroxyethoxyethyl group, hydroxypolyethoxyethyl group, hydroxypolyethoxypropyl group, hydroxypolypropoxypropyl group, hydroxypolyethoxypolypropoxy (block or random) propyl And the like]. Among these, a hydroxyalkyl group, particularly preferably a hydroxypropyl group, is preferred from the viewpoint of reactivity.

Among the above (c1), preferred are compounds represented by the general formula (3) and particularly compounds represented by the formula (1) from the viewpoint of reactivity.

As the compounds (e3) and (e4) having a radical polymerizable unsaturated group capable of reacting with (c1), the same compounds as those described in (e1) can be used. The method for producing (C) is not particularly limited, but (c1): (e)
The equivalent ratio of 3) or (e4) is preferably 1: 1.03
~ 15 equivalents. As a manufacturing method, for example, the following method can be exemplified. The active hydrogen-containing group is a hydroxyl group (c
In the case of 1), the esterification reaction or transesterification reaction is carried out in the same manner as described above with an equivalent ratio of 1 to 10 equivalents (preferably 1.03 to 8 equivalents) of (meth) acrylic acid to 1 equivalent of the hydroxyl group of (c1). Obtained by

The number of unsaturated groups in (C) is usually from 1 to
10, preferably 1 to 3, more preferably 1 or 2
It is. The number average molecular weight of (C) is usually 500 to 50,0.
00, preferably 500 to 10,000. Also,
The molecular weight per unsaturated group is usually from 250 to 20,000.
0, preferably 300-15,000.

% By mass of (C) in the composition of the present invention
(In the following,% is based on mass unless otherwise specified) is preferably 0.1 to 20%, more preferably 0.3 to 10%, particularly preferably 0.5 to 5%.
If (C) is less than 0.1, the lubricating properties of the resulting coating film are reduced, so that the scratch resistance is reduced. If it exceeds 20, the gloss of the obtained coating film is reduced.

The composition of the present invention has sufficient thermosetting properties as it is, but may contain a crosslinking agent (D) if necessary. Examples of the (D) include an amino resin (D1), a polyepoxy compound (D2) and a combination thereof.

As (D1), alkyl (C 1 -C 1)
8) etherified melamine resin, alkyl (1 to 1 carbon atoms)
8) an etherified benzoguanamine resin, an alkyl (C1-8) etherified urea resin, a spiroguanamine resin, an alkyl (C1-8) etherified resin of diguanamine having two triazine rings bonded to a phenylene nucleus, and / or Alternatively, a mixture of two or more of these may be used. Of these, alkyl etherified melamine resins and alkyl etherified benzoguanamine resins are preferred, and alkyl etherified benzoguanamine resins are particularly preferred.

The degree of polymerization of (D1) is usually from 1.1 to 5, preferably from 1.3 to 3, particularly preferably from 1.4 to 2. If the degree of polymerization is less than 1.1, the volatile components during heat curing will increase, and if it exceeds 5, the viscosity will increase and the workability will tend to decrease.

Examples of (D2) include those having 2 to 10 or more epoxy groups in one molecule, for example, the following. (A) Polyhydric phenols (monocyclic dihydric phenols (resorcinol, pyrocatechol, hydroquinone, etc.), bisphenols (bisphenol A, halogenated bisphenol A, bisphenol B, bisphenol S, bisphenol AD, bisphenol F, 4,4 '-Dihydroxybiphenyl, 4,4'-dihydroxy-2,
2 ′, 4,4′-tetramethylbiphenyl, etc.), polynuclear phenols (1,5-hydroxynaphthalene etc.),
(B) polyhydric alcohols such as polyglycidyl ethers of 10-valent condensed polynuclear phenols (phenol novolak, cresol novolak, phenol-dicyclopentadiene copolymer, etc.) ) Oxyalkylene ether (number of oxyalkylene units 1 to 20 or more)
A polyglycidyl ether of [for example, those described in (a12) above], a polyglycidyl ester of (c) a polycarboxylic acid [for example, those described in (a11) above],
(D) Alicyclic polyepoxides (such as vinylcyclohexene diepoxide), and mixtures of two or more of these. Of these, preferred is bisphenol A
Is a diglycidyl ether obtained by adding epichlorohydrin to glycidyl ether.

The epoxy equivalent of (D2) is usually 180
-5,000 eq / g, preferably 220-3,000
eq / g, more preferably 400 to 1,500 eq / g
g. When the epoxy equivalent is 180 eq / g or more, the flexibility of the obtained coating film is not reduced, and the workability such as deep drawing is improved. When the epoxy equivalent is 5,000 eq / g or less, the viscosity of the coating material is low. , The workability tends to be improved.

When (D) is used, the compounding amounts are (A),
The total mass of (B) and (C) is usually 1 to 10
0%, preferably 2 to 50%, more preferably 3 to 3
0%. If it is 100% or less, the flexibility of the obtained coating film is improved, so that workability such as deep drawing is improved. This (D) may be previously mixed with a mixture consisting of (A), (B) and (C), or may be mixed at the time of use.

The coating resin composition of the present invention may contain, if necessary, a known acrylic resin (having no radically polymerizable unsaturated group) other than the present invention (for example, the above-mentioned (a2) and the like), and a polyester resin. [For example, the aforementioned (a1) and the like]
Can be blended. Further, phenolic resins [condensates of phenols (phenol, cresol, etc.) and formalin, etc., having 3 to 20 nuclei and the like], polyurethane resins [for example, polyisocyanates (the above-mentioned polyisocyanates having 2 to 18 carbon atoms, A modified product thereof) and an active hydrogen-containing compound [the above-mentioned polyhydric alcohol, its polyoxyalkylene ether, and the above-mentioned (a) having a hydroxyl group at its terminal.
1) etc.] can also be blended.
The amount of these components is preferably 30% or less, more preferably 20% or less, and particularly preferably 10% or less, based on the total mass of (A), (B) and (C).

The coating resin composition of the present invention may contain, if necessary, known additives (such as curing catalysts, pigments, leveling agents, defoamers, antioxidants, and ultraviolet absorbers) which are usually used in coatings. Can be appropriately blended. The amount of the additive is preferably 20% or less, more preferably 10% or less, particularly preferably 5% or less, based on the total mass of (A), (B) and (C).

The coating resin composition of the present invention may optionally contain a diluent (viscosity is usually from 0.2 to 100 mPa · s / 25).
And the boiling point is usually 40 ° C to 200 ° C). Water as the diluent; alcohols [methanol, ethanol, n-propanol, isopropanol, n-, sec- or t-butanol, ethyl cellosolve, butyl cellosolve, ethyl carbitol, propylene glycol monoethyl ether, hexylene glycol, etc.] And their (poly) oxyalkylenes (degree of polymerization 1 to 4) ethers and the like｝; ketones [acetone, methyl ethyl ketone, methyl isobutyl ketone and the like]; esters [ethyl acetate, butyl acetate, cellosolve acetate and the like]; Alicyclic hydrocarbons [n-hexane, n-heptane, cyclohexane, etc.];
Aromatic hydrocarbons [toluene, xylene, trimethylbenzene and the like] and a mixture of two or more thereof are exemplified. Of these, water and alcohol are preferred, and particularly preferred are water, butyl cellosolve, hexylene glycol and (poly) oxyalkylene ethers of hexylene glycol. The compounding amount of the diluent is preferably 30% or less, more preferably 20% or less, particularly preferably 10% or less, based on the total mass of (A), (B) and (C).

The total amount of (A) + (B) in the non-volatile content of the coating composition comprising the resin composition of the present invention is preferably 50-9.
9.8%, more preferably 70 to 99.5%.
The total amount of (A) + (B) + (C) in the nonvolatile components is preferably 50 to 100%, more preferably 70 to 100%.
It is. (A) + (B) + (C) + (D) in non-volatile content
Is preferably 50 to 100%, more preferably 80 to 100%.

The viscosity (20 ° C.) of the paint comprising the resin composition of the present invention is usually 50 to 5,000 mPa · s, preferably 100 to 3,000 mPa · s.

Examples of the method of applying the coating composition comprising the resin composition of the present invention to a coating substrate include a spray coating method, a knife coating method, a roll coating method, a flow coating method, and the like. It is. The coating amount is appropriately selected according to the purpose, but the dry film thickness is usually 3 to 30 μm.
m, preferably 5 to 30 μm. The coating applied to the metal is subjected to a heat treatment to form a cured coating. The heat treatment temperature is preferably 150 ° C to 300 ° C.
° C, more preferably 190-250 ° C. The heat treatment time is usually 10 seconds to 20 minutes, preferably 1 minute to 10 minutes.

Metals are suitable as the coating substrate to which the coating comprising the resin composition of the present invention is applied, for example, aluminum, steel, tinplate, various chemical treatments (for example, chromium treatment), aluminum, various chemical treatment steels, Steel laminated with polyester or the like, tin-plated steel, galvanized steel, copper, brass and the like can be mentioned. Among them, in the case of the production of metal cans, a paint composed of the resin composition of the present invention is applied to a flat plate for a three-piece can or a cylindrical molded product for a two-piece can in advance, and after drying and curing, deep drawing (deep drawing) Squeezing molding; a molding method in which the neck portion is squeezed to form the mouth of the can in order to make the can into a narrow can. In this case, the material to be coated is chemical conversion treated aluminum, chemical conversion treated steel, steel laminated with a resin (such as polyester), and the like.
Such metal cans are useful as containers for foods such as soft drinks, fish meat, fruits, and edible oils.

[0063]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.
In the following, parts are by mass unless otherwise specified.

Production Example 1 To a four-necked flask equipped with a thermometer, a stirrer, a water separation tube and a gas injection tube, 10 parts of toluene, 5 parts of methyl isobutyl ketone (MIBK), and 2-butyl-2-ethyl-
33 parts of 1,3-propanediol, 10 parts of 1,6-hexanediol, 4 parts of pentaerythritol, 18 parts of sebacic acid, and 34 parts of isophthalic acid were charged, and stirred at a temperature of 180 ° C. while introducing nitrogen gas. After dehydration esterification, toluene and MIBK were distilled off under reduced pressure, and a liquid polyester resin (al-) having an acid value of 1 mgKOH / g, a hydroxyl value of 60 mgKOH / g, and a number average molecular weight of 3,500 was used.
1) was obtained.

Production Example 2 Using the same apparatus as in Production Example 1, 100 parts of toluene, Production Example 1
90 parts of (a1-1) obtained in the above, 10 parts of acrylic acid, 1 part of paratoluenesulfonic acid, and 0.2 part of hydroquinone were charged and subjected to dehydration esterification at 105 ° C. while introducing an air-nitrogen mixed gas. An aqueous solution of sodium hydroxide was added and neutralized at 40 ° C. or lower, and after removing excess acrylic acid, paratoluenesulfonic acid, and hydroquinone together with the aqueous phase,
The toluene was distilled off under reduced pressure, and a polyester resin having an acryloyl group having an acid value of 2 mgKOH / g, a number average molecular weight of 3,600 (number average molecular weight per one acryloyl group of 1,000), and a viscosity of 500 mPa · s / 25 ° C. A1-
1) was obtained.

Production Example 3 In a four-necked flask equipped with a thermometer, a stirrer, a water separation tube and an air blowing tube, 100 parts of toluene, pentaerythritol polyoxyethylene ether having a number average molecular weight of 660 (number of oxyethylene units of 7 ) 55 parts, 1 part of paratoluenesulfonic acid and 0.2 part of hydroquinone were charged, and 45 parts of acrylic acid were charged while introducing air while stirring, and dehydration esterification was performed at a temperature of 120 ° C for 8 hours. The temperature was cooled to 60 ° C., excess acrylic acid was neutralized with an aqueous sodium hydroxide solution, and then removed together with the aqueous phase. Further, toluene was distilled off under reduced pressure, and the number average molecular weight was 650.
(Number average molecular weight 170 per acryloyl group),
A polyfunctional acrylate (B-1) having a viscosity of 200 mPa · s / 20 ° C. was obtained.

Production Example 4 In Production Example 3, 100 parts of toluene and "KF-600
1 "[Same as Production Example 3 except that 70 parts of [dimethylpolysiloxane modified at both ends hydroxyalkyl group, hydroxyl value 60 mg KOH / g, manufactured by Shin-Etsu Silicone Co., Ltd.], 1 part of paratoluenesulfonic acid and 30 parts of methacrylic acid were used. Thus, an organopolysiloxane (C-1) having a viscosity of 30 mPa · s / 25 ° C. and having a methacryl group was obtained.

Examples 1-3 and Comparative Examples 1-2 (a1-1), (A1-1), (B-1), (C-
1) KF-600 manufactured by Shin-Etsu Silicone as an organopolysiloxane having no radically polymerizable unsaturated group
1. Cymel 3 manufactured by Mitsui Cytec as amino resin
03 (CY303), Epicoat 1001 (EP1001) manufactured by Yuka Shell Epoxy as an epoxy resin, and hexylene glycol (HG) as a diluent.
And thermosetting paints were obtained. Table 2 shows the evaluation results of these paints. These coatings were dried on an aluminum plate with a bar coater to a thickness of 5 μm.
Various evaluations were performed on the coating film after application for 180 seconds in a circulating air dryer at 230 ° C. for 180 seconds. Table 3 shows the evaluation results.

[0069]

[Table 1]

[0070]

[Table 2]

[Evaluation Method] Paint appearance: The condition of the paint was visually evaluated according to the following criteria. ；: No abnormalities in paint, △: Separated solution, ×: Solidified over time Paint viscosity: Viscosity at 20 ° C. (m
Pa · s) was measured. Misting property: 10 g of paint is applied to an incometer (manufactured by Yasuda Seiki Co., Ltd.), and 2,000 at roll temperature of 40 ° C.
The ratio of the amount scattered around to the applied paint after the roll was rotated for 10 seconds under the condition of rpm / min.

[0072]

[Table 3]

[Evaluation method] Appearance of coating film: The surface condition of the coating film was visually evaluated according to the following criteria. ；: No abnormality of coating film, Δ: Whitening of coating film or disorder of coating film Pencil hardness: Measured based on JIS K 5400.6.14. Hardness in hot water: After immersing the coated plate in hot water of 80 ° C for 30 minutes,
The pencil hardness was measured in hot water. Impact resistance: The highest height without delamination by increasing the weight drop height at 5 cm intervals in a DuPont impact test (500 g, 1/2 inch). Dynamic friction coefficient: 1Kg using Haydon Tribogear
It was measured at a load of 3 points with a steel ball supporting method and a pulling speed of 1.5 m / min. Retort resistance: After treating the coated plate at 130 ° C. for 30 minutes,
The state of the coating film was visually evaluated according to the following criteria. ；: No abnormality of coating film, Δ: Whitening of coating film or disorder of coating film Adhesion: After retort treatment, cross-cut peeling was performed and evaluated according to the following criteria. ○: no peeling, △: partial peeling, ×: full peeling

[0074]

The resin composition for thermosetting paints of the present invention comprises:
It has the following effects compared to conventional paints and the like. (1) A coating film having excellent scratch resistance and the like is provided in order to maintain high slip properties even after hot water treatment such as retort treatment. (2) Even if the conventional coating method and heat curing method are used, the workability is excellent and the organic solvent is not dissipated, so that the environment for the installation place of the coating equipment and the surroundings can be remarkably improved. (3) The paint can be made non-solvable or highly solid, and the efficiency of storing and transporting the paint can be greatly improved, and it is excellent in terms of environmental and health safety. Because of the above-mentioned effects, the coating composed of the resin composition of the present invention is extremely useful as a metal coating, particularly as an outer coating for metal cans (aluminum cans, steel cans, resin laminate cans, etc.).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 183/07 C09D 183/07 // C08F 299/08 C08F 299/08

Claims (7)

[Claims] 1. A polyester resin having at least one radically polymerizable unsaturated group at a molecular terminal and having a number average molecular weight of 500 to 20,000 per unsaturated group, and / or a radically polymerizable unsaturated resin. An acrylic resin (A) having at least one group in a molecular side chain and having a number average molecular weight of 1,000 to 20,000 per unsaturated group;
Number average molecular weight per one (meth) acryloyl group is 8
A resin composition for a thermosetting coating, comprising, as essential components, 5 to 300 polyfunctional (meth) acrylates (B) and an organopolysiloxane (C) having a radically polymerizable unsaturated group. 2. The resin composition for a thermosetting paint according to claim 1, wherein (A) is a polyester resin. 3. The resin composition for a thermosetting paint according to claim 1, wherein the mass% of (C) in the resin composition for a thermosetting paint is 0.1 to 20% by mass. 4. The composition according to claim 1, further comprising a crosslinking agent (D) comprising an amino resin and / or a polyepoxy compound. 5. The composition according to claim 1, and one or more additives selected from the group consisting of a curing catalyst, a pigment, a leveling agent, an antifoaming agent, an antioxidant and an ultraviolet absorber, if necessary. Thermosetting paint containing. 6. A metal can having a coating layer obtained by curing the paint according to claim 5. 7. A metal can formed by deep drawing of a metal material having a coating layer obtained by curing the coating material according to claim 5.