JP2015196812A - Thermosetting composition and coating composition for can - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new coating composition from which a coating film excellent in water resistance, retort resistance, solvent resistance, and adhesiveness can be formed without contaminating the inside of a furnace during curing or without generating formaldehyde during curing.SOLUTION: A thermosetting composition is provided, which comprises: an acrylic resin (A) having a hydroxy group and a carboxy group; a copolymer (B1) obtained by copolymerization of a maleic acid anhydride as an essential component and/or a half-esterified compound (B2) of the copolymer (B1), which is obtained by allowing an acid anhydride group in the copolymer (B1) obtained by copolymerization of maleic acid anhydride as an essential component to react with a monofunctional alcohol (b); and a β-hydroxyalkylamide (C) represented by general formula (1).

Description

The present invention relates to a thermosetting composition, more particularly to a coating composition suitable for can coating, and more particularly to a coating composition suitable for coating the outer surface of a can containing beverages and foods.

Conventionally, there are paints in which an acrylic resin or a polyester resin is combined with an amino resin or a compound having an isocyanate group as a curing agent. However, when an amino resin is used as a curing agent, the coating film is weak against acid rain and has the disadvantages of poor retort resistance. In addition, the amino resin has a relatively low molecular weight and has a problem of volatilizing at the time of curing and contaminating the inside of the furnace. Furthermore, amino resins also have a problem that formaldehyde is generated during curing. Moreover, when using the compound which has an isocyanate group as a hardening | curing agent, it is necessary to use a 2 liquid type or to use what blocked the isocyanate group. The former is used after mixing an acrylic resin or the like as a main agent and a curing agent before use, but has a problem that the pot life after mixing is relatively short and has a drawback that it is difficult to use. On the other hand, when using the latter, i.e., blocked isocyanate, the dissociation temperature of the blocking agent is generally high, so a great amount of heat energy is required for curing the coating film, and there are difficulties in terms of energy saving. There was a problem that the agent contaminated the furnace. Furthermore, the compound which has an isocyanate group also has the problem that it is unsuitable for the coating material for coat | covering the can for food-drinks.

Therefore, a paint using a styrene maleic anhydride resin has been proposed as a paint that does not contaminate the inside of the furnace at the time of curing and does not generate formaldehyde at the time of curing (Patent Documents 1 and 2). However, although the above-mentioned problems have been cleared, there is no one compatible with physical properties such as adhesion and solvent resistance.

On the other hand, β-hydroxyalkylamide is a crosslinking agent that reacts with a carboxy group (Patent Document 3). The only by-product during the reaction is water, and there is little effect on the cured product, and there is a merit that there is no effect on the worker or the environment. Further, it can be cured at 150 ° C. Currently available commercially available β-hydroxyalkylamides include Primid XL-552 manufactured by Ems Chemie, and are mainly used as a crosslinking agent for powder coatings (Patent Document 4).

However, commercially available β-hydroxyalkylamides have very poor solubility and are rarely used as liquid paints. It is a compound having a large number of hydroxy groups, and it is considered that the high crystallinity and the high polarity deteriorate the solubility. If the paint has poor solubility and cannot be mixed uniformly, there is a problem that a part of the film physical properties are lowered or the physical properties are not stable.

JP 2003-213915 A JP 2003-306635 A Japanese Patent Laid-Open No. 51-17970 JP 2008-255197 A

The present invention is a novel coating composition that can form a coating film excellent in water resistance, retort resistance, solvent resistance, and adhesion without contaminating the furnace during curing and without generating formaldehyde during curing. The purpose is to provide.

In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, by using a copolymer containing maleic anhydride as an essential component or a half esterified product (B) thereof and β-hydroxyalkylamide, I found out to solve the problem.

That is, the present invention provides an acrylic resin (A) having a hydroxy group and a carboxy group,
The acid anhydride group in the copolymer (B1) obtained by copolymerization with maleic anhydride as an essential component and / or copolymer (B1) obtained by copolymerization with maleic anhydride as an essential component is converted to a monofunctional alcohol ( a half esterified product (B2) of the copolymer (B1) obtained by reacting with b), and
Β-hydroxyalkylamide (C) represented by the general formula (1),
It relates to the thermosetting composition characterized by containing.

［一般式（１）中、Ｘは炭素、水素、酸素、窒素、硫黄、または、ハロゲンのいずれかを含むｎ価の基であり、カルボニル基に直接結合するＸ中の原子が炭素原子である官能基を表し、ｎは２〜６の整数であり、Ｒ₁およびＲ₂は、それぞれ独立に、水素原子、一般式（２）で表される基、一般式（３）で表される基、または炭化水素基を表し、分子中少なくとも１つは、一般式（２）で表される基である。］ General formula (1)

[In General Formula (1), X is an n-valent group containing any of carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen, and the atom in X directly bonded to the carbonyl group is a carbon atom. Represents a functional group, n is an integer of 2 to 6, R ₁ and R ₂ are each independently a hydrogen atom, a group represented by the general formula (2), a group represented by the general formula (3) Or at least one in the molecule is a group represented by the general formula (2). ]

［一般式（２）中、Ｒ₃〜Ｒ₆は、それぞれ独立に、水素原子、炭化水素基、またはヒドロキシ基で置換された炭化水素基を表す。］ General formula (2)

[In General Formula (2), R _{3 to} R ₆ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group. ]

［一般式（３）中、Ｒ₃〜Ｒ₆は、それぞれ独立に、水素原子、炭化水素基、またはヒドロキシ基で置換された炭化水素基を表し、Ｒ₇は、ヒドロキシ基と反応しうる官能基を有する化合物の残基を表す。］ General formula (3)

[In General Formula (3), R _{3 to} R ₆ each independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group, and R ₇ is a functional group capable of reacting with a hydroxy group. It represents the residue of a compound having a group. ]

  Moreover, this invention relates to the said thermosetting composition characterized by containing the organic solvent (D) further.

  Further, the present invention relates to the thermosetting composition, further comprising a quaternary ammonium salt or a quaternary phosphonium salt (E).

The present invention also provides an acrylic resin (A) having a hydroxy group and a carboxy group,
Half esterified product (B2) of the copolymer (B1) obtained by reacting an acid anhydride group in the copolymer (B1) obtained by copolymerizing maleic anhydride as an essential component with a monofunctional alcohol (b) As well as
Β-hydroxyalkylamide (C) represented by the general formula (1),
It contains the said thermosetting composition characterized by containing.

The present invention also provides that the monofunctional alcohol (b) is at least one monofunctional alcohol (b1) selected from the group consisting of methanol, ethanol, 1-propanol, and 2-propanol;
And a monofunctional alcohol (b2) having 8 or more carbon atoms.

  The present invention also relates to the thermosetting composition, wherein the monofunctional alcohol (b2) is a linear alkyl group-containing monofunctional alcohol having 12 or more carbon atoms.

  Moreover, this invention relates to the coating composition for cans characterized by containing the said thermosetting composition.

  Furthermore, the present invention relates to an aqueous can coating composition comprising the can coating composition, a volatile base compound, and water.

A novel thermosetting that can form a coating film excellent in water resistance, retort resistance, solvent resistance, and adhesion without contaminating the inside of the furnace during curing and without generating formaldehyde during curing. A composition could be provided.

<Acrylic resin (A) having a hydroxy group and a carboxy group>
The acrylic resin (A) having a hydroxy group and a carboxy group includes a monomer (a1) having a hydroxy group, a monomer (a2) having a carboxy group, and, if necessary, another monomer (a3). ) Can be obtained by copolymerization according to a conventional method.

[Monomer (a1) having a hydroxy group]
Examples of the monomer (a1) having a hydroxy group include the following. (Hereinafter, “” is used to indicate an alias for the same compound.)

Monomers having a primary hydroxy group; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ethyl-α-hydroxymethyl acrylate, 1,4-cyclohexane Dimethanol mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, cyclohexane di Methanol monovinyl ether,

Monomers having secondary hydroxy groups; 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate,

A monomer having a tertiary hydroxy group; 2-hydroxy-2-methylpropyl (meth) acrylate,

Macromonomer having a hydroxy group; mono (meth) acrylate of polyols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, polyester, polycaprolactone, and polybutadiene.

Those having a primary hydroxy group are preferred from the viewpoint of curability, and 2-hydroxyethyl (meth) acrylate is particularly preferred.

[Monomer (a2) having carboxy group]
As the monomer (a2) having a carboxy group, for example,
Acrylic acid, methacrylic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic anhydride, maleic acid monoster, fumaric acid, fumaric acid monoester, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyl Examples thereof include oxyethylhexahydrophthalic acid and 2- (meth) acryloyloxyethylphthalic acid, and acrylic acid and methacrylic acid are preferable.

[Other monomer (a3)]
As other monomer (a3), for example,
Styrenes: Styrene, α-methyl styrene, vinyl toluene, chloromethyl styrene, 4-hydroxystyrene, vinyl naphthalene, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl- o-vinylbenzylglycidyl ether, α-methyl-m-vinylbenzylglycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2 , 5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-trig Glycidyloxy-methylstyrene, 3,4,5-glycidyloxy-methylstyrene, 2,4,6-glycidyloxy-methylstyrene,

Aliphatic (meth) acrylates; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl ( (Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl ( (Meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate << lauryl (meth) acrylate >>, tridecyl (meth) acrylate, hexadecyl (meth) acrylate, oct Decyl (meth) acrylate "stearyl (meth) acrylate", docosyl (meth) acrylate "behenyl (meth) acrylate",

Cycloaliphatic (meth) acrylates; cyclohexyl (meth) acrylate, 3-cyclohexenylmethyl (meth) acrylate, 2,2,4-trimethylcyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) ) Acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, perfluoro- 1-adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate,

(Meth) acrylates having an oxygen atom; glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4- (glycidyloxy) butyl (meth) acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, 3-ethyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 5-methyl-5,6-epoxyhexyl (meth) acrylate, α-ethylacrylic acid Glycidyl, crotonyl glycidyl ale, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate,
3-methyl-3- (meth) acryloyloxymethyl-1-oxetane, 3-ethyl-3- (meth) acryloyloxymethyl-1-oxetane, 5-ethyl-5- (meth) acryloyloxymethyl-1,3 -Dioxane, tetrahydrofurfuryl (meth) acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, 1,4-dioxaspiro [4,5] dec-2- Yl) methyl (meth) acrylate, 3- (meth) acryloyloxy-1-oxolan-2-one, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate , 2- (2-Ethoxyethoxy) ethyl (meth) acrylate, methoxypolyethylene Glycol (meth) acrylate, ethoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate,

(Meth) acrylates having a nitrogen atom; N- (meth) acryloyloxyethylhexahydrophthalimide, 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, 2,2,6,6- Tetramethyl-4-piperidyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate,

(Meth) acrylamides; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, isobutyl (meth) ) Acrylamide, tert-butyl (meth) acrylamide, tert-octyl (meth) acrylamide, N- (methoxymethyl) (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, N- (3 , 5-dimethyl-4-glycidyl) benzylacrylamide, (meth) acryloylmorpholine,

(Meth) acrylonitriles; (meth) acrylonitrile

Vinyl ether, allyl ethers; ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, allyl glycidyl ether, 2-methoxypropene,

Vinyl esters; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate

Maleimides; maleimide, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (2-hydroxyethyl) maleimide, N- (2-carboxyethyl) maleimide,

N-vinyl compounds; N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, 1-vinylimidazole and the like can be mentioned.

<Manufacture of acrylic resin (A)>
[Polymerization initiator]
In the polymerization, it is preferable to arbitrarily use 0.001 to 15 parts by weight of a polymerization initiator with respect to 100 parts by weight in total of the monomers (a1) to (a3). As the polymerization initiator, known polymerization initiators can be used. Examples of the azo compound preferably using an azo compound and an organic peroxide include 2,2′-azobisisobutyronitrile, '-Azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane 1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2 , 4-dimethyl-4-methoxyvaleronitrile), 2,2′-azobis (methyl isobutyrate), 2,2 ′-[N- (2-propenyl) -2-methylpropionamide], 2,2′- Azobis (N-butyl-2-methylpropionamide), 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis (2-methylpropionamidine), 2, 2 ' Azobis [N- (2-carboxyethyl) -2-methylpropionamidine], 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis (1-imide- 1-pyrrolidino-2-methylpropane), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 4,4′-azobis (4-cyanovaleric acid), 2, 2′-azobis (2-hydroxymethylpropionitrile), and the like. Examples of organic peroxides include benzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, dilauroyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n -Propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, Examples include dipropionyl peroxide and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

[Chain transfer agent]
During the polymerization, a chain transfer agent may be used for the purpose of adjusting the molecular weight. It is preferable to arbitrarily use 0.001 to 15 parts by weight of a chain transfer agent with respect to 100 parts by weight of the total of the monomers (a1) to (a3). The chain transfer agent is not particularly limited as long as it is a compound capable of adjusting the molecular weight, and a known chain transfer agent can be used. For example, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thioapple Mercaptans such as acids, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, butylthioglycolate;
Disulfides such as dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropylxanthogen disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide;
Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, carbon tetrabromide, ethylene bromide;
Secondary alcohols such as isopropanol, glycerin;
Phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, and salts thereof (sodium hydrogen sulfite) Lower oxides and salts thereof, such as potassium bisulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite);
And allyl alcohol, 2-ethylhexyl thioglycolate, α-methylstyrene dimer, terpinolene, α-terpinene, γ-terpinene, dipentene, anisole and the like. These may be used alone or in combination of two or more.

[Polymerization solvent]
In the polymerization, an organic solvent can be used as a polymerization solvent. As an organic solvent, it is preferable to use the solvent used for the thermosetting composition concerning this invention. For example, water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethyl acetate , Butyl acetate, isobutyl acetate , Toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethoxydiethylene glycol, ethyl 3-ethoxypropionate, butanediol diacetate, etc. are used, but are not particularly limited thereto. . These polymerization solvents may be used as a mixture of two or more.

The molecular weight of the acrylic resin (A) is preferably 1,000 to 100,000, more preferably 2,000 to 30,000, and particularly preferably 5,000 to 15,000. When the molecular weight is less than 1,000, solvent resistance and coating film hardness may not be sufficient. On the other hand, when the molecular weight exceeds 100,000, problems may occur in the coating process, such as an increase in the viscosity of the coating composition and inability to obtain flatness during coating.

The hydroxyl value of the acrylic resin (A) is preferably 50 mgKOH / g or more, more preferably 100 to 350 mgKOH / g, and particularly preferably 200 to 300 mgKOH / g. When the hydroxyl value is less than 50, the solvent resistance and coating film hardness may not be sufficient.

The acid value of the acrylic resin (A) having a hydroxy group and a carboxy group is preferably 20 to 300 mgKOH / g, particularly preferably 30 to 100 mgKOH / g in the resin before neutralization.

<Copolymer (B1) formed by copolymerizing maleic anhydride as an essential component>
Since maleic anhydride alone cannot be radically polymerized, a copolymer can be obtained by copolymerizing with other monomers. Examples of the other monomer include those listed in the above (a1) to (a3), and it is preferable to use styrenes and vinyl ethers that are excellent in copolymerizability with maleic anhydride. Of these, styrene is particularly preferred from the viewpoint of film hardness.

The maleic anhydride for constituting the copolymer (B1) is preferably 10 to 50 mol%, more preferably 30 to 50 mol%, of the monomers constituting the copolymer. Maleic anhydride serves as a reaction point for crosslinking with the hydroxy group in the acrylic resin (A) having a hydroxy group and a carboxy group. Therefore, if it is less than 10 mol%, the number of crosslinking points decreases, and the solvent resistance and coating film hardness of the coating film may not be sufficient.

As for the molecular weight of the copolymer (B1), the weight average molecular weight is preferably 1,000 to 10,000. When the molecular weight is less than 1,000, solvent resistance and coating film hardness may not be sufficient. On the other hand, when the molecular weight exceeds 10,000, the viscosity of the coating composition becomes high, and problems may occur in the coating process, such as inability to obtain flatness during coating.

<Half-esterified product (B2) of the copolymer (B1) obtained by reacting the acid anhydride group in the copolymer (B1) obtained by copolymerizing maleic anhydride as an essential component with the monofunctional alcohol (b) )>
The half esterified product (B2) is obtained by reacting a part or all of the acid anhydride group in the copolymer (B1) with the monofunctional alcohol (b) to make a half ester.
As the thermosetting composition of the present application, it is preferable to use a half esterified product (B2).

[Monofunctional alcohol (b)]
Examples of the monofunctional alcohol (b) used for the half esterification include the following.
Saturated alcohols: methanol, ethanol, 1-propanol, 2-propanol (isopropyl alcohol), 1-butanol, 2-butanol << sec-butyl alcohol >>, 2-methyl-1-propanol << isobutyl alcohol >>, 2-methyl- 2-propanol << tert-butyl alcohol >>, 1-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2- Butanol, 2,2-dimethyl-1-propanol << neopentyl alcohol >>, 1-hexanol, 2-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 3,3-dimethyl-2 -Butanol, 2-ethyl-1-butanol, 1-heptanol, 2 Heptanol, 3-heptanol, 2,4-dimethyl-3-pentanol, 1-octanol, 2-octanol, 3-octanol, 2-ethyl-1-hexanol, 6-methyl-1-heptanol, isooctyl alcohol, 1 -Nonanol, 2-nonanol, 2,6-dimethyl-4-heptanol, 3,3,5-trimethyl-1-hexanol, 7-methyl-1-octanol, isononyl alcohol, 1-decanol, 3,7-dimethyl -1-octanol, 3,7-dimethyl-3-octanol, 2-propyl-1-heptanol, isodecyl alcohol, 1-undecanol, 1-dodecanol <lauryl alcohol>, tridecanol, tetradecanol, 7-ethyl-2 -Methyl-4-undecanol, pentadecanol Hexadecanol, heptadecanol, octadecanol "stearyl alcohol", isostearyl alcohol, nonadecanol, eicosanol, 2-octyl-1-dodecanol, Hen'ikosanoru, docosanol "behenyl alcohol"

Unsaturated alcohols; 2-propen-1-ol "allyl alcohol", 2-buten-1-ol "crotyl alcohol", 2-methyl-2-propen-1-ol "methallyl alcohol", 3-methyl 2-buten-1-ol << prenol >>, 5-hexen-1-ol, 7-octen-1-ol, 2,7-octadien-1-ol, 9-decene-1-ol, 3,7- Dimethyl-6-octen-1-ol << β-citronellol >>, 3,7-dimethyl-6-octen-3-ol << dihydrolinalool >>, 3,7-dimethyl-2,6-octadien-1-ol << geraniol , Nerol >>, 3,7-dimethyl-1,6-octadien-3-ol << linalool >>, 10-undecen-1-ol, 9-octadecene-1-ol Oleyl alcohol "3,7,11,15-tetramethyl-1-hexadecene-3-ol" isophytol ", 3-phenyl-2-propen-1-ol" cinnamyl alcohol "

Ether alcohol: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monovinyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoallyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol Mono-tert-butyl ether, ethylene glycol monohexyl ether, ethylene glycol mono (2-ethylhexyl) ether, 2-phenoxyethanol,
Diethylene glycol monomethyl ether, diethylene glycol monovinyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,
Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether,
1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether , Dipropylene glycol monobutyl ether,
Tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether,
1-methoxy-2-butanol, 3-methoxy-1-butanol 3-methoxy-3-methyl-1-butanol,
Furfuryl alcohol, tetrahydrofurfuryl alcohol.

(Monofunctional alcohol (b1) (b2))
The monofunctional alcohol (b) includes at least one monofunctional alcohol (b1) selected from the group consisting of methanol, ethanol, 1-propanol, and 2-propanol,
It preferably contains a monofunctional alcohol (b2) having 8 or more carbon atoms.
The monofunctional alcohol (b1) having a short chain length functions as a crosslinking reaction point at the time of forming a coating film, and the monofunctional alcohol (b2) having a long chain length contributes to the adhesion to the ink of the coating film base. Therefore, a half ester compound obtained by reacting the acid anhydride group in the copolymer (B1) with the monofunctional alcohols (b1) and (b2) is more preferable.

As monofunctional alcohol (b2), adhesiveness with the ink of a coating-film base | substrate can be acquired by using C8 or more monofunctional alcohol. From the viewpoint of adhesion, the above saturated alcohols are preferable, and a linear alkyl group-containing monofunctional alcohol having 12 or more carbon atoms is more preferable. Among these, 1-dodecanol is particularly preferable.

The molar ratio of the monofunctional alcohol (b1) to the monofunctional alcohol (b2) is preferably 2: 8 to 8: 2, and more preferably 3: 7 to 6: 4. If it is out of this range, either adhesiveness or curability may not be sufficiently exhibited.

The weight ratio of the acrylic resin (A) and the copolymer (B1) or half-esterified product (B2) is preferably 2: 8 to 8: 2, and more preferably 6: 4 to 7: 3. If it does not fall within this range, any of the appearance, adhesion and curability of the coating film may be deteriorated.

［一般式（１）中、Ｘは炭素、水素、酸素、窒素、硫黄、または、ハロゲンのいずれかを含むｎ価の基であり、カルボニル基に直接結合するＸ中の原子が炭素原子である官能基を表し、
ｎは２〜６の整数であり、
Ｒ₁およびＲ₂は、それぞれ独立に、水素原子、一般式（２）で表される基、一般式（３）で表される基、または炭化水素基を表し、分子中少なくとも１つは、一般式（２）で表される基である。］ <Β-Hydroxyalkylamide (C)>
Β-hydroxyalkylamide (C) in the present invention is a compound represented by the following general formula (1).
General formula (1)

[In General Formula (1), X is an n-valent group containing any of carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen, and the atom in X directly bonded to the carbonyl group is a carbon atom. Represents a functional group,
n is an integer of 2-6,
R ₁ and R ₂ each independently represent a hydrogen atom, a group represented by the general formula (2), a group represented by the general formula (3), or a hydrocarbon group, and at least one in the molecule is It is group represented by General formula (2). ]

［一般式（２）中、Ｒ₃〜Ｒ₆は、それぞれ独立に、水素原子、炭化水素基、またはヒドロキシ基で置換された炭化水素基を表す。］ General formula (2)

[In General Formula (2), R _{3 to} R ₆ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group. ]

［一般式（３）中、Ｒ₃〜Ｒ₆は、それぞれ独立に、水素原子、炭化水素基、またはヒドロキシ基で置換された炭化水素基を表し、
Ｒ₇は、ヒドロキシ基と反応しうる官能基を有する化合物の残基を表す。］ General formula (3)

[In General Formula (3), R _{3 to} R ₆ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group,
R ₇ represents a residue of a compound having a functional group capable of reacting with a hydroxy group. ]

β-Hydroxyalkylamide (C) is a monofunctional alcohol (b) in which an acid anhydride group in a copolymer (B1) obtained by copolymerizing a carboxy group in acrylic resin (A) and maleic anhydride as essential components is copolymerized. ) And the carboxylic group in the half esterified product (B2) of the copolymer (B1) formed by reacting with the acid anhydride group in the copolymer (B1), the half esterified product ( The ester group in B2) can also be crosslinked, and a coating film having a higher crosslinking density can be formed to improve the solvent resistance.

In general formula (1), the n-valent group in X is a group obtained by removing n hydrogen atoms from a compound, and the atom in X directly bonded to the carbonyl group is a carbon atom.
Examples of the compound include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, heptadecane, hexadecane, octadecane, nonadecane, icosane, heicosane, docosane, isobutane. , Isopentane, neopentane, methylpentane, dimethylpentane, ethylmethylpentane, diethylpentane, methylhexane, tetramethylheptane, ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, undecene, docene, tridecene, tetracene , Pentadecene, heptadecene, hexadecene, octadecene, nonadecene, icosene, henicosene, docosene, methylpentene, Chin, propyne, butyne, pentyne, hexyne, peptin, octyne, nonine, decyne, undecine, dodecin, tridecine, icosin, henicosin, docosin, cyclopropane, cyclobutane, cyclopentane, methylcyclopentane, dimethylcyclopentane, trimethylcyclopentane, Benzene, naphthalene, biphenyl, anthracene, toluene, xylene, ethylbenzene, tert-butylbenzene, diphenylethane, diphenylacetylene, 9,9-diphenylfluorene, ethanol, ethylene glycol, ethylene diacetate, ethylene dipivalate, ethylene dibenzoate, Ethylene bis (methylbenzoate), ethylene bis (methoxybenzoate), propanol, isopropanol, ethyl acetate, Lithritol, ethylene oxide, acetaldehyde, acetone, dipropyl ketone, γ-pentadecanolactone, 1,2-epoxycyclohexane, γ-butyrolactone, ethylamine, ethylmethylamine, propylamine, N-propylacetamide, ethanethiol, ethanedithiol, Tetrafluoroethane, dibromoethane, hexafluoropropane, octofluorobutane, dodecafluorohexane, hexadecafluorooctane, 1,2,3,4,7,7-hexachloronorbornene, anisole, fluorobenzene, tetrafluorobenzene, trifluoro Methylbenzene, chlorobenzene, dichlorobenzene, tetrachlorobenzene, bromobenzene, tetrabromobenzene, nitrobenzene, phenol, aniline, Benzenesulfonic acid, anthraquinone, butanephosphonic acid, triethyltriazine, tripropyltriazine, triethylisocyanurate, tripropylisocyanurate, benzophenone, thiophene, diethylsulfide, diphenylsulfone, 2,2-diphenyl-1,1,1,3 3,3-hexafluoropropane, diphenyl ether, etc. are mentioned.

Furthermore, a part of hydrogen atoms and carbon atoms in X may be substituted with nitrogen, oxygen, sulfur, fluorine, chlorine, bromine and iodine.

From the viewpoint of reactivity, it is more preferable that the carbon atom in X bonded to the carbonyl group in the general formula (1) does not form an aromatic ring. Furthermore, X is preferably an aliphatic or alicyclic hydrocarbon group having 6 or more carbon atoms, and more preferably a linear aliphatic hydrocarbon group having 6 to 12 carbon atoms.

Examples of the hydrocarbon group in the general formulas (1) to (3) include monovalent hydrocarbon groups among the n-valent groups in X described above.

  The monovalent hydrocarbon group is preferably a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, Octyl, decyl, dodecyl, pentadecyl, octadecyl, vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-octenyl Group, 1-decenyl group, 1-octadecenyl group, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-octynyl group, 1-decynyl group, 1-octadecynyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl , Cyclooctyl group, cyclooctadecyl group, 2-indeno group, decahydronaphthyl group, adamantyl group, dicyclopentanyl group, phenyl group, benzyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, p-cumenyl group, mesityl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 5-anthryl group, 1-phenanthryl group, 9-phenanthryl group, Examples include 1-acenaphthyl group, 2-azurenyl group, 1-pyrenyl group, 2-triphenylyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group and the like.

From the viewpoint of solubility, R ₁ is preferably a monovalent hydrocarbon group, and R ₂ is preferably a group represented by the general formula (2).

Examples of the hydrocarbon group substituted with a hydroxy group in the general formulas (2) and (3) include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxyphenyl group, and a hydroxycyclohexyl group. It is done.

<Production of β-hydroxyalkylamide (C)>
The β-hydroxyalkylamide (C) of the present invention comprises a divalent or higher carboxylic acid or derivative thereof (c1) and a primary or secondary amine (c2) having at least one hydroxy group at the β-position (that is, nitrogen It can be prepared by reacting an atom with a hydrogen atom, an amine in which R ₁ and R ₂ are bonded.

[Divalent or higher carboxylic acid or derivative thereof (c1)]
Examples of the divalent or higher carboxylic acid include the following.
Linear saturated aliphatic dicarboxylic acid:
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid , Heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, icosanedioic acid, henicosanedioic acid, docosanedioic acid,

Branched saturated aliphatic dicarboxylic acid:
Methylmalonic acid, dimethylmalonic acid, ethylmalonic acid, dipropylmalonic acid, isopropylmalonic acid, methylsuccinic acid, dimethylsuccinic acid, butylsuccinic acid, octylsuccinic acid, decylsuccinic acid, dodecylsuccinic acid, tetradecylsuccinic acid, hexadecylsuccinic acid Acid, octadecyl succinic acid, methyl glutaric acid, dimethyl glutaric acid, ethyl methyl glutaric acid, diethyl glutaric acid, methyl adipic acid, tetramethyl pimelic acid,

Unsaturated aliphatic dicarboxylic acids: allyl succinic acid, methallyl succinic acid, hexenyl succinic acid, octenyl succinic acid, dodecenyl succinic acid, dococenyl succinic acid, tetradecenyl succinic acid, hexadecenyl succinic acid, octadecenyl succinic acid, decadien-1 , 2-dicarboxylic acid, fumaric acid, maleic acid, acetylenedicarboxylic acid, muconic acid, itaconic acid, citraconic acid, mesaconic acid,

Alicyclic dicarboxylic acids:
Cyclopropanedicarboxylic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, cyclopentylmalonic acid, cyclopentanediacetic acid,

Aliphatic dicarboxylic acid having an aromatic ring (the carbon atom bonded to carboxy does not form an aromatic ring):
Phenylmalonic acid, benzylmalonic acid, thiophenmalonic acid, phenylsuccinic acid, diphenylsuccinic acid,

Aliphatic or alicyclic carboxylic acid containing an oxygen atom in addition to the carboxy group:
Tartaric acid, diacetyltartaric acid, dipivaloyltartaric acid, dibenzoyltartaric acid, ditoluoyltartaric acid, di (p-anisoyl) tartaric acid, malic acid, acetylmalic acid, citric acid, citramalic acid, hydroxymethylglutaric acid, galactaric acid, epoxysuccinic acid, oxalacetic acid, Oxoglutaric acid, oxoazeleic acid, 4,5-dicarboxy-γ-pentadecanolactone, 3,6-epoxy-1,2,3,6-hexahydrophthalic acid, butyrolactone dicarboxylic acid,

Aliphatic or alicyclic dicarboxylic acids containing nitrogen atoms:
Aspartic acid, N-methylaspartic acid, N- (tert-butoxycarbonyl) -aspartic acid, N- (benzyloxycarbonyl) aspartic acid, N-carbamoylaspartic acid, N-[(9H-fluoren-9-ylmethoxy) carbonyl ] Aspartic acid, glycylaspartic acid, 3-hydroxyaspartic acid, glutamic acid, N-acetylglutamic acid, N- (tert-butoxycarbonyl) -glutamic acid, N- (benzyloxycarbonyl) glutamic acid, N-benzoylglutamic acid, N- ( 4-Aminobenzoyl) glutamic acid, N-[(9H-fluoren-9-ylmethoxy) carbonyl] glutamic acid, methylglutamic acid, glycylglutamic acid, guadininoglutaric acid, N-phthalylglutamine , Amino adipic acid, aminopimelic acid, diaminopimelic acid, aminosuberic acid, folic acid, methotrexate,

Aliphatic or alicyclic dicarboxylic acids containing sulfur atoms:
Dimercaptosuccinic acid, thiomalic acid,

Aliphatic or alicyclic dicarboxylic acids containing halogen atoms:
Tetrafluorosuccinic acid, dibromosuccinic acid, hexafluoroglutaric acid, octafluoroadipic acid, dodecafluorosuberic acid, hexadecafluorosebacic acid, chlorendic acid 《Het's acid》,

Aromatic dicarboxylic acids:
Phthalic acid, methylphthalic acid, tert-butylphthalic acid, ethynylphthalic acid, (phenylethynyl) phthalic acid, methoxyphthalic acid, fluorophthalic acid, tetrafluorophthalic acid, trifluoromethylphthalic acid, chlorophthalic acid, dichlorophthalic acid, tetrachloro Phthalic acid, bromophthalic acid, tetrabromophthalic acid, nitrophthalic acid, hydroxyphthalic acid, aminophthalic acid, sulfophthalic acid, isophthalic acid, methylisophthalic acid, tert-butylisophthalic acid, methoxyisophthalic acid, tetrafluoroisophthalic acid, bromoisophthalic acid, Nitroisophthalic acid, Hydroxyisophthalic acid, Aminoisophthalic acid, Aminotriiodoisophthalic acid, Sulfoisophthalic acid, Terephthalic acid, Dimethylterephthalic acid, Tetrafluoroterephthalic acid, Dichloromethane Roterefutaru acid, tetrachlorophthalic terephthalic acid, bromo terephthalic acid, tetrabromophthalic terephthalic acid, nitroterephthalic acid, dihydroxy terephthalic acid, aminoterephthalic acid, sulfoterephthalic acid,
Naphthalenedicarboxylic acid, anthracene dicarboxylic acid, anthraquinone dicarboxylic acid, 1,3-dibenzyl-2-oxo-4,5-imidazolidine dicarboxylic acid,

Aliphatic or alicyclic tricarboxylic acids:
Tricarballylic acid << 1,2,3-propanetricarboxylic acid >>, anicotic acid, butenetricarboxylic acid, cyclohexanetricarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 3-butene-1,2,3-tricarboxylic acid Acid, cyclohexanetricarboxylic acid, pentanetricarboxylic acid, tris (2-carboxyethyl) -1,3,5-triazine, tris (3-carboxypropyl) -1,3,5-triazine, isocyanuric acid tris (2-carboxyethyl) ), Isocyanuric acid tris (3-carboxypropyl),

Aromatic tricarboxylic acid:
Trimellitic acid, hemimellitic acid, benzene-1,3,5-tricarboxylic acid, benzophenone tricarboxylic acid,

Aliphatic or alicyclic tetracarboxylic acid:
Butanetetracarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, thiodisuccinic acid, tetrahydrofurantetracarboxylic acid, bicyclo [2.2.2] oct-7-ene-2,3,5,6 -Tetracarboxylic acid, 5- (1,2-dicarboxyethyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 4- (1,2-dicarboxyethyl) 1,2,3,4 -Tetrahydronaphthalene-1,2-dicarboxylic acid,

Aromatic tetracarboxylic acid:
Pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, oxydiphthalic acid, hexafluoroisopropylidenediphthalic acid, naphthalene tetracarboxylic acid, fluorene-9,9-bisphthalic acid,

Aliphatic or alicyclic pentacarboxylic acid or hexacarboxylic acid:
Cyclohexane hexacarboxylic acid,

Aliphatic or alicyclic pentacarboxylic acid or hexacarboxylic acid:
Benzene pentacarboxylic acid, merit acid

Further, as the divalent or higher carboxylic acid (c1), a polyester, polybutadiene, polyisoprene, acrylic oligomer, or polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene having a carboxylic acid at the terminal and / or side chain. Polyols such as polyols and polyacrylic polyols are modified with acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. The compound obtained by doing is also mentioned.

Examples of carboxylic acid derivatives include acid anhydrides, acid chlorides, acid bromides, methyl esters, ethyl esters, and phenyl esters of the above carboxylic acids.

[Primary or secondary amine (c2) having one or more hydroxy groups at β-position]
Examples of the primary or secondary amine (c2) having one or more hydroxy groups at the β-position include the following.
Primary amine (R ₁ is a hydrogen atom and R ₂ is an amine represented by the general formula (2)):
Ethanolamine, 1-amino-2-propanol <isopropanolamine>, 2-amino-1-propanol, 2-amino-1-butanol, 2-amino-2-phenyl-ethanol, 2-amino-2-methyl-1 -Propanol, isoleucinol << 2-amino-3-methyl-1-pentanol >>, 2-isopropylamino-3-methyl-1-butanol, leucinol << 2-amino-4-methyl-1-pentanol >>, tert- Leucinol << 2-amino-3,3-dimethyl-1-butanol >>, phenylalaninol << 2-amino-3-phenyl-1-propanol >>, 1-amino-2-butanol, 2-amino-1-phenylethanol 2-amino-1-phenyl-1-propanol,

A secondary amine in which R ₁ is a hydrocarbon group and R ₂ is represented by the general formula (2):
N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-tert-butylethanolamine, 3-tert-butylamino-1,2-propanediol, N-cyclohexylethanolamine, N-phenylethanol Amine, N-benzylethanolamine,

A secondary amine represented by the general formula (2) for both R ₁ and R ₂ :
Diethanolamine, diisopropanolamine,

Amines containing a hydroxy-substituted hydrocarbon group in R _{3 to} R ₆ :
2-[(hydroxymethyl) amino] ethanol, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, tris (hydroxymethyl) aminomethane, 3-amino-1 , 2-propanediol, 3- (methylamino) -1,2-propanediol, N-methylglucamine << 6- (methylamino) -1,2,3,4,5-hexanepentaol >>, 3-bis [tris (hydroxymethyl) methylamino] propane, 2-amino-1-phenyl-1,3-propanediol, phenylephrine << 1- (3-hydroxyphenyl) -2- (methylamino) ethanol >>, ethylephrine << 2-ethylamino-1- (3-hydroxyphenyl) ethanol >>

The β-hydroxyalkylamide (C) of the present invention comprises a divalent or higher carboxylic acid or derivative thereof (c1) and a primary or secondary amine (c2) having one or more hydroxy groups at the β-position. Can be manufactured.

There are various methods for amidating a divalent or higher carboxylic acid or derivative thereof (c1) and a primary or secondary amine (c2) having one or more hydroxy groups at the β-position. When the acid or its derivative (c1) is a carboxylic acid, the reaction can be carried out by removing water, when the acid is a carboxylic acid ester, by removing the acid, when the carboxylic acid ester is a carboxylic acid anhydride or halide. In the case of water or alcohol, it is easy to remove out of the reaction system by heating. In the case of acid, triethylamine, tributylamine, dimethylbenzylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. The basic compound can be removed.

A catalyst can be used in the amidation. For example, acid catalysts such as sulfuric acid, hydrochloric acid, methanesulfonic acid, p-toluenesulfonic acid, base catalysts such as sodium hydroxide, sodium carbonate, sodium methoxide, triethylamine, tributylamine, trioctylamine, tetramethylethylenediamine, N, N-dimethylethanolamine, N, N-dimethylbenzylamine, pyridine, 4- (dimethylamino) pyridine, imidazole, amines such as N-methylimidazole, iron (III), zirconium (IV), scandium (III), Examples thereof include salts and complexes containing metal ions such as titanium (IV), tin (IV), and hafnium (IV), and ammonium salts such as diphenylammonium triflate and pentafluorophenylammonium triflate.

In the amidation reaction, a solvent or a catalyst can be used as necessary. The solvent to be used can be used as long as it is other than a solvent that reacts with a reaction substrate such as alcohol, amine, or carboxylic acid. For example, hexane, heptane, octane, cyclohexane, benzene, toluene, ethylbenzene, xylene, ethyl acetate, butyl acetate, isobutyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dichloromethane, chloroform, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, etc. It is done.

In particular, the amidation with carboxylic acid can be performed using a condensing agent. A condensing agent activates a carboxylic acid or an amine, and the esterification reaction can be carried out under mild conditions. At the same time, the by-product water is combined with the condensing agent to form another compound. And a compound having a water removing action. Such condensing agents include, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, p-toluenesulfonyl chloride, 1-ethyl-3- (N, N-dimethylaminopropyl) carbodiimide hydrochloride, carbonyldiimidazole, ethyl chloroformate, chloroformate Acid isobutyl, 2,4,6-trichlorobenzoic acid chloride, 2-methyl-6-nitrobenzoic anhydride, O- (7-azabenzotriazol-1-yl) -N, N, N ′, N′— Examples thereof include tetramethyluronium hexafluorophosphate.

From the viewpoint of solubility in an organic solvent and compatibility with other resins, it is preferable to have at least a group of the general formula (3) in the molecule of β-hydroxyalkylamide (C). That is, in R ₁ and R ₂ of the general formula (1), at least one in the molecule is preferably a group represented by the general formula (3). Specifically, a β-hydroxyalkylamide obtained by amidating a divalent or higher carboxylic acid or derivative thereof (c1) and a primary or secondary amine (c2) having one or more hydroxy groups at the β-position. A part of the hydroxy group can be obtained by reacting with a compound (c3) having one or more functional groups capable of reacting with the hydroxy group.

[Compound (c3) having at least one functional group capable of reacting with a hydroxy group]
Examples of the compound (c3) having one or more functional groups capable of reacting with a hydroxy group include isocyanate compounds, carboxylic acids, carboxylic acid halides, carboxylic acid anhydrides, carboxyl group-containing compounds such as carboxylic acid esters, silanols, alkoxysilanes And silanol compounds such as silanol esters, and epoxy compounds.

(Isocyanate compound)
Examples of the isocyanate include the following.
Monofunctional isocyanate:
Methyl isocyanate, butyl isocyanate, hexyl isocyanate, heptyl isocyanate, lauryl isocyanate, stearyl isocyanate, phenyl isocyanate, cyclopropyl isocyanate, phenethyl isocyanate, tosyl isocyanate, acryloyloxyethyl isocyanate, methacryloyloxyethyl isocyanate, vinyl isocyanate, allyl isocyanate,

Bifunctional isocyanate:
Tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, tolidine isocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, isopropylidenebis (Cyclohexyl isocyanate), 3- (2′-isocyanatocyclohexyl) propyl isocyanate, dianisidine isocyanate, diphenyl ether diisocyanate, dimer isocyanate, tetramethylxylylene diisocyanate,

Trifunctional isocyanate:
Lysine triisocyanate, tris (isocyanatophenyl) methane, tris (isocyanatophenyl) thiophosphate,

Further, biurets, uretdiones, isocyanurates, and adducts of the above polyfunctional isocyanates are also included.

Isocyanate selected from the above-mentioned polyfunctional isocyanate, biuret of polyfunctional isocyanate, uretdione, isocyanurate, adduct, and methanol, ethanol, propanol, butanol, pentanol, phenol, benzyl alcohol, methylamine, ethylamine, dibutylamine, The compound formed by making it react with active hydrogen compounds, such as polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, and polycaprolactone, is also mentioned.

Among the above, considering the solubility, storage stability, ease of production, etc., the above monofunctional isocyanate, or one of the polyfunctional isocyanate or biuret of polyfunctional isocyanate, uretdione, isocyanurate, adduct It is preferable to use a monofunctional isocyanate which is obtained by leaving a group and reacting the remainder with an active hydrogen compound.

(Carboxyl group-containing compound)
Examples of the compound having a carboxy group among the compounds having at least one functional group capable of reacting with a hydroxy group (c3) include the following.
Aliphatic saturated monofunctional carboxylic acid:
Formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid "pentanoic acid", 2-methylbutyric acid, isovaleric acid "3-methylbutyric acid", pivalic acid "2,2-dimethylpropionic acid", caproic acid "hexane" Acid, methylvaleric acid, dimethylbutyric acid, ethylbutyric acid, enanthic acid <heptanoic acid>, caprylic acid <octanoic acid>, 2-ethylhexanoic acid, pelargonic acid <nonanoic acid>, capric acid <decanoic acid>, undecanoic acid, Lauric acid <dodecanoic acid>, tridecanoic acid, myristic acid <tetradecanoic acid>, pentadecanoic acid, palmitic acid <hexadecanoic acid>, margaric acid <heptadecanoic acid>, stearic acid <octadecanoic acid>, isostearic acid <2-heptylundecanoic acid> , Nonadecanoic acid, arachidic acid <icosanoic acid>, heicosanoic acid, behenic acid <docosanoic acid> Tricosanoic acid, lignoceric acid "tetracosanoic acid", pentacosanoic acid, cerotic "hexacosanoic acid", heptacosanoic acid, montan acid "octacosanoic acid", nonacosanoic acid, melissic acid "triacontanoic acid",

Aliphatic unsaturated monofunctional carboxylic acid:
Acrylic acid, methacrylic acid, crotonic acid, undecenoic acid, palmitoleic acid <9-hexadecenoic acid>, petrothelic acid <6-octadecenoic acid>, oleic acid <9-octadecenoic acid>, elaidic acid <9-octadecenoic acid>, vaccenic acid , Linoleic acid << 9,12-octadecadienoic acid >>, linolenic acid << 9,12,15-octadecatrienoic acid >>, gamma-linolenic acid << 6,9,12-octadecatrienoic acid >>, eleostearic acid Aragydonic acid << 5,8,11,14-eicosatetraenoic acid >>, 5,8,11,14,17-eicosapentaenoic acid, erucic acid << 13-docosenoic acid >>, docosahexaenoic acid, 22-tricosenoic acid, 15-tetracosenoic acid, nervonic acid,

Aromatic monofunctional carboxylic acid:
Benzoic acid, toluic acid, dimethylbenzoic acid, trimethylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, isopropylbenzoic acid, butylbenzoic acid, tert-butylbenzoic acid, vinylbenzoic acid, fluorobenzoic acid, chlorobenzoic acid, bromobenzoic acid Acid, iodobenzoic acid, trifluoromethylbenzoic acid, cyanobenzoic acid, hydroxybenzoic acid, hydroxymethylbenzoic acid, aminobenzoic acid, mercaptobenzoic acid, naphthoic acid, methylnaphthoic acid, hydroxynaphthoic acid, anthronic acid << anthracenecarboxylic acid >>, pyrenecarboxylic acid,

Alicyclic monofunctional carboxylic acid:
Cyclopropanecarboxylic acid, dimethylcyclopropanecarboxylic acid, tetramethylcyclopropanecarboxylic acid, mercaptomethylcyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclopentylacetic acid, aminocyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid , Cyclohexylacetic acid, cyclohexylpropionic acid, cyclohexylbutyric acid, methylcyclohexanecarboxylic acid, propylcyclohexanecarboxylic acid, isopropylcyclohexanecarboxylic acid, butylcyclohexanecarboxylic acid, tert-butylcyclohexanecarboxylic acid, hydroxycyclohexanecarboxylic acid, (hydroxymethyl) cyclohexanecarboxylic acid , Cyclohexene carboxylic acid, norbornene carbo Acid, norbornane carboxylic acid, noradamantane carboxylic acid, adamantane carboxylic acid,

Monofunctional carboxylic acid having an oxygen atom in addition to the carboxy group:
Glycolic acid, lactic acid, hydroxypalmitic acid, ricinoleic acid, hydroxystearic acid, alloyed acid << trihydroxyhexadecanoic acid >> jasmonic acid << 3-oxo-2- (2-pentenyl) cyclopentaneacetic acid >>, cucurbic acid << 3-hydroxy -2- (2-pentenyl) cyclopentaneacetic acid >>

And monovalent carboxylic acids such as the above, and compounds listed above for the divalent or higher carboxylic acid (c1).

Among the compounds having at least one functional group capable of reacting with a hydroxy group (c3), a compound having a carboxy group is esterified with an alcohol or an amine with a part of the compound mentioned as a divalent or higher carboxylic acid or derivative thereof. Also included are amidated compounds. For example, alcohol, amine such as methanol, ethanol, propanol, butanol, pentanol, phenol, benzyl alcohol, methylamine, ethylamine, dibutylamine, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polycaprolactone, and the above 2 Examples thereof include monofunctional carboxylic acids in which a compound listed with a carboxylic acid (c1) of a valence or higher is partially esterified to leave one carboxy group in the molecule. In particular, it is preferable to use a cyclic carboxylic acid anhydride of a divalent carboxylic acid because one carboxy group is generated after reacting with a hydroxy group or an amino group in a 1: 1 ratio.

Furthermore, acid anhydrides and acid halides of the compounds having the carboxy group are also included.

Among the above, in consideration of solubility, storage stability, ease of production, etc., some of the monofunctional carboxylic acid, acid halide, acid anhydride, or polyfunctional carboxylic acid or derivative thereof Monofunctional carboxylic acid or derivative thereof in which carboxylic acid is reacted with alcohol or amine to leave one carboxy group, or monofunctional carboxylic acid produced by reacting monofunctional alcohol or amine with a cyclic acid anhydride of divalent carboxylic acid It is preferable to use.

(Silanol compound)
Silanol is a compound having a Si—OH structure in the molecule, and OH in the silanol reacts with a hydroxy group. Alkoxysilane, silanol sulfuric acid, sulfonic acid ester, and halogenated silane (hereinafter collectively referred to as “silanol derivatives”) generate silanol by hydrolysis and can be used in the same manner as silanol. A silanol derivative is commercially available from the viewpoint of storage stability.

The following are mentioned as a silanol derivative.
Monofunctional silanol derivative:
Trimethylsilyl triflate, triethylsilyl triflate, tert-butyldimethylsilyl triflate, diethylisopropylsilyl triflate, tripropylsilyl triflate, bis (trimethylsilyl) sulfate, chlorotrimethylsilane, chlorotriethylsilane, trimethylmethoxysilane,

Multifunctional silanol derivative:
Dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycosoxypropyltriethoxysilane, p-styryl Triethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxy Lan, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropyltrimethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminomethyl) -3-amino Propyltrimethoxysilane, N- (2-aminomethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3 -Dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3- Chloropropyltrimethoxysila , 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl methyl dimethoxy silane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane,

Among these, considering the solubility, storage stability, ease of production, etc., it is preferable to use the monofunctional silanol derivative.

(Epoxy compound)
Examples of the compound having an epoxy group among the compounds (c3) having one or more functional groups capable of reacting with a hydroxy group include the following.

Monofunctional epoxy:
Allyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, phenyl glycidyl ether, phenylphenol glycidyl ether, sec-butylphenol monoglycidyl ether, polyethylene glycol monophenyl ether monoglycidyl ether, N-glycidyl phthalimide, styrene oxide, 1,2 -Epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexane-1-carboxylic acid ester, 3,4-epoxycyclohexane-1-methanol, 3,4-epoxycyclohexane-1-carbaldehyde, 4,5-epoxy- 1,2-dicarboxylic acid ester,

Multifunctional epoxy:
Sorbitol polyglycidyl ether, polyglycerin polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerin polyglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 -Hexanediol polyglycidyl ether, bis (hydroxycyclopropyl) propane diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tert-butylphenol glycidyl ether, polybutadiene diglycidyl ether, diglycidyl phthalate, diglycidyl cyclohexanedicarboxylate, Terephthal Glycidyl acid, hydroquinone diglycidyl ether, dibromophenol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, condensate of bisphenol A and epichlorohydrin, condensate of bisphenol F and epichlorohydrin, phenol novolac polyglycidyl ether, Cresol novolac polyglycidyl ether, condensate of brominated bisphenol A and epichlorohydrin, N, N, N ′, N′-tetraglycidylbis (aminophenyl) methane, diglycidyl dimer, hydrogenated bisphenol A and epichlorohydride Phosphorus condensate, di-tert-butylhydroquinone diglycidyl ether, tetramethylbisphenol F diglycidyl ether, bis (N, N-diglycidylaminomethyl) benzene, (N, N-diglycidylaminomethyl) cyclohexane, and the like.

Among the above, in consideration of solubility, storage stability, ease of production, etc., it is preferable to use the above monofunctional epoxy.

When the compound (c3) is an isocyanate, the reaction proceeds by adding a non-catalyst or an appropriate catalyst and heating. Suitable catalysts include, for example, amines such as triethylamine, tributylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, and salts thereof, tetrabutyl titanate, dibutyltin dilaurate, tin octylate. And metal salts and complexes.

When the compound (c3) is a carboxylic acid, the dehydration condensation reaction proceeds by heating to 100 ° C. or higher, preferably 140 ° C. or higher without using a catalyst. Alternatively, the reaction can be allowed to proceed at a lower temperature by adding an appropriate catalyst. The catalysts, condensing agents, etc. described for the amidation reaction can be used for this reaction.

When the compound (c3) is a carboxylic acid anhydride or a carboxylic acid halide, it is preferable to add a base catalyst or an amine catalyst and react at 0 to 100 ° C. At this time, it is preferable to use 1 mol or more of the base catalyst or amine catalyst with respect to 1 mol of carboxylic acid anhydride or carboxylic acid halide.

When the compound (c3) is silanol, it is preferable to add a base catalyst or an amine catalyst and react at 0 to 100 ° C. At this time, it is preferable to use 1 mol or more of the base catalyst or amine catalyst with respect to 1 mol of carboxylic acid anhydride or carboxylic acid halide.

When compound (c3) is an epoxy group, a strong base catalyst such as potassium hydroxide, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium hydride, or a metal such as tetrafluoroboric acid or tin (IV) chloride It is preferable to make it react at 0-200 degreeC using a catalyst.

In the thermosetting composition of the present invention, β-hydroxyalkylamide (C) is based on a total of 100 parts of acrylic resin (A) and copolymer (B1) and / or its half-esterified product (B2). 1 to 30 parts, and more preferably 5 to 20 parts. When it is less than 1 part, curability is insufficient and solvent resistance may be insufficient. On the other hand, if it exceeds 30 parts, the excess β-hydroxyalkylamide (C) is not incorporated into the cross-linking, so that the film strength may be insufficient.

<Organic solvent (D)>
The organic solvent (D) contained in the thermosetting composition of the present invention is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl- 2-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether , Ethyl acetate, butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethoxydiethylene glycol, ethyl 3-ethoxypropionate, butanediol diacetate, etc. It is not limited to these.

<Additives>
[Halide of quaternary ammonium salt or quaternary phosphonium salt]
In the composition of the present invention, a catalyst may be added to the crosslinking reaction between the acrylic resin (A) and the copolymer (B1) and / or a half-esterified product (B2) thereof. Examples of the catalyst include quaternary ammonium salts and quaternary phosphonium salts. Specifically, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, tetraoctylammonium salt, butyltrimethylammonium salt, dodecyltrimethylammonium salt, tetradecyltrimethylammonium salt, hexadecyltrimethylammonium salt , Octadecyl trimethyl ammonium salt, where sil trimethyl ammonium salt, phenyl trimethyl ammonium salt, benzyl trimethyl ammonium salt, didecyl dimethyl ammonium salt, dicocoyl dimethyl ammonium salt, distearyl dimethyl ammonium salt, dioleyl dimethyl ammonium salt, benzyl dimethyl dodecyl ammonium Salt, tributylmethylammonium salt, trioctylmethylammonium salt Monium salt, hexamethyldimethylethylammonium salt, butyltriethylammonium salt, benzyltriethylammonium salt, benzyltributylammonium salt, tetraphenylphosphonium salt, benzyltriphenylphosphonium salt, methyltriphenylphosphonium salt, ethyltriphenylphosphonium salt, propyltri Examples thereof include phenylphosphonium salt and butyltriphenylphosphonium salt.

Examples of the counter anion of the ammonium salt or phosphonium salt include fluoride ion, chloride ion, bromide ion, iodide ion, tribromide ion, triiodide ion, cyanide ion, hydroxide ion, and hydrogen sulfate ion. , Methanesulfonate ion, trifluoromethanesulfonate ion, bis (trifluoromethanesulfonyl) imide ion, tris (trifluoromethanesulfonyl) methide ion, p-toluenesulfonate ion, tetrafluoroborate ion, tetraphenylborate ion, tetrakis (penta Fluorophenyl) borate ion, hexafluorophosphate ion, hexafluoroantimonate ion, acetate ion, perchlorate ion, thiocyanate ion, and the like.

The added amount of the quaternary ammonium salt or quaternary phosphonium salt halide is preferably 0.1 to 5 parts, more preferably 0.3 to 2 parts with respect to 100 parts of the resin solid content. When the amount is less than 0.1 part, the performance as a catalyst may not be exhibited and the curability may deteriorate. Moreover, when more than 5 parts, corrosivity becomes strong and there exists a possibility of making a metal base material rust.

In addition to the above, additives such as leveling agents, antioxidants, light stabilizers, adhesion promoters, waxes and fillers can be added to the composition of the present invention.

<Coating composition for cans>
The thermosetting composition of the present invention can be preferably used as a can coating material. The coating composition for cans can be applied to various substrates by known means such as roll coating, spraying, and brush coating. For example, the can coating composition of the present invention is applied to an electroplated tin steel plate, an aluminum steel plate, a stainless steel plate, or a laminated steel plate obtained by laminating a polyester film such as polyethylene terephthalate or polybutylene terephthalate on these metal plates, and heated. It can be cured to obtain an object to be coated. In particular, the can coating composition of the present invention is optimally applied to the outer surface side of a metal plate, a bottomed cylindrical metal or a polyester film-coated drawn can and forms a coating.

The above-described coating composition obtained by applying the coating composition for cans of the present invention to a metal plate, a bottomed cylindrical metal or a polyester film-coated drawn can, dried, and cured, has an appearance, workability, scratch resistance, and retort resistance. Has an excellent effect. The can coating composition of the present invention is preferably cured under conditions of 140 to 240 ° C. for 5 seconds to 10 minutes.

<Water-based (water-based can coating composition)>
The can coating composition of the present invention preferably contains water together with the above-mentioned organic solvent (D) as a solvent, particularly from the viewpoints of the environment such as low VOC and safety in coating. . At this time, the other organic solvent (D) is more preferably soluble in water (miscible with water at an arbitrary blending ratio).

When the can coating composition of the present invention is made aqueous, the acrylic resin (A) having a hydroxy group and a carboxy group, a copolymer (B1) obtained by copolymerizing maleic anhydride as an essential component and / or anhydrous A half esterified product (B2) of the copolymer (B1) obtained by reacting an acid anhydride group in the copolymer (B1) obtained by copolymerizing maleic acid as an essential component with the monofunctional alcohol (b); The carboxy group contained in β-hydroxyalkylamide (C) represented by the general formula (1) can be neutralized with a base to increase the water solubility of the resin. Examples of the base used for neutralization include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, ammonia, trimethylamine, triethylamine, tributylamine, 2- (dimethylamino) ethanol, 2 -(Diethylamino) ethanol, diethanolamine, triethanolamine, morpholine and the like.

A novel coating composition capable of forming a coating film excellent in water resistance, retort resistance, solvent resistance, and adhesion without contaminating the furnace during curing and without generating formaldehyde during curing. Can be obtained.

The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.

[Weight average molecular weight measurement]
The measurement of a weight average molecular weight is the value of polystyrene conversion measured by Tosoh GPC-8020. As a column, Tskel Super HM-L and HM-M were connected and used, and THF was used as a developing solvent.

<Synthesis of acrylic resin (A)>
[Synthesis Example 1: Synthesis of acrylic resin (A-1)]
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 144 parts of diethylene glycol monobutyl ether and 56 parts of propylene glycol monomethyl ether, heated to 110 ° C. under a nitrogen stream, A mixed solution in which 132 parts of acrylate, 28 parts of acrylic acid, 240 parts of 2-hydroxyethyl methacrylate, 24 parts of benzoyl peroxide, 130 parts of diethylene glycol monobutyl ether and 51 parts of propylene glycol monomethyl ether were uniformly mixed in advance was dropped over 2 hours. The reaction was continued for 1 hour at 110 ° C. after completion of the dropping. Thereafter, 2.4 parts of benzoyl peroxide were added twice every hour. One hour later, the pressure was reduced while maintaining the temperature at 110 ° C., and all propylene glycol monomethyl ether was distilled off. When the distillation was completed, cooling was performed, and 43 parts of dimethylaminoethanol and 103 parts of ion-exchanged water were added. The solution was finally diluted with diethylene glycol monobutyl ether so that the solid content was 50% to obtain an acrylic resin solution (A-1).

[Synthesis Examples 2 to 15: Synthesis of acrylic resins (A-2) to (A-15)]
(A-2) to (A-15) were synthesized in the same manner as in the synthesis example of (A-1) except that the formulation shown in Table 1 was changed.

Abbreviations and the like in Table 1 are as follows.
HEMA: 2-hydroxyethyl methacrylate 4HBA: 4-hydroxybutyl acrylate HPA: hydroxypropyl acrylate AA: acrylic acid MAA: methacrylic acid EA: ethyl acrylate BA: butyl acrylate EHA: 2-ethylhexyl acrylate LA: lauryl acrylate (dodecyl acrylate)
BPO: benzoyl peroxide BDG: diethylene glycol monobutyl ether DMAE: 2- (dimethylamino) ethanol hydroxyl value, acid value: calculated from monomer composition

<Synthesis of half esterified product (B2)>
[Synthesis Example 16: Synthesis of half-esterified product (B2-1)]
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 68 parts of styrene-maleic anhydride resin (SMA 1000 manufactured by Cray Valley), 10 parts of 1-propanol, 22 parts of 1-dodecanol, 1,8 -Diazabicyclo [5.4.0] -7-undecene (0.4 parts) and diethylene glycol dimethyl ether (33 parts) were charged and heated at 110 ° C for 8 hours. Thereafter, the mixture was cooled and diluted with diethylene glycol monobutyl ether to a solid content of 55% to obtain a half-esterified product solution (B2-1).

[Synthesis Examples 17 to 35: Synthesis Examples of Half-Esterified Products (B2-2) to (B2-20)]
(B2-2) to (B2-20) were synthesized in the same manner as in the synthesis example of (B1) except that the formulations shown in Tables 2 and 3 were changed.

The abbreviations in Tables 2 and 3 are as follows.
SMA 1000, 2000, 3000: Styrene maleic anhydride resin (manufactured by Cray Valley)
GSM301: Styrene maleic anhydride resin (manufactured by Gifu Shellac Co., Ltd.)
Isoban-600: isobutylene maleic anhydride resin (manufactured by Kuraray)
AN-139: Methyl vinyl ether maleic anhydride resin (GANTREZ AN-139 manufactured by ISP Japan)
DBU: 1,8-diazabicyclo [5.4.0] -7-undecene DMDG: diethylene glycol dimethyl ether SMA molecular weight: weight average molecular weight of copolymer (B1) MAH mol%: anhydrous contained in half esterified product (B2) Ratio of maleic acid expressed in mol% b1 / b2: molar ratio of monofunctional alcohols (b1) and (b2)

<Synthesis of β-hydroxyalkylamide (C)>
[Synthesis Example 36: Synthesis Example of β-Hydroxyalkylamide (C-1)]
Under a nitrogen atmosphere, in a reaction vessel equipped with a stirrer, thermometer, Dean-Stark tube, reflux condenser, and decompression device, 216.28 parts of dimethyl azelate (dimethyl nonanedioate), 210.28 parts of diethanolamine, sodium ethoxide 3 4 parts were added and stirred under normal pressure until the internal temperature reached 90 ° C. When the internal temperature reached 90 ° C., the pressure was reduced to 500 hPa, the mixture was heated and stirred at 100 ° C. for 2 hours, and the reaction was allowed to proceed while distilling off the produced methanol. After 2 hours, the mixture was further heated and stirred for 1 hour under a reduced pressure of 200 hPa, and all remaining methanol was distilled off. Thereafter, purification was performed, and ¹ H-NMR measurement and IR measurement were performed to confirm that the target product (N, N, N ′, N′-tetrakis (hydroxyethyl) azelainamide) was produced.

[Synthesis Examples 37 to 47: Synthesis Examples of β-hydroxyalkylamides (C-2) to (C-12)]
(C-2) to (C-12) were synthesized in the same manner as in the synthesis example of (C-1) except that the formulation shown in Table 4 was changed.

[Synthesis Example 48: Synthesis of β-hydroxyalkylamide (C-13)]
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 404.55 parts of β-hydroxyalkylamide (C-3) is placed and heated to 150 ° C. with stirring. Thawed. In this, 144.21 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. ¹ H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., cyclohexanone was added to adjust the solid content to 50%, and a cyclohexanone solution of β-hydroxyalkylamide (C-13) was taken out.

[Synthesis Examples 49 to 55: Synthesis Examples of β-Hydroxyalkylamides (C-14) to (C-20)]
(C-14) to (C-20) were synthesized in the same manner as in the synthesis example of (C-13) except that the formulation shown in Table 5 was changed.

[Synthesis Example 56: Synthesis of β-hydroxyalkylamide (C-21)]
Put 404.55 parts of β-hydroxyalkylamide (C-3) in a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, and heat and stir to 80 ° C. Thawed. Into this, 210.27 parts of octenyl succinic anhydride was dropped from a dropping apparatus over 1 hour and aged for 4 hours. ¹ H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., cyclohexanone was added, the solid content was adjusted to 50%, and a cyclohexanone solution of β-hydroxyalkylamide (C-21) was taken out.

[Synthesis Examples 57 to 62: Synthesis Examples of β-hydroxyalkylamides (C-22) to (C-27)]
(C-22) to (C-27) were synthesized in the same manner as in the synthesis example of (C-21) except that the formulation shown in Table 6 was changed.

The structures of the synthesized β-hydroxyalkylamides (C-1) to (C-27) are shown below.

<Manufacture of thermosetting composition (coating material for cans)>
[Example 1]
43.2 parts of an acrylic resin solution (A-1) having a hydroxy group and a carboxy group, a copolymer containing maleic anhydride as an essential component or a half ester solution (B2-1) thereof, 28.8 parts, β- Hydroxyalkylamide (C-3) 4.0 parts, tetraethylammonium chloride 10% aqueous solution 2.4 parts, diethylene glycol monobutyl ether 7.3 parts, 2- (dimethylamino) ethanol 3.5 parts, water 10.8 parts Was used to prepare a coating solution.

[Examples 2 to 66, Comparative Examples 1 to 6]
Except having changed into the prescription shown to Tables 7-13, it carried out similarly to Example 1, and manufactured the composition of Examples 2-66 and Comparative Examples 1-5.

<Evaluation of thermosetting composition (paint for can)>
The test piece which apply | coated the thermosetting composition (coating material for cans) obtained by the Example and the comparative example on the aluminum plate so that it might become a coating amount of 5 g / m < ² > -dry was prepared (test piece (1)). . Further, a black ink containing an oil-modified polyester resin as a main component of a vehicle is applied on an aluminum plate so that the application amount is 1 g / m ² -dry, and the above-described coating liquid is applied thereon from an application amount 5 g / m ^2. A test piece coated so as to be prepared separately was prepared (test piece (2)). Each test piece was tested for appearance, adhesion, work adhesion, curability, and hardness. The results are shown in Tables 7-13.

The appearance was visually evaluated according to the following criteria.
◎: No problem ○: Slightly weak gloss
Δ: Unevenness or pattern is seen or whitened.
X: A film cannot be formed.

Adhesion was performed by cross-cutting the coating film and peeling the cellophane tape. Evaluation was performed according to the following criteria.
◎: No peeling ○: Slightly peeled off (less than 5% peeling)
Δ: Partially peeled off (peeled part 5% or more and less than 20%)
X: Most peeled off (peeling part 20% or more)

The processing adhesion was processed from the back side of the test piece (the one without the coating film) using a DuPont impact tester (a convex part was formed on the coating film side), and the adhesiveness of the convex part was performed by cellophane tape peeling. Evaluation was performed according to the following criteria.
◎: No peeling ○: Slightly peeled off (less than 5% peeling)
Δ: Partially peeled off (peeled part 5% or more and less than 20%)
X: Most peeled off (peeling part 20% or more)

Curability was rubbed with gauze (16 sheets) moistened with methyl ethyl ketone, and the number of rubbing until the film was peeled was measured. Evaluation was performed according to the following criteria.
◎: More than 200 times ○: More than 150 times and less than 200 times △: More than 100 times and less than 150 times ×: Less than 100 times

Hardness was measured by pencil hardness. Evaluation was performed according to the following criteria.
◎: 5H or more ○: 3H-4H
Δ: H to 2H
X: Less than H

All of the above evaluations are considered to be practically acceptable with ◎ and ○.

Abbreviations and the like in Tables 7 to 13 are as follows.
TEAC-10W: 10% aqueous solution of tetraethylammonium chloride B1-1: SMA1000 Styrene maleic anhydride resin (manufactured by Cray Valley)
B1-2: SMA2000 styrene maleic anhydride resin (manufactured by Cray Valley)
B1-3: SMA1000 Styrene maleic anhydride resin (manufactured by Cray Valley)
B1-4: GSM301 Styrene maleic anhydride resin (manufactured by Gifu Shellac Co., Ltd.)
B1-5: Isoban-600 isobutylene maleic anhydride resin (manufactured by Kuraray)
B1-6: AN-139 Methyl vinyl ether maleic anhydride resin (GANTREZ AN-139 manufactured by ISP Japan)

As in Examples 1 to 66, the thermosetting composition of the present invention satisfies the necessary physical properties such as appearance, adhesion, work adhesion, curability and hardness in a well-balanced manner and can be suitably used as a paint for cans. all right.

Claims (8)

An acrylic resin (A) having a hydroxy group and a carboxy group,
The acid anhydride group in the copolymer (B1) obtained by copolymerization with maleic anhydride as an essential component and / or copolymer (B1) obtained by copolymerization with maleic anhydride as an essential component is converted to a monofunctional alcohol ( a half esterified product (B2) of the copolymer (B1) obtained by reacting with b), and
Β-hydroxyalkylamide (C) represented by the general formula (1),
A thermosetting composition comprising:
General formula (1)

[In General Formula (1), X is an n-valent group containing any of carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen, and the atom in X directly bonded to the carbonyl group is a carbon atom. Represents a functional group, n is an integer of 2 to 6, R ₁ and R ₂ are each independently a hydrogen atom, a group represented by the general formula (2), a group represented by the general formula (3) Or at least one in the molecule is a group represented by the general formula (2). ]

General formula (2)

[In General Formula (2), R _{3 to} R ₆ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group. ]

General formula (3)

[In General Formula (3), R _{3 to} R ₆ each independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group, and R ₇ is a functional group capable of reacting with a hydroxy group. It represents the residue of a compound having a group. ]   Furthermore, an organic solvent (D) is contained, The thermosetting composition of Claim 1 characterized by the above-mentioned.   The thermosetting composition according to claim 1 or 2, further comprising a quaternary ammonium salt or a quaternary phosphonium salt (E). An acrylic resin (A) having a hydroxy group and a carboxy group,
Half esterified product (B2) of the copolymer (B1) obtained by reacting an acid anhydride group in the copolymer (B1) obtained by copolymerizing maleic anhydride as an essential component with a monofunctional alcohol (b) As well as
Β-hydroxyalkylamide (C) represented by the general formula (1),
The thermosetting composition according to claim 1, comprising: The monofunctional alcohol (b) is at least one monofunctional alcohol (b1) selected from the group consisting of methanol, ethanol, 1-propanol, and 2-propanol;
The thermosetting composition according to any one of claims 1 to 4, comprising a monofunctional alcohol (b2) having 8 or more carbon atoms.   6. The thermosetting composition according to claim 5, wherein the monofunctional alcohol (b2) is a linear alkyl group-containing monofunctional alcohol having 12 or more carbon atoms.   A can coating composition comprising the thermosetting composition according to claim 1.   An aqueous can coating composition comprising the can coating composition according to claim 7, a volatile base compound, and water.