JP2017082050A - Paint composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition capable of suppressing the generation amount of fume such as silica fume at the time of baking, maintaining a stain resistance for a long period of time when exposed outdoors, and forming a coating film having good coating film hardness and workability. To provide.
[Solution]
1. A coating composition containing a hydroxyl group-containing resin (a), a crosslinking agent (b) and a specific antifouling agent (c), wherein the total solid content of the hydroxyl group-containing resin (a) and the crosslinking agent (b) is 100. The coating composition which contains 0.1-10 mass parts of antifouling agents (c) with respect to mass parts.
2. The coating composition according to 1, wherein the solid content of the hydroxyl group-containing resin (a) and the crosslinking agent (b) is 100 parts by mass in total and the anionic surfactant (d) is contained in an amount of 0.1 to 20 parts by mass. .
[Selection] Figure 1

Description

  The present invention is a coating composition that can suppress the generation amount of fume such as silica fume at the time of baking, can maintain stain resistance for a long period of time when exposed outdoors, and can form a coating film with good coating film hardness and workability. Related to things.

  Traditionally, outdoor substrates (for example, buildings, display objects, guard fences, appliances, machines, etc.) are stained on the surface of the paint due to the effects of smoke, dust, iron powder, rain (acid rain) and sunlight. Problems may arise and stain resistant paints containing silicates may be applied. In the stain-resistant paint containing such a silicate, fumes generated when the coating film is baked and dried accumulate in the drying furnace and fall on the coated plate, which may reduce the finish.

  For example, Patent Document 1 discloses a coating composition containing various coating resins such as an acrylic polyol resin, a specific fluorine compound, and dimethyl silicone oil having a fluoroalkyl group. However, the coating film obtained by applying Patent Document 1 was insufficiently contaminated by outdoor exposure.

  Patent Document 2 discloses a stain-resistant coating composition containing a specific polyester resin (A), a butyl etherified melamine resin (B), an organosilicate and / or a condensate thereof (C). However, although the coating composition described in Patent Document 2 is improved in stain resistance, the amount of fumes generated during baking of the coating film is large.

Japanese Patent Laid-Open No. 11-217540 International Publication 2012/002095 Pamphlet

 The problem to be solved by the present invention is that the amount of fume generated during baking can be suppressed, the anti-contamination property can be maintained for a long time when exposed outdoors, and a coating film having good coating film hardness and workability can be formed. It is to provide a coating composition.

  As a result of intensive studies, the present inventors have found that the problem can be achieved by a coating composition containing a hydroxyl group-containing resin (a), a crosslinking agent (b) and a specific antifouling agent (c).

That is, the present invention
1. A coating composition containing a hydroxyl group-containing resin (a), a crosslinking agent (b) and a stain resistance agent (c) represented by the following formula (1), wherein the hydroxyl group-containing resin (a) and the crosslinking agent (b) A coating composition containing 0.1 to 10 parts by mass of the antifouling agent (c) with respect to 100 parts by mass of the total solid content of
Antifouling agent (c):

Formula (1)
(In Formula (1), X represents a group selected from a sulfonic acid group, a sulfonic acid group, a carboxyl group, and a carboxylic acid group, and Y has a sulfur atom, an oxygen atom, and a linear or branched nitrogen atom. Represents an atom or group selected from a group, R ¹ represents a group selected from an alkylene group, a phenylene group and a phenylalkylene group having 1 to 8 carbon atoms, and R ² represents an alkylene group having 1 to 8 carbon atoms. And R ³ represents a group selected from an alkyl group, a fluorinated alkyl group, a phenyl group, and an aralkyl group having 6 to 24 carbon atoms.
2. The coating material according to 1, which contains 0.1 to 20 parts by mass of the following anionic surfactant (d) with respect to 100 parts by mass of the total solid content of the hydroxyl group-containing resin (a) and the crosslinking agent (b). Composition,
Anionic surfactant (d):
Alkyldiphenyl ether disulfonate-based anionic surfactant (d1), polyoxyethylene alkyl ether sulfate-based anionic surfactant (d2), alkylbenzenesulfonate-based anionic surfactant (d3) and 2. at least one anionic surfactant selected from sulfosuccinate-based anionic surfactants (d4); In item 1 or item 2 containing 0.1 to 20 parts by mass of nitrogen atom-containing resin (e) having the following characteristics with respect to a total of 100 parts by mass of the solid content of the hydroxyl group-containing resin (a) and the crosslinking agent (b) The coating composition according to the description,
Nitrogen atom-containing resin (e):
An amino group or a quaternary ammonium base-containing polymerizable unsaturated monomer (e11), a polymerizable unsaturated monomer having a nitrogen atom-containing heterocyclic ring (e12) and N-substituted with respect to the total amount of all the constituent monomers. 5 to 70% by mass of at least one nitrogen atom-containing polymerizable unsaturated monomer (e1) selected from the (meth) acrylamide compound (e13), and 30 to 95% by mass of other polymerizable unsaturated monomer (e2). % Copolymer resin of monomer mixture 4. The term described in any one of items 1 to 3, containing 0.1 to 20 parts by mass of the ionic liquid (f) with respect to 100 parts by mass of the total solid content of the hydroxyl group-containing resin (a) and the crosslinking agent (b). Coating composition of the
It is related with the manufacturing method of a coating metal plate including the process of coating the coating composition as described in any one of 5.1-4.

The coating composition of the present invention can achieve both suppression of fume generation during baking and improvement of stain resistance. Specifically, the coating composition of the present invention can reduce the maintenance of the drying furnace because the amount of generated fume is small, and obtain a coated article having excellent finish because there is little dropping of fumes from the ceiling of the drying furnace. be able to.

  Further, if necessary, the contamination resistance can be improved by containing at least one of an anionic surfactant (d), a nitrogen atom-containing resin (e) and an ionic liquid (f).

The model figure of the apparatus which tests the fume generation amount at the time of baking is shown.

   The coating composition of the present invention is a coating composition containing a hydroxyl group-containing resin (a), a crosslinking agent (b) and a specific antifouling agent (c), wherein the hydroxyl group-containing resin (a) and a crosslinking agent ( Containing 0.1 to 10 parts by mass of the antifouling agent (c) with respect to 100 parts by mass of the total solid content with b).

  The coating composition of the present invention may further contain at least one of a specific anionic surfactant (d), a specific nitrogen atom-containing resin (e) and an ionic liquid (f) as necessary. it can. Details will be described below.

[Coating composition]
Hydroxyl-containing resin (a)
The hydroxyl group-containing resin (a) is a resin having two or more hydroxyl groups in one molecule, and may have a carboxyl group as necessary. Specific examples of the hydroxyl group-containing resin (a) include acrylic resin, polyester resin, epoxy resin, polyurethane resin, and the like, but a hydroxyl group-containing polyester resin is preferable in terms of improving stain resistance, coating film hardness, and processability. . The hydroxyl group-containing polyester resin can be usually produced by an esterification reaction or a transesterification reaction with a polybasic acid component and a polyhydric alcohol component.

  As said polybasic acid component, an alicyclic polybasic acid component, an aliphatic polybasic acid component, an aromatic polybasic acid component, etc. can be used, for example.

  As the alicyclic polybasic acid component, generally, a compound having one or more alicyclic structures (mainly 4 to 6-membered rings) and two or more carboxyl groups in one molecule, an acid anhydride of the compound And an esterified product of the compound. Examples of the alicyclic polybasic acid component include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 3- Alicyclic polycarboxylic acids such as methyl-1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid An anhydride of these alicyclic polyvalent carboxylic acids; a lower alkyl esterified product of these alicyclic polyvalent carboxylic acids, and the like. An alicyclic polybasic acid component can be used individually or in combination of 2 or more types.

  As the alicyclic polybasic acid component, in particular, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic anhydride, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene- 1,2-dicarboxylic acid and 4-cyclohexene-1,2-dicarboxylic anhydride can be preferably used. Among the above, 1,2-cyclohexanedicarboxylic acid and 1,2-cyclohexanedicarboxylic anhydride can be particularly preferably used from the viewpoint of hydrolysis resistance.

  The aliphatic polybasic acid component is generally an aliphatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aliphatic compound, and an esterified product of the aliphatic compound, for example, Aliphatic polycarboxylic acids such as acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, octadecanedioic acid, citric acid; An anhydride of a polyvalent carboxylic acid; a lower alkyl esterified product of these aliphatic polyvalent carboxylic acids. An aliphatic polybasic acid component can be used individually or in combination of 2 or more types.

As the aliphatic polybasic acid component, it is preferable to use a dicarboxylic acid having an alkylene chain having 4 to 18 carbon atoms. Examples of the dicarboxylic acid having an alkylene chain having 4 to 18 carbon atoms include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, and octadecanedioic acid. Among them, adipic acid can be preferably used.
The aromatic polybasic acid component is generally an aromatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aromatic compound and a lower alkyl esterified product of the aromatic compound, For example, aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, trimellitic acid, pyromellitic acid; anhydrides of these aromatic polycarboxylic acids And lower alkyl esterified products of these aromatic polycarboxylic acids. An aromatic polybasic acid component can be used individually or in combination of 2 or more types.

  As the polyhydric alcohol component, a polyhydric alcohol having two or more hydroxyl groups in one molecule can be preferably used. Examples of the polyhydric alcohol include alicyclic diols, aliphatic diols, aromatic diols, and trihydric or higher polyhydric alcohols.

  The alicyclic diol is generally a compound having one or more alicyclic structures (mainly 4- to 6-membered rings) and two hydroxyl groups in one molecule. Examples of the alicyclic diol include dihydric alcohols such as 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F; ε-caprolactone and the like in these dihydric alcohols. Examples include polylactone diol to which a lactone compound is added, and these can be used alone or in combination of two or more.

  The aliphatic diol is generally an aliphatic compound having two hydroxyl groups in one molecule. Examples of the aliphatic diol include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3 -Butanediol, 1,2-butanediol, 3-methyl-1,2-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-pentanediol, 1,5-pentanediol 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3 -Pentanediol, 1,6-hexanediol, 1, -Hexanediol, 1,4-hexanediol, 2,5-hexanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, neopentyl glycol; polyethylene glycol, polypropylene glycol and poly Examples include polyether diol compounds such as butylene glycol, and these can be used alone or in combination of two or more.

  The aromatic diol is generally an aromatic compound having two hydroxyl groups in one molecule. Examples of the aromatic diol include ester diol compounds such as bis (hydroxyethyl) terephthalate; alkylene oxide adducts of bisphenol A and the like, and these can be used alone or in combination of two or more.

  Examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, sorbitol, and mannitol. A trilactone or higher alcohol; a polylactone polyol compound obtained by adding a lactone compound such as ε-caprolactone to the trihydric or higher alcohol; tris (2-hydroxyethyl) isocyanurate, tris (2-hydroxypropyl) isocyanurate, And tris (hydroxyalkyl) isocyanurate such as tris (2-hydroxybutyl) isocyanurate. Of these, trimethylolpropane is particularly preferable.

  The production of the hydroxyl group-containing polyester resin used in the present invention is not particularly limited, and can be performed according to a usual method. For example, it is produced by reacting an acid component having the polybasic acid component as an essential component and a polyhydric alcohol component at 150 to 250 ° C. for 5 to 10 hours in a nitrogen stream and performing an esterification reaction or a transesterification reaction. can do. In the esterification reaction or transesterification reaction, the acid component and alcohol component may be added at once, or may be added in several portions. Moreover, after synthesize | combining a carboxyl group-containing polyester resin first, you may esterify some carboxyl groups in this carboxyl group-containing polyester resin using the said alcohol component. Furthermore, after first synthesizing the hydroxyl group-containing polyester resin, the acid anhydride may be reacted to half-esterify the hydroxyl group-containing polyester resin.

In the esterification or transesterification reaction, a catalyst may be used to promote the reaction. As the catalyst, known catalysts such as dibutyltin oxide, antimony trioxide, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, and tetraisopropyl titanate can be used.
Further, the hydroxyl group-containing polyester resin can be modified with a fatty acid, an oil, a fat, a monoepoxy compound, a monoalcohol compound, a polyisocyanate compound or the like during the preparation of the resin, or after the esterification reaction or the transesterification reaction.

  Examples of the fatty acid include coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor Examples include fatty acids such as oil fatty acids and safflower oil fatty acids; lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and the like. Examples of the fat include coconut oil, cottonseed oil, hemp seed oil, rice bran oil, fish oil, tall oil, soybean oil, linseed oil, tung oil, rapeseed oil, castor oil, dehydrated castor oil, safflower oil and the like.

Examples of the polyisocyanate compound used for the modification include aliphatic diisocyanate compounds such as lysine diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane. -Aliphatic diisocyanate compounds such as 2,6-diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,3- (isocyanatomethyl) cyclohexane; aromatics such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate Diisocyanate compounds; organic poly- such as tri- or higher polyisocyanates such as lysine triisocyanate Isocyanate itself, or an adduct of each of these organic polyisocyanates with polyhydric alcohol, low molecular weight polyester resin or water, or a cyclized polymer of each of the above organic diisocyanates (for example, isocyanurate), biuret type addition And the like. These can be used alone or in combination of two or more.
The number average molecular weight of the hydroxyl group-containing polyester resin is preferably 2,000 to 30,000, particularly within the range of 3,000 to 25,000, from the viewpoints of coating film hardness, workability, and finish of the resulting coating film. It is preferred to have a number average molecular weight.

  In addition, the number average molecular weight or the weight average molecular weight in the present specification is a value obtained by converting the number average molecular weight and the weight average molecular weight measured using a gel permeation chromatograph (GPC) on the basis of the molecular weight of standard polystyrene. .

  Specifically, “HLC8120GPC” (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph, and “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL” and “TSKgel G-2500HXL” are used as columns. Four TSKgel G-2000HXL (trade names, all manufactured by Tosoh Corporation) can be used, and measurement can be performed under conditions of mobile phase tetrahydrofuran, measurement temperature 40 ° C., flow rate 1 mL / min, and detector RI. However, the nitrogen atom-containing resin (d) having at least one group selected from an amino group, an ammonium group, and a nitrogen atom-containing heterocyclic ring in the molecule can be obtained by a measurement method described later.

  The hydroxyl value of the hydroxyl group-containing polyester resin is preferably in the range of 10 to 200 mgKOH / g, particularly 60 to 185 mgKOH / g, from the viewpoint of the coating film hardness and stain resistance of the resulting coating film. The acid value of the hydroxyl group-containing polyester resin is 30 mgKOH / g or less, preferably in the range of 1 to 20 mgKOH / g, from the viewpoint of processability and the like.

Crosslinking agent (b) The crosslinking agent (b) in the coating composition of the present invention may be used without particular limitation as long as it can react with the hydroxyl group of the hydroxyl group-containing resin (a) by heating to be cured. Melamine resin, benzoguanamine resin, urea resin, polyisocyanate compound, and the like.

  As said melamine resin, a part or all of methylol group of methylolation melamine is C1-C8 monohydric alcohol, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol , Partially etherified or fully etherified melamine resins etherified with i-butyl alcohol, 2-ethylbutanol, 2-ethylhexanol and the like.

  Examples of commercially available melamine resins include Cymel 202, Cymel 232, Cymel 235, Cymel 238, Cymel 254, Cymel 266, Cymel 267, Cymel 272, Cymel 285, Cymel 301, Cymel 303, Cymel 325, Cymel 327, and Cymel 350. , Cymel 370, Cymel 701, Cymel 703, Cymel 1141 (Nippon Cytec Industries, Inc.), Uban 20SE60 (Mitsui Cytec, Inc.), and the like.

  Examples of the benzoguanamine resin include methylolated benzoguanamine resins obtained by reaction of benzoguanamine and aldehyde. Examples of the aldehyde include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like. In addition, those obtained by etherifying this methylolated benzoguanamine resin with one or more alcohols are also included in the benzoguanamine resin. Examples of the alcohol used for etherification include monohydric alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethylbutanol, and 2-ethylhexanol. . Among these, a benzoguanamine resin obtained by etherifying at least a part of the methylol group of the methylolated benzoguanamine resin with a monohydric alcohol having 1 to 4 carbon atoms is preferable.

  Specific examples of the benzoguanamine resin include, for example, My Coat 102, My Coat 105, My Coat 106 (all of which are manufactured by Mitsui Cytec Co., Ltd.), Nicalac SB-201, Nicalac SB-203, Nicalac SB-301, Nicalac SB. -303, Nicalac SB-401 (all of which are manufactured by Sanwa Chemical Co., Ltd.), etc .; methyl etherified benzoguanamine resins such as Cymel 1123 (manufactured by Mitsui Cytec Co., Ltd.); mixed etherified benzoguanamine resins of ethyl ether; A mixture of methyl ether and butyl ether such as Coat 136 (Mitsui Cytec Co., Ltd.), Nicalac SB-255, Nicalac SB-355, Nicalac BX-37, Nicalac BX-4000 (all of which are manufactured by Sanwa Chemical Co., Ltd.) , And the like butyl etherified benzoguanamine resins such as Mycoat 1128 (manufactured by Mitsui Cytec Ltd.); Le benzoguanamine resin. The urea resin is obtained by a condensation reaction of urea and formaldehyde, and can be dissolved or dispersed in a solvent or water.

  Examples of the polyisocyanate compound include compounds having two or more isocyanate groups in one molecule, for example, aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and naphthalene diisocyanate; tetramethylene diisocyanate, hexamethylene diisocyanate, dimer Aliphatic diisocyanates such as acid diisocyanate and lysine diisocyanate; Alicyclic diisocyanates such as methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, methylcyclohexane diisocyanate, cyclohexane diisocyanate, and cyclopentane diisocyanate; Addendum; this Et polyisocyanate and a low molecular weight or high molecular weight polyol compound (e.g., acrylic polyols, polyester polyols, polyether polyols, etc.) and there may be cited an isocyanate group excess obtained by reacting the free isocyanate group-containing prepolymer.

  Furthermore, as the polyisocyanate compound, the free isocyanate group of the polyisocyanate compound is a phenol compound, oxime compound, active methylene compound, lactam compound, alcohol compound, mercaptan compound, acid amide compound, imide compound, amine compound, imidazole. A blocked polyisocyanate compound blocked with a blocking agent such as a series compound, a urea series compound, a carbamic acid series compound, or an imine series compound can also be used.

  As a mixing ratio of the hydroxyl group-containing resin (a) and the crosslinking agent (b), based on the total solid content of both, the hydroxyl group-containing resin (a) is 60 to 95 parts by mass, preferably 70 to 70 parts by mass. 90 parts by mass and 5 to 40 parts by mass, preferably 10 to 30 parts by mass of the crosslinking agent (b) are preferable from the viewpoint of coating film hardness and workability.

Antifouling agent (c)
The coating composition of the present invention contains a stain resistance agent (c) represented by the following formula (1).

  Antifouling agent (c):

Formula (1)
(In Formula (1), X represents a group selected from a sulfonic acid group, a sulfonic acid group, a carboxyl group, and a carboxylic acid group, and Y represents a linear or branched group having a sulfur atom, an oxygen atom, and a nitrogen atom. Represents an atom or group selected from a group, R ¹ represents a group selected from an alkylene group, a phenylene group and a phenylalkylene group having 1 to 8 carbon atoms, and R ² represents an alkylene group having 1 to 8 carbon atoms. And R ³ represents a group selected from an alkyl group, a fluorinated alkyl group, a phenyl group, and an aralkyl group having 6 to 24 carbon atoms.
The antifouling agent (c) represented by the above formula (1) can be produced by a conventionally known method. Examples of the production method include a production method by Michael addition reaction and a production method by sultone ring-opening reaction.

Antifouling agent (c1)
As the antifouling agent (c), for example, the antifouling agent (c1), which is a product of a Michael addition reaction between the electrophilic compound (c11) and the nucleophilic compound (c12), can be used. The electrophilic compound (c11) and the nucleophilic compound (c12) are described below.

Electrophilic compound (c11)
Examples of the electrophilic compound (c11) include hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and dodecyl (meth). Acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclo Pentenyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, nonafluorohexyl (meth) acrylate, dodecafluor Heptyl (meth) acrylate, acrylic acid esters such as tridecafluorooctyl (meth) acrylate compound or a methacrylate compound, and the like.

Nucleophilic compound (c12)
Examples of the nucleophilic compound (c12) include 2-mercaptoethanesulfonic acid, sodium 2-mercaptoethanesulfonate, sodium 3-mercaptopropanesulfonate, tetramethylammonium 3-mercaptopropanesulfonate, and 3-mercaptopropanesulfone. Mercapto compounds having a sulfonic acid group such as benzyltrimethylammonium acid and salts of the mercapto compounds; mercapto compounds having a carboxyl group such as thioglycolic acid, thiolactic acid, 3-mercaptopropionic acid, 3-mercaptoisobutyric acid, and the mercapto compounds Aminomethanesulfonic acid, aminoethanesulfonic acid, sodium aminoethanesulfonic acid, tetramethylammonium aminoethanesulfonic acid, sodium N-methylaminoethanesulfonic acid N-cyclohexylaminopropanesulfonic acid, sodium N-cyclohexylaminopropanesulfonate, 5-aminopentanesulfonic acid, sodium 5-aminopentanesulfonate, 6-aminohexanesulfonic acid, sodium 6-aminohexanesulfonate, 7-amino Heptanesulfonic acid, sodium 7-aminoheptanesulfonate, 8-aminooctanesulfonic acid, sodium 8-aminooctanesulfonate, aminobenzenesulfonic acid, sodium aminobenzenesulfonate, N-methylaminoethanesulfonic acid, N-methylamino Sodium ethanesulfonate, N-cyclohexylaminoethanesulfonic acid, N-cyclohexylaminoethanesodium sodium, N-cyclohexylaminopropanesulfonic acid, N-cycl Aminosulfonic acid such as sodium hexylaminopropane sulfonate and the aminosulfonic acid salt; aminoacetic acid, sodium aminoacetic acid, aminopropionic acid, sodium aminopropionic acid, aminobutanoic acid, sodium aminobutanoate, aminoheptanoic acid, sodium aminoheptanoate, Aminohexanoic acid, sodium aminohexanoate, aminobenzoic acid, aminobenzoic acid sodium and the like amino acids and salts thereof; hydroxysulfonic acid such as phenolsulfonic acid and phenolsulfonic acid salt; and the hydroxysulfonic acid salt; hydroxybenzoic acid, Hydroxy acids such as hydroxybenzoate, hydroxyphenylacetic acid, hydroxyphenylacetate, hydroxyphenylpropionic acid, hydroxyphenylpropionate and the like Examples include silicates.

  In addition, the Michael addition reaction in the production of the antifouling agent (c1) is carried out by converting the electrophilic compound (c11) and the nucleophilic compound (c12) into compound (c11) / compound (c12) = 0.8 / 1. To 5.0 / 1 (molar ratio), preferably compound (c11) / compound (c12) = 0.9 / 1 to 2.2 / 1 (molar ratio). In the range of 0 ° C. to 200 ° C., preferably 0 ° C. to 50 ° C., it is preferable from the viewpoint of the yield of the antifouling agent (c1).

  The Michael addition reaction can be carried out in the presence of water or an organic solvent, if necessary. Examples of the organic solvent include known organic solvents such as ester, ether, and alcohol. In order to accelerate the Michael addition reaction, the solid content concentration of the reaction solution in the Michael addition reaction is preferably 5% by mass or more, and more preferably 30% by mass or more. The reaction time is usually 30 minutes to 5 hours, preferably 1 to 4 hours.

  In the Michael addition reaction, a catalyst can be used as necessary. The catalyst is not particularly limited. For example, metal alkoxides such as sodium methoxide, sodium ethoxide and magnesium ethoxide; metal phenoxides such as sodium phenoxide; metal carboxylates such as sodium benzoate and potassium benzoate; triethylamine , Triethylenediamine, N, N-diethylaniline, N, N-dimethylaniline, N, N-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N, N'-dimethylpiperazine, pyridine, picoline, 1, Tertiary amines such as 8-diaza-bicyclo (5,4,0) undecene-7; tetraethylammonium bromide, tetrabutylammonium bromide, benzyltriethylammonium chloride, trioctylmethylammonium chloride, cetyltrimethyl bromide Quaternary ammonium salts such as ruammonium, tetrabutylammonium iodide, dodecyltrimethylammonium iodide, benzyldimethyltetradecylammonium acetate; quaternary such as tetraphenylphosphonium chloride, triphenylmethylphosphonium chloride, tetramethylphosphonium bromide Phosphonium salt; 2-methylimidazole, 2-ethylimidazole, 2-methyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, Basicity of imidazole compounds such as 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-azine-2-methylimidazole and the like Compounds. The catalyst is not limited to one type, and a plurality of types can be used as necessary.

Antifouling agent (c2)
As the antifouling agent (c) used in the coating composition of the present invention, for example, the antifouling agent which is a product of the ring-opening addition reaction between the nucleophilic compound (c21) and the sultone compound (c22). (C2) can be used. Hereinafter, the nucleophilic compound (c21) and the sultone compound (c22) will be described.

Nucleophilic compound (c21)
Examples of the nucleophilic compound (c21) include mercaptopropionic acid n-octyl ester, mercaptopropionic acid 2-ethylhexyl ester, mercaptopropionic acid decyl ester, mercaptopropionic acid undecyl ester, mercaptopropionic acid dodecyl ester, mercaptopropionic acid. Tridecyl ester, mercaptopropionic acid stearyl ester, mercaptopropionic acid isostearyl ester, mercaptopropionic acid cyclohexyl ester, mercaptopropionic acid isobornyl ester, mercaptopropionic acid dicyclopentanyl ester, mercaptopropionic acid dicyclopentenyl ester, mercaptopropion Acid phenyl ester, mercaptopropionic acid benzyl ester, mercaptop Mercapto group-containing compound such as phenyl ethyl ester of pion; glycine octyl ester, alanine octyl ester, glycine decyl ester, alanine decyl ester, glycine dodecyl ester, alanine dodecyl ester, glycine hexadecyl ester, alanine hexadecyl ester, glycine octadecyl ester, Amino group-containing compounds such as alanine octadecyl ester, glycine cyclohexyl ester, alanine cyclohexyl ester, glycine phenyl ester, alanine phenyl ester, glycine benzyl ester, alanine benzyl ester, glycine phenyl ethyl ester, alanine phenyl ethyl ester; lactic acid hexyl ester, hexyl salicylate Ester, hexyl hydroxybenzoate Stell, hydroxyphenylacetic acid hexyl ester, hydroxyphenylpropionic acid hexyl ester, lactate octyl ester, salicylic acid octyl ester, hydroxybenzoic acid octyl ester, hydroxyphenylacetic acid octyl ester, hydroxyphenylpropionic acid octyl ester, lactate decyl ester, salicylic acid decyl ester, Hydroxybenzoic acid decyl ester, hydroxyphenylacetic acid decyl ester, hydroxyphenylpropionic acid decyl ester, lactate dodecyl ester, salicylic acid dodecyl ester, hydroxybenzoic acid dodecyl ester, hydroxyphenylacetic acid dodecyl ester, hydroxyphenylpropionic acid dodecyl ester, lactate hexadecyl ester , Salicylic acid hexadecyl ester, Hydroxybenzoic acid hexadecyl ester, hydroxyphenylacetic acid hexadecyl ester, hydroxyphenylpropionic acid hexadecyl ester, lactic acid octadecyl ester, salicylic acid octadecyl ester, hydroxybenzoic acid octadecyl ester, hydroxyphenylacetic acid octadecyl ester, hydroxyphenylpropionic acid octadecyl ester, lactic acid Cyclohexyl ester, salicylic acid cyclohexyl ester, hydroxybenzoic acid cyclohexyl ester, hydroxyphenylacetic acid cyclohexyl ester, hydroxyphenylpropionic acid cyclohexyl ester, lactate phenyl ester, salicylic acid phenyl ester, hydroxybenzoic acid phenyl ester, hydroxyphenylacetic acid phenyl ester, hydro Cyphenylpropionic acid phenyl ester, lactate benzyl ester, salicylic acid benzyl ester, hydroxybenzoic acid benzyl ester, hydroxyphenylacetic acid benzyl ester, hydroxyphenylpropionic acid benzyl ester, lactate phenylethyl ester, salicylic acid phenylethyl ester, hydroxybenzoic acid phenylethyl ester And hydroxyl group-containing compounds such as hydroxyphenylacetic acid phenylethyl ester and hydroxyphenylpropionic acid phenylethyl ester.

Sultone compound (c22)
Examples of the sultone compound (c22) include propane sultone, butane sultone, pentane sultone, hexane sultone, heptane sultone, octane sultone and the like. The ring-opening addition reaction between the nucleophilic compound (c21) and the sultone compound (c22) is, for example, the method described in Yukagaku, Vol. 15, No. 9 (1966), page 469. It is done.
The ring-opening addition reaction in the production of the antifouling agent (c2) is carried out by converting the nucleophilic compound (c21) and the sultone compound (c22) into compound (c21) / compound (c22) = 1 / 0.8 to 1 / 5.0 (molar ratio), preferably compound (c21) / compound (c22) = 1 / 0.9 to 1 / 2.2 (molar ratio), and usually 10 to 10. It is preferable to carry out within a range of 200 ° C., preferably within a range of 20 to 100 ° C., in view of the yield of the antifouling agent (c2).

  The ring-opening addition reaction can be carried out in the presence of an organic solvent, if necessary. As an organic solvent, well-known organic solvents, such as ester type and ether type, are mentioned, for example.

  In order to accelerate the ring-opening addition reaction, the solid content concentration in the reaction solution is preferably 5% by mass or more, and more preferably 30% by mass or more. The reaction time is usually 30 minutes to 5 hours, preferably 1 to 4 hours. In addition, the said ring-opening addition reaction can also use a catalyst as needed. Examples of the catalyst include sodium methoxide and sodium ethoxide.

  The blending amount of the antifouling agent (c) in the coating composition of the present invention is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the hydroxyl group-containing resin (a) and the crosslinking agent (b). In view of coating film hardness, stain resistance and workability, it is preferable to contain 1 to 8 parts by mass, more preferably 2 to 7 parts by mass.

Anionic surfactant (d)
The coating composition of the present invention can contain an anionic surfactant (d) as necessary for the purpose of improving stain resistance.

  Examples of the anionic surfactant (d) include alkyldiphenyl ether disulfonate-based anionic surfactant (d1), polyoxyethylene alkyl ether sulfate-based anionic surfactant (d2), and alkylbenzene. Examples thereof include at least one anionic surfactant selected from a sulfonate-based anionic surfactant (d3) and a sulfosuccinate-based anionic surfactant (d4).

Alkyl diphenyl ether disulfonate anionic surfactant (d1)
The alkyldiphenyl ether disulfonate-based anionic surfactant (d1) (hereinafter sometimes abbreviated as anionic surfactant (d1)) is an alkyldiphenyl ether having the structural formula represented by the following formula (2). A disulfonic acid or its metal salt can be mentioned. Among these, alkyl diphenyl ether disulfonic acid sodium salt is particularly preferable from the viewpoint of improving stain resistance.

Formula (2)
(R in the formula (2) represents an alkyl group having 1 to 15 carbon atoms, and M ⁺ represents H ⁺ , Na ⁺ , K ⁺ , Li ⁺ , NH ⁴⁺ or an organic ammonium ion)
Examples of commercially available anionic surfactants (d1) include Perex SS-L, Perex SS-H (Kao Corporation), New Coal 261-A, New Coal 271-A (Nippon Emulsifier Co., Ltd.) and the like. It is done.

Polyoxyethylene alkyl ether sulfate anionic surfactant (d2)
As the polyoxyethylene alkyl ether sulfate ester-based anionic surfactant (d2) (hereinafter sometimes abbreviated as anionic surfactant (d2)), a structure represented by the following general formula (3) Mention may be made of the polyoxyethylene alkyl ether sulfates of the formula or their metal salts. Among these, polyoxyethylene alkyl ether sulfate sodium salt is particularly preferable from the viewpoint of improving stain resistance.

Formula (3)
(R in Formula (3) represents a hydrocarbon group having 1 to 50 carbon atoms, n represents 1 to 30, M ⁺ represents H ⁺ , Na ⁺ , K ⁺ , Li ⁺ , NH ₄ ⁺ or an organic ammonium ion. Represent)
Commercially available products of the anionic surfactant (d2) include, for example, New Coal 707SN, New Coal 714SF, New Coal 2308SF, New Coal 2360SN (Nippon Emulsifier Co., Ltd.), Latemle E-118B, Laterum E-150, Latemuru WX, Laterum PD-140 (Kao Corporation) and the like.
Alkylbenzenesulfonate anionic surfactant (d3)
Examples of the alkylbenzene sulfonate-based anionic surfactant (d3) (hereinafter sometimes abbreviated as anionic surfactant (d3)) include alkylbenzene sulfonic acids having the structural formula represented by the following formula (4): Or the metal salt can be mentioned. Among these, alkylbenzenesulfonic acid sodium salt is particularly preferable from the viewpoint of improving the stain resistance.

Formula (4)
(R in Formula (4) represents a hydrocarbon group having 1 to 15 carbon atoms, and M ⁺ represents H ⁺ , Na ⁺ , K ⁺ , Li ⁺ , NH ₄ ⁺ or an organic ammonium ion)
Examples of commercial products of the anionic surfactant (d3) include New Coal 210, New Coal 220-L (Nippon Emulsifier Co., Ltd.), Neoperex G-15, Neoperex G-25 (Kao Co., Ltd.) and the like. It is done.

Sulfosuccinate anionic surfactant (d4)
The sulfosuccinate-based anionic surfactant (d4) (hereinafter sometimes abbreviated as anionic surfactant (d4)) is a dialkylsulfosuccinate having the structural formula represented by the following general formula (5). An acid or its metal salt can be mentioned.

^R 1, ^{R 2} in the formula (5) (Equation (5) are the same or different and each represents an alkyl group having 1 to 15 carbon atoms, ^{M +} is ^{H +, Na +, K +} , Li +, NH ₄ represents a ⁺ or organic ammonium ion).

  Specifically, for example, monoalkyl sulfosuccinic acid ester salt, dialkyl sulfosuccinic acid ester salt, sulfosuccinic acid alkyl disalt, polyoxyethylene alkyl sulfosuccinic acid disalt, alkylamine oxide bistridecyl sulfosuccinate sodium, dioctyl sulfosuccinate sodium, dihexyl Sodium sulfosuccinate, sodium dicyclohexylsulfosuccinate, sodium diamylsulfosuccinate, sodium diisobutylsulfosuccinate, disodium isodecylsulfosuccinate, N-octadecylsulfosuccinamide disodium, N- (1,2-dicarboxyethyl) -N- And octadecyl sulfosuccinamide tetrasodium. Among these, a dialkylsulfosuccinic acid sodium salt is particularly preferable from the viewpoint of improving stain resistance.

  Commercially available products of the anionic surfactant (d4) include Perex OT-P, Perex TR, Perex CS, Perex TA (Kao Corporation), New Coal 290-A, New Coal 290-M, New Coal 291- M, New Coal 291-PG, New Coal 291-GL, New Coal 292-PG, New Coal 293 (Nippon Emulsifier Co., Ltd.), Neo Coal SW-C, Neo Coal YSK, Neo Coal P (Daiichi Kogyo Seiyaku Co., Ltd.) It is done.

Also, the alkyldiphenyl ether disulfonate anionic surfactant (d1), the polyoxyethylene alkyl ether sulfate ester anionic surfactant (d2), and the alkylbenzene sulfonate anionic surfactant ( At least one anionic surfactant selected from d3) and at least one surfactant selected from the sulfosuccinate anionic surfactant (d4) are based on the total mass part of the solid content. [Anionic surfactant (d1) + anionic surfactant (d2) + anionic surfactant (d3)] / anionic surfactant (d4) = 20/80 to 75/25 (mass ratio) ), Preferably in the range of 44/56 to 70/30 (mass ratio) is desirable for obtaining a coating film excellent in stain resistance, coating film hardness and workability. There.
When the anionic surfactant (d) is blended in the coating composition of the present invention, the blending ratio is 0 with respect to a total solid content of 100 parts by mass of the hydroxyl group-containing resin (a) and the crosslinking agent (b). 0.1 to 20 parts by mass, preferably 2 to 10 parts by mass, more preferably 2 to 6 parts by mass, because a coating film excellent in stain resistance, coating film hardness, and workability can be obtained. Is preferred.

Nitrogen-containing resin (e)
The coating composition of this invention can improve stain resistance by containing nitrogen atom containing resin (e) as needed. Examples of the nitrogen atom-containing resin (e) include resins having nitrogen atom-containing groups such as amino groups, ammonium bases, and amide groups in the molecule, nitrogen atom-containing heterocycles, and the like, for example, epoxy containing nitrogen atoms Examples thereof include resins, modified epoxy resins, acrylic resins, alkyd resins, and polyester resins. Further, the nitrogen atom-containing resin (e) can be used after being neutralized.

  Among the nitrogen atom-containing resins (e), an amino group or quaternary ammonium base-containing polymerizable unsaturated monomer (e11), a polymerizable unsaturated monomer having a nitrogen atom-containing heterocyclic ring (e12), and N-substituted. Copolymerizing a monomer mixture of at least one nitrogen atom-containing polymerizable unsaturated monomer (e1) selected from the (meth) acrylamide compound (e13) which may be added and the other polymerizable unsaturated monomer (e2). The acrylic resin obtained by is preferable for improving the stain resistance.

  Hereinafter, an amino group or quaternary ammonium base-containing polymerizable unsaturated monomer (e11), a polymerizable unsaturated monomer having a nitrogen atom-containing heterocyclic ring (e12), and an N-substituted (meth) acrylamide compound ( At least one nitrogen atom-containing polymerizable unsaturated monomer (e1) selected from e13) may be referred to as “nitrogen atom-containing polymerizable unsaturated monomer (e1)”.

  Examples of the amino group or quaternary ammonium base-containing polymerizable unsaturated monomer (e11) include 2-aminoethyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate, and N, N-dimethylamino. Ethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl ( Amino group-containing aminoalkyl (meth) acrylate monomers such as (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) Acrylamide, N, N-diethylami Amino group-containing (meth) acrylamide compounds such as ethyl (meth) acrylamide, N, N-dipropylaminoethyl (meth) acrylamide, methacryloyloxyethyltrimethylammonium chloride (acrylic ester DMC, trade name, manufactured by Mitsubishi Rayon Co., Ltd.), etc. Examples include quaternary ammonium base-containing unsaturated monomers.

  As the polymerizable unsaturated monomer (e12) having a nitrogen atom-containing heterocyclic ring, (1) for example, a vinylpyropidone compound such as 1-vinyl-2-pyrrolidone and 1-vinyl-3-pyrrolidone, (2) for example, Vinyl pyridine compounds such as 2-vinyl pyridine, 4-vinyl pyridine, 5-methyl-2-vinyl pyridine, 5-ethyl-2-vinyl pyridine, (3) for example, 1-vinyl imidazole, 1-vinyl-2-methyl Vinyl imidazole compounds such as imidazole, (4) vinyl quinoline compounds such as 2-vinyl quinoline, (5) vinyl piperidine compounds such as 3-vinyl piperidine, N-methyl-3-vinyl piperidine, (6) , Morpholine compounds having a polymerizable unsaturated group such as acryloylmorpholine and methacryloylmorpholine It can be mentioned. Among these polymerizable unsaturated monomers (e12) having a nitrogen atom-containing heterocyclic ring, (1) a vinylpyrrolidone compound (preferably 1-vinyl-2-pyrrolidone etc.), (3) a vinylimidazole compound, (6) polymerization A morpholine compound having a polymerizable unsaturated group is preferred, and (1) a vinylpyrrolidone compound and (6) a morpholine compound having a polymerizable unsaturated group are more preferred.

  The N-substituted (meth) acrylamide compound (e13) is a monomer having no amino group, such as acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide butyl ether. N-methylol methacrylamide butyl ether, N-ethyl acrylamide, N-ethyl methacrylamide, Nn-propyl acrylamide, Nn-propyl methacrylamide, N-isopropyl acrylamide, N-isopropyl methacrylamide, N-cyclopropyl acrylamide N-cyclopropyl methacrylamide, diacetone acrylamide, diacetone methacrylamide, N-hydroxymethyl acrylamide, N-hydroxymethyl methacryl Mido, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N-methyl, N -Ethyl acrylamide, N-methyl, N-ethyl methacrylamide, N-methylol acrylamide methyl ether, N-methylol methacrylamide methyl ether, N-methylol acrylamide ethyl ether, N-methylol methacrylamide ethyl ether, N-methylol acrylamide propyl ether N-methylol methacrylamide propyl ether, N-methylol acrylamide butyl ether, N-methylol methacrylamide butyl ether, etc. Can. These monomers can be used alone or in combination of two or more.

  Examples of the other polymerizable unsaturated monomer (e2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. C2-C8 hydroxyalkyl ester of acrylic acid or methacrylic acid, monoesterified product of polyhydric alcohol such as polyethylene glycol mono (meth) acrylate and acrylic acid or methacrylic acid, polyether polyol such as polybutylene glycol Monoether of a hydroxyl group-containing polymerizable unsaturated monomer such as 2-hydroxyethyl (meth) acrylate; ε-caprolactone-modified vinyl obtained by ring-opening polymerization of ε-caprolactone to 2-hydroxyethyl (meth) acrylate Nil monomer (for example, “Placcel FA-1” “Placcel FA-2” “Placcel FA-3” “Placcel FA-4” “Placcel FA-5” “Placcel FM-1” “Placcel FM-2” “Placcel FM-” 3 ”,“ Placcel FM-4 ”,“ Placcel FM-5 ”(all of which are manufactured by Daicel Chemical Industries, Ltd., trade names)) and the like; for example, methyl (meth) acrylate, ethyl ( (Meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, decyl (meth) acrylate, undecyl (Meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate “Osaka Organic Chemical Co., Ltd.”, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, di Acrylic ester compound or methacrylic ester compound which may contain a ring structure having 1 to 24 carbon atoms such as cyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, etc .; styrene, vinyl Aromatic ring-containing vinyl compounds such as toluene and α-methylstyrene; vinyl ester compounds such as vinyl propionate and vinyl acetate; nitrile compounds of acrylonitrile and methacrylonitrile; glycidyl (meth) acrylate , 3,4-epoxycyclohexylmethyl (meth) acrylate, vinylcyclohexene monoepoxide, N-glycidyl acrylamide, allyl glycidyl ether and other epoxy group-containing vinyl compounds; acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc. Carboxylic group-containing vinyl compounds; acid anhydride group-containing vinyl compounds such as maleic anhydride, itaconic anhydride, and hymic anhydride. These can be used alone or in combination of two or more.

  The compounding amount of the nitrogen atom-containing polymerizable unsaturated monomer (e1) and the other polymerizable unsaturated monomer (e2) when producing the nitrogen atom-containing resin (e) is the total amount of the nitrogen atom-containing resin (e). Nitrogen atom-containing polymerizable unsaturated monomer (e1): 5 to 70% by mass, preferably 15 to 65% by mass, other polymerizable unsaturated monomer (e2): 30 to 95% by mass with respect to the total amount of monomer components %, Preferably in the range of 35 to 85% by mass is desirable for improving the coating film performance.

  In particular, the amino group or quaternary ammonium base-containing polymerizable unsaturated monomer (e11) is 1 to 30% by mass, preferably 5 to 25% by mass, based on the total amount of all monomers constituting the nitrogen atom-containing resin (e). %, A polymerizable unsaturated monomer having a nitrogen atom-containing heterocyclic ring (e12) 4 to 60% by mass, preferably 10 to 55% by mass, and an N-substituted (meth) acrylamide compound (e13) 0 to 20 % By mass, preferably 0-15% by mass ("0% by mass" means not blended), and other polymerizable unsaturated monomer (e2) 30-95% by mass, preferably 35-85% by mass It is preferable that it is in the range from the viewpoint of the durability of the coating film to stain resistance, the coating film hardness, and the workability.

  As a method for obtaining a nitrogen atom-containing resin (e) by copolymerizing a monomer mixture comprising the nitrogen atom-containing polymerizable unsaturated monomer (e1) and the other polymerizable unsaturated monomer (e2), a radical known per se is used. A polymerization method is preferably used, and a bulk polymerization method, a solution polymerization method, a bulk-suspension two-stage polymerization method in which suspension polymerization is performed after the bulk polymerization, and the like can be used.

  As a method for obtaining the nitrogen atom-containing resin (e), any known method can be used, and the solution polymerization method is particularly preferable. Examples of the method by the solution polymerization method include a method in which the monomer mixture is dissolved or decomposed in an organic solvent and heated in the presence of a polymerization initiator with stirring at a temperature of usually about 80 ° C to 200 ° C. . The reaction time is usually preferably 1 to 10 hours.

  In the production of the nitrogen atom-containing resin (e), as the polymerization initiator, a polymerization initiator generally used in a production method such as an acrylic polymer is used, and the amount thereof is usually a nitrogen atom-containing polymerizable unsaturated monomer. It exists in the range of 0.1-20 mass% with respect to the total amount of (e1) and another polymerizable unsaturated monomer (e2).

    Examples of the polymerization initiator include azo polymerization initiators such as 2,2′-azobisisobutylnitrile, azobis-2-methylbutyronitrile, azobisdivaleronitrile; t-butylperoxyisobutyrate, t -Butylperoxy-2-ethylhexanoate, t-amylperoxy 3,5,5-trimethylhexanoate, t-butylperoxyisopropyl carbonate, 2,2-bis (4,4-di-t-butyl Peroxycyclohexyl) propane and other organic peroxide polymerization initiators.

    Examples of the organic solvent include hydrocarbon solvents such as heptane, toluene, xylene, octane and mineral spirit; ester solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, and diethylene glycol monobutyl ether acetate; Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone; alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, sec-butanol, isobutanol; n-butyl ether, dioxane, ethylene glycol monomethyl ether, ethylene Ether solvents such as glycol monoethyl ether; SWAZOL 310, SWAZOL 1000, SWAZOL 15 manufactured by Cosmo Oil Co., Ltd. Aromatic such as 0 petroleum solvents and the like.

    These organic solvents can be used alone or in combination of two or more. At the time of copolymerization, the organic solvent is usually used in a range of 400% by mass or less based on the total amount of the nitrogen atom-containing polymerizable unsaturated monomer (e1) and the other polymerizable unsaturated monomer (e2). Is done.

    In the copolymerization reaction to obtain the nitrogen atom-containing resin (e), the method for adding the monomer component and the polymerization initiator is not particularly limited, but the polymerization initiator is from the initial polymerization stage to the late polymerization stage rather than being charged all at the initial stage of polymerization. It is preferable to divide and drop over the range from the viewpoint of suppressing the formation of defective cross-linked products.

    The nitrogen atom-containing resin (e) obtainable by the copolymerization reaction has a weight average molecular weight of 5,000 to 30,000, more preferably 8,000 to 20,000. It is suitable from the viewpoint of easy handling (resin viscosity not very high), coating film hardness, and workability.

  The weight average molecular weight is when the nitrogen atom-containing resin (e) is a nitrogen atom-containing resin (e) having at least one group selected from an amino group, an ammonium group, and a nitrogen atom-containing heterocyclic ring in the molecule. , "HLC-8120GPC" (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph, and "TSKgel Super-H3000" and two "TSKgel Super-H2500" (Tosoh) are used as columns. Using a differential refractometer as a detector, tetrahydrofuran (containing 0.5% by mass of triethanolamine), measurement temperature 25 ° C., flow rate It can be determined under the condition of 0.6 mL / min.

When the nitrogen atom-containing resin (e) is blended in the coating composition of the present invention, the blending ratio is:
0.1 to 20 parts by weight, preferably 2 to 16 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the total solid content of the hydroxyl group-containing resin (a) and the crosslinking agent (b). Is preferable because a coating film excellent in stain resistance, coating film hardness and processability can be obtained.

Ionic liquid (f)
The coating composition of this invention can contain an ionic liquid (f) as needed for the purpose of improving stain resistance. The ionic liquid (f) is a liquid compound salt composed only of ions (anions, cations). Examples of the anionic component of such an ionic liquid (f) include halide ions, SCN ⁻ , BF ⁴⁻ , ClO ⁴⁻ , PF ^6−, (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ CF ₂ SO ₂ ) ₂ N ⁻ , CF ₃ SO ₃ ⁻ , CF ₃ COO ⁻ , Ph ₄ B ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , PF ₃ (C ₂ F ₅ ) ₃ ^{— and the} like. Examples of the cation component include ammonium ions. Specifically, as the ionic liquid (f), for example, an ionic liquid described in JP 2012-72130 A can be used.

  Commercially available ionic liquids (f) include, for example, amino ion AS100, amino ion AS200, amino ion AS300, amino ion AS400 (above, Japanese emulsifier, trade name); Elexcel IL-110, Elexcel IL-120, Elexcel IL -220, Elexcel IL-230 (above, Daiichi Kogyo Seiyaku, trade name).

  When the ionic liquid (f) is used in the coating composition of the present invention, the blending ratio is 0.1 with respect to 100 parts by mass of the total solid content of the hydroxyl group-containing resin (a) and the crosslinking agent (b). It is suitable for improving paint stability and stain resistance to be in the range of ˜20 parts by mass, preferably 0.2 to 10 parts by mass, more preferably 0.5 to 6 parts by mass.

Other components In addition, the coating composition of the present invention includes, as necessary, other components such as a lubricity imparting agent, a pigment such as a coloring pigment, an extender pigment, and a rust preventive pigment, a curing catalyst, a pigment dispersant, and an ultraviolet absorber. Agents, UV stabilizers, antifoaming agents, surface conditioners, cationic surfactants, fluorosurfactants, matting agents such as resin particles and fine silica powder, organic solvents, etc. A known material can be contained.

  As the above-mentioned lubricity-imparting agent, conventionally known lubricants in the paint field can be used as long as they can impart slipperiness to the coating surface without deteriorating the appearance of the coating surface. Examples include polyolefin waxes such as polyethylene wax; polyether-modified silicone oil, higher fatty acid ester-modified silicone oil, modified silicone oil such as higher alkoxy-modified silicone oil; paraffin wax such as microcrystalline wax; montan wax, lanolin wax, carna Examples thereof include fatty acid ester waxes such as uba wax, beeswax and whale wax, and fluorine waxes such as ethylene tetrafluoride.

  Specific examples of the pigment include white pigments such as titanium white and zinc white; blue pigments such as cyanine blue and indanthrene blue; green pigments such as cyanine green and patina; organic red pigments such as azo and quinacridone. Inorganic red pigments such as Bengala; organic yellow pigments such as benzimidazolone, isoindolinone, isoindoline, and quinophthalone; yellow pigments such as titanium yellow, yellow lead, and yellow iron oxide; carbon black, graphite, pine Color pigments such as black pigments such as smoke; extender pigments such as clay, talc, barita and calcium carbonate; rust preventive pigments such as aluminum tripolyphosphate, zinc molybdate and vanadium pentoxide;

  The cationic surfactant can be appropriately selected depending on the purpose, and examples thereof include alkylamine cationic surfactants and quaternary ammonium salt cationic surfactants.

  Specifically, alkylamine cationic surfactants such as coconut amine acetate and stearylamine acetate; lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, And quaternary ammonium salt cationic surfactants such as alkylbenzyldimethylammonium chloride.

  Commercially available products of the above-mentioned cationic surfactants include acetamine 24, acetamine 86 (above, manufactured by Kao Corporation, alkylamine-based cationic surfactant), DISPER BYK-108, DISPER BYK-109, DISPER BYK-116, DISPER. BYK-161 (above, manufactured by Big Chemie Japan, alkylamine-based cationic surfactant), Coatamine 24P, Cotamin 86P Conch, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizole C, Sanizole B-50 (above, Kao Corporation Manufactured, quaternary ammonium salt cationic surfactant), cationogen TML, cationogen TMP, cationogen TMS, cationogen ES-O, cationogen ES-L, cationogen ES-P, cationogen DDM-PG, kathi Gen S, Kachiogen BC-50, Kachiogen D2, Kachiogen TBB (or, Dai-ichi Kogyo Seiyaku Co., quaternary ammonium salt type cationic surfactant), and the like.

  Examples of the fluorosurfactant include a sulfonate type containing a perfluoroalkyl group, a carboxylate type containing a perfluoroalkyl group, a sulfonate type containing a perfluoroalkenyl group, and a perfluoroalkenyl. Carboxylate type anionic fluorosurfactant containing a group; Betaine amphoteric fluorosurfactant containing a perfluoroalkyl group; Quaternary ammonium containing a perfluoroalkyl group or a perfluoroalkenyl group Salt-type cationic fluorosurfactants; nonionic fluorosurfactants such as ethylene oxide adducts containing perfluoroalkyl groups, amine oxides containing perfluoroalkyl groups, and oligomers containing perfluoroalkyl groups Agents.

  Among the above-mentioned fluorosurfactants, a quaternary ammonium salt type cationic fluorosurfactant containing a perfluoroalkyl group or a perfluoroalkenyl group is preferred for improving the stain resistance. Commercially available products can be used as the fluorosurfactant. For example, aftergent 100, aftergent 310, aftergent 320, aftergent 501L (above, manufactured by Neos), BYK-300, BYK-333, BYK-355. , BYK-356, BYK-358N (above, manufactured by BYK Japan, Inc., trade name) and the like. The above-mentioned fluorosurfactants can be used alone or in combination of two or more.

  The curing catalyst is blended as necessary to promote the reaction between the hydroxyl group-containing resin (a) and the crosslinking agent (b). When the crosslinking agent (b) is an amino resin, A sulfonic acid compound or an amine neutralized product of a sulfonic acid compound is preferably used.

  Representative examples of the sulfonic acid compound include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, and the like. The amine in the amine neutralized product of the sulfonic acid compound may be any of primary amine, secondary amine, and tertiary amine. Among these, the amine neutralized product of p-toluenesulfonic acid and / or the amine neutralized product of dodecylbenzenesulfonic acid is preferable from the viewpoints of coating stability, reaction promoting effect, and obtained coating film properties.

  When the crosslinking agent (b) is a blocked polyisocyanate compound, examples of the curing catalyst include tin octylate, dibutyltin di (2-ethylhexanoate), dioctyltin di (2-ethylhexanote), Mention may be made of organometallic compounds such as dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, monobutyltin trioctate, lead 2-ethylhexinate and zinc octylate.

  When a curing catalyst is used in the coating composition of the present invention, the blending ratio is 0.1 to 5. with respect to 100 parts by mass of the total solid content of the hydroxyl group-containing resin (a) and the crosslinking agent (b). 0 mass part, Preferably 0.2-1.5 mass parts is suitable from the surface of coating-film hardness.

Examples of the resin particles include powdered products obtained by pulverizing a resin obtained by a condensation reaction between urea and an aldehyde component, and an average particle size of 1 to 10 μm, preferably 2 to 8 μm is suitable. ing. The average particle diameter is a median diameter (d50) value of a volume-based particle size distribution measured by a laser diffraction scattering method using MT3300 (manufactured by Nikkiso Co., Ltd., trade name, Microtrac particle size distribution measuring device). As the aldehyde component, formaldehyde, acetaldehyde, crotonaldehyde, benzaldehyde or the like can be used. Among these, when formaldehyde is used, the condensation reaction is easy to proceed, which is convenient.
Examples of commercially available resin particles include Pergo Pack M3, Pergo Pack M4, Pergo Pack M5 (Lonza Japan, trade name), SOOFINE JJ POWDER (Hangzhou Seika Kogyo, trade name), and the like.

  The resin particles to be blended in the coating composition of the present invention can be blended according to the degree of the desired matte coating film when the matte coating film is used. Usually, resin particles are in the range of 1 to 50 parts by weight, preferably 2 to 30 parts by weight, more preferably 3 to 15 parts by weight with respect to 100 parts by weight of the total solid content of a) and the crosslinking agent (b). It is desirable from the viewpoint of obtaining paint stability and a matte coating film.

  The coating composition of the present invention comprises a hydroxyl group-containing resin (a), a crosslinking agent (b), an antifouling agent (c), if necessary, an anionic surfactant (d), a nitrogen atom-containing resin (e). The ionic liquid (f) and the other components can be uniformly mixed.

  When applying the coating composition of the present invention, Ford Cup No. It is desirable to adjust the solid content concentration within a range of 20 to 60% by mass, preferably 30 to 50% by mass so that a viscosity in a range of 10 to 100 seconds is obtained at 4 (20 ° C.).

Coating film forming method A coating film forming method using the coating composition of the present invention comprises forming a primer coating film on one side or both sides of a metal plate, and using the coating composition on at least one side of the primer coating film. Form a top coat.

  Examples of the metal plate to be coated include cold-rolled steel plate, hot-dip galvanized steel plate, electrogalvanized steel plate, alloy galvanized steel plate (alloy galvanized steel plate such as iron-zinc, aluminum-zinc, nickel-zinc). , Aluminum plate, stainless steel plate, copper plate, copper plated steel plate, tin plated steel plate and the like.

  If the surface of the metal plate is not contaminated with oil or other contaminants, the primer may be applied as it is, but it is desirable to perform degreasing and metal surface treatment in order to improve adhesion to the coating film and corrosion resistance. . Known surface treatment methods for metal plates include phosphate surface treatment, chromate surface treatment, zirconium surface treatment and the like.

  As a primer paint for forming a primer coating on a metal plate, a primer paint used in the colored color steel sheet coating field, industrial machine coating field, metal part coating field and the like can be applied. From the viewpoint of environmental protection, it is preferable to use a chromium-free primer coating that does not contain a chromium-based rust preventive component.

  The chromium-free primer coating is appropriately selected depending on the type of metal plate or metal surface treatment, and in particular, an epoxy-based primer coating, a polyester-based primer coating, and their modified primer coating are suitable, and workability is particularly required. In this case, a polyester primer paint is suitable. The primer coating is applied by a known coating method such as roll coating or spray coating so that the dry film thickness is 1 to 30 μm, preferably 2 to 20 μm, and usually at an ambient temperature of 80 to 300 ° C. When coil coating is applied for about 5 seconds to 1 hour, a primer coating film can be obtained by heating and curing for 15 seconds to 120 seconds under the condition that the maximum material reaching temperature is 140 to 250 ° C.

  The primer coating film may be a single layer or two layers in which a second primer coating film (intermediate coating film) is formed on the first primer coating film. When the primer film has two layers, the first primer film has an anticorrosion function, and the second primer film (intermediate film) has processability and chipping resistance. The primer coating can also have different functions.

  In the coating film forming method, the coating composition of the present invention which is a top coating is applied on at least one side of the primer coating. Examples of the coating method include curtain coating, roll coater coating, dip coating, and spray coating. Usually, the coating is performed so that the dry film thickness is in the range of 5 to 50 μm, preferably 8 to 30 μm.

  When the coating composition of the present invention is applied by coil coating, the coating method is not limited, but curtain coating and roll coater coating are recommended in view of the economics of coil coating. When roll coater coating is applied, the bottom feed method (so-called reverse coating or natural coating) using a normal two-roll system is practically performed, but the uniformity of the coating surface is best. Therefore, a top feed or bottom feed method using three rolls can be performed.

  The conditions for curing the coating film with the coating composition of the present invention are usually about 15 to 30 minutes at a material maximum temperature of 120 to 260 ° C. In the field of pre-coating, which is applied by coil coating or the like, it is usually carried out at a raw material maximum temperature of 160 to 260 ° C. for a baking time of 15 to 90 seconds.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The present invention is not limited in any way by the following examples. Hereinafter, both “parts” and “%” are based on mass.

Production and Production Example 1 of Polyester Resin Polyester Resin Solution No. Production of No. 1 A reactor equipped with a thermometer, a stirrer, a heating device and a rectifying tower was charged with the following “mixture (1)”, heated to 160 ° C., and gradually from 160 ° C. to 230 ° C. over 3 hours. The temperature was raised to. Next, after continuing the reaction at 230 ° C. for 30 minutes, the rectifying column is replaced with a water separator, xylene is added to the contents, xylene is also added to the water separator, and water and xylene are azeotropically condensed. After removing water and reacting until the acid value reached 5 mgKOH / g, the reaction mixture was cooled, cyclohexanone was added to the reaction product, and a polyester resin solution No. 5 having a solid content of 55% was added. 1 was obtained. The obtained resin had an acid value of 5 mgKOH / g, a hydroxyl value of 72 mgKOH / g, and a number average molecular weight of 3,100.
“Mixture (1)”
Isophthalic acid 0.6 mol
Adipic acid 0.3 mol
1,4-cyclohexanedimethanol 0.3 mol
Neopentyl glycol 0.6 mol
Trimethylolpropane 0.1 mol.

Production Example 2 Polyester resin solution No. 2. Production of polyester resin solution No. 2 in the same manner as in Production Example 1 except that the contents of Table 1 are used. 2 was obtained.

Production Example 3 Polyester resin solution No. Production of No. 3 A reactor equipped with a thermometer, a stirrer, a heating device and a rectifying tower was charged with “mixture (2)”, heated to 160 ° C. and gradually from 160 ° C. to 230 ° C. over 3 hours. The temperature rose. Next, after continuing the reaction at 230 ° C. for 30 minutes, the rectifying column is replaced with a water separator, xylene is added to the contents, xylene is also added to the water separator, and water and xylene are azeotropically condensed. Water was removed, the reaction was allowed to proceed until the acid value became 3 mgKOH / g or less, the mixture was cooled, 0.5 mol of hexahydrophthalic anhydride was added at 140 ° C., held at 140 ° C. for 2 hours, and then cooled.
Thereafter, cyclohexanone was added to the reaction product to obtain polyester resin No. 5 having a solid content of 55%. Three solutions were obtained. The obtained resin had an acid value of 33 mgKOH / g, a hydroxyl value of 137 mgKOH / g, and a number average molecular weight of 2,400.
"Mixture (2)"
Hexahydrophthalic anhydride 0.5 mol Isophthalic acid 0.4 mol 3,3-pentanedimethanol 0.2 mol Neopentyl glycol 0.2 mol Trimethylolpropane 0.6 mol.

Production Example 4 Polyester resin solution No. 4 Production of polyester resin No. 4 in the same manner as in Production Example 3 except that the contents of Table 1 were used. Four solutions were obtained.

Production Example of Nitrogen Atom-Containing Resin (e) Production Example 5 Nitrogen atom-containing resin No. 5 1 Preparation of solution To a 4 liter flask equipped with a thermometer, reflux condenser and stirrer, 28 parts of Swazol 1000 (Cosmo Oil Co., Ltd., aromatic hydrocarbon organic solvent) and 85 parts of toluene were added. A mixture of 15 parts N, N-dimethylaminoethyl methacrylate, 50 parts 1-vinyl-2-pyrrolidone, 15 parts 2-hydroxyethyl methacrylate, 20 parts 2-ethylhexyl methacrylate and 4 parts azobismethylbutyronitrile, The reaction was carried out at 110 ° C. under nitrogen gas. Next, solid content was adjusted with toluene, and nitrogen atom-containing resin No. 5 having a solid content of 55% by mass was obtained. One solution was obtained. Nitrogen atom-containing resin no. The solid content of one solution had an amine value of 35 mgKOH / g, a hydroxyl value of 33 mgKOH / g, and a weight average molecular weight of 11,000.

  Production Examples 6 to 9 Nitrogen atom-containing resin No. 2 solution to No. 2 5 Production of Solution A nitrogen atom-containing resin No. 5 was prepared in the same manner as in Production Example 5 except that the monomer mixture having the composition shown in Table 2 was used. 2 solution to No. 2 Five solutions were obtained.

(Note 1) Acryester DMC78: Mitsubishi Rayon Co., Ltd., trade name, methacryloyloxyethyltrimethylammonium chloride, quaternary ammonium base-containing polymerizable saturated monomer
(Note 2) Plaxel FM-3: Daicel Chemical Industries, trade name, ε-caprolactone modified vinyl monomer of 2-hydroxyethyl methacrylate.

Production Example 10 of Antifouling Agent (c) Production Example 10 Production of Antifouling Agent A Air in a 1 liter flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet was replaced with nitrogen, and isostearyl 100 parts of acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 310 parts of propylene glycol monomethyl ether were added and stirred at room temperature.
Next, a solution prepared by dissolving 54.8 parts of sodium mercaptopropanesulfonate and 0.16 part of triethylamine in 55 parts of deionized water was added to the flask over 30 minutes. Thereafter, the reaction solution in the flask was kept at 40 ° C. or lower for 3 hours while stirring to obtain a compound. As a result of 1H-NMR measurement analysis, the obtained compound was antifouling agent A (Note 5) having the following structural formula.

  (Note 5) Antifouling agent A:

Production Example 11 Production of Antifouling Agent B Air in a 1 liter flask equipped with a stirrer, thermometer, condenser, nitrogen gas inlet was replaced with nitrogen, 100 parts of 2-ethylhexyl acrylate, propylene glycol monomethyl ether 360 Part was added and stirred at room temperature.
Next, a solution prepared by dissolving 96.9 parts of sodium mercaptopropanesulfonate and 0.20 part of triethylamine in 100 parts of deionized water was added to the flask over 30 minutes. Thereafter, the reaction solution in the flask was kept at 40 ° C. or lower for 3 hours while stirring to obtain a compound. As a result of 1H-NMR measurement analysis, the obtained compound was antifouling agent B (Note 6) having the following structural formula.

  (Note 6) Antifouling agent B:

Production Example 12 Production of Antifouling Agent C Air in a 1 liter flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet was replaced with nitrogen, and isostearyl acrylate (Osaka Organic Chemical Co., Ltd.) 100 And 100 parts of methanol were added and stirred at room temperature.

  Next, a solution prepared by dissolving 70.6 parts of trimethylammonium mercaptopropanesulfonate and 1.8 parts of triethylamine in 298 parts of methanol was added to the flask over 30 minutes. Thereafter, the reaction solution in the flask was kept at 40 ° C. or lower for 3 hours while stirring to obtain a compound. As a result of 1H-NMR measurement analysis, the obtained compound was antifouling agent C (Note 7) having the following structural formula.

  (Note 7) Antifouling agent C:

Production Example 13 Production of antifouling agent D Air in a 1 liter flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet was replaced with nitrogen, and 100 parts of 2- (perfluorobutyl) ethyl acrylate, 62 parts of methanol was added and stirred at room temperature.

  Next, a solution prepared by dissolving 56 parts of sodium mercaptopropanesulfonate and 0.16 part of triethylamine in 102 parts of deionized water was added to the flask over 30 minutes. Thereafter, the reaction solution in the flask was kept at 40 ° C. or lower for 3 hours while stirring to obtain a compound. As a result of 1H-NMR measurement analysis, the obtained compound was antifouling agent D (Note 8) having the following structural formula.

  (Note 8) Antifouling agent D:

Production Example 14 Production of Antifouling Agent E The air in a 1 liter flask equipped with a stirrer, thermometer, condenser, nitrogen gas inlet was replaced with nitrogen, and isostearyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 300 parts of propylene glycol monomethyl ether was added and stirred at room temperature.
Next, a solution prepared by dissolving 45.3 parts of sodium aminoethanesulfonate in 200 parts of methanol and 18 parts of deionized water was added to the flask over 30 minutes. Thereafter, the reaction solution in the flask was kept at 40 ° C. or lower for 3 hours while stirring to obtain a compound.
As a result of 1H-NMR measurement analysis, the obtained compound was antifouling agent E (Note 9) having the following structural formula.

  (Note 9) Antifouling agent E:

Production Example 15 Production of Antifouling Agent F Air in a 1-liter flask equipped with a stirrer, thermometer, condenser, nitrogen gas inlet was replaced with nitrogen, 100 parts of 4-hydroxybenzoic acid benzyl ester, sodium methoxy 23.7 parts of toluene and 200 parts of toluene were added and stirred at room temperature for 2 hours. Thereafter, the produced methanol was distilled off under reduced pressure.
Next, a solution prepared by dissolving 53.5 parts of 1,3-propane sultone in 200 parts of toluene was added to the flask over 30 minutes. Thereafter, the reaction solution in the flask was kept at 60 ° C. for 3 hours with stirring to obtain a compound. As a result of 1H-NMR measurement analysis, the obtained compound was antifouling agent F (Note 10) having the following structural formula.

  (Note 10) Antifouling agent F:

Production Example 16 Production of antifouling agent G Air in a 1 liter flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet was replaced with nitrogen, and 50 parts of glycine benzyl ester and 200 parts of methanol were added. And stirred at room temperature for 2 hours.
Next, a solution prepared by dissolving 79 parts of 1,3-propane sultone in 185 parts of methanol was added to the flask over 30 minutes. The reaction solution in the flask is kept at room temperature for 3 hours while stirring, and then kept at 35 ° C. for 3 hours. Next, 48.5 parts of 50% aqueous sodium hydroxide solution is added and stirred for 30 minutes to obtain a compound. It was. As a result of 1H-NMR measurement analysis, the obtained compound was antifouling agent G (Note 11) having the following structural formula.

  (Note 11) Antifouling agent G:

Production Example 17 Production of Antifouling Agent H Air in a 1 liter flask equipped with a stirrer, thermometer, condenser, nitrogen gas inlet was replaced with nitrogen, and isostearyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 100 parts and 300 parts of propylene glycol monomethyl ether were added and stirred at room temperature.

  Next, a solution prepared by dissolving 22.6 parts of sodium aminoethanesulfonate in 100 parts of methanol and 9 parts of deionized water was added to the flask over 30 minutes. Thereafter, the reaction solution in the flask was kept at 40 ° C. or lower for 5 hours while stirring to obtain a compound. As a result of 1H-NMR measurement analysis, the obtained compound was antifouling agent H (Note 12) having the following structural formula.

  (Note 12) Antifouling agent H:

Production Example 18 Production of Antifouling Agent I Air in a 1 liter flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet was replaced with nitrogen, and isostearyl acrylate (Osaka Organic Chemical Industries, Ltd.) 100 And 200 parts of propylene glycol monomethyl ether were added and stirred at room temperature.
Next, a solution obtained by dissolving 39.5 parts of sodium mercaptopropionate in 42 parts of propylene glycol monomethyl ether and 6 parts of ionic water was added to the flask over 30 minutes. Thereafter, the reaction solution in the flask was kept at 40 ° C. or lower for 3 hours while stirring to obtain a compound. As a result of 1H-NMR measurement analysis, the obtained compound was antifouling agent I (Note 13) having the following structural formula.

  (Note 13) Antifouling agent I:

Production Example 19 Production of Antifouling Agent J Air in a 1 liter flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet was replaced with nitrogen, and isostearyl acrylate (Osaka Organic Chemical Co., Ltd.) 100 And 200 parts of propylene glycol monomethyl ether were added and stirred at room temperature.
Next, a solution prepared by dissolving 49.6 parts of sodium N-methylaminoethanesulfonate in 100 parts of propylene glycol monomethyl ether and 25.5 parts of deionized water was added to the flask over 30 minutes. Thereafter, the reaction solution in the flask was kept at 40 ° C. or lower for 3 hours while stirring to obtain a compound. As a result of 1H-NMR measurement analysis, the obtained compound was antifouling agent J (Note 14) having the following structural formula.

  (Note 14) Antifouling agent J:

Comparative Production Example 1 Production of antifouling agent K In a 1 liter flask equipped with a stirrer, thermometer, condenser, and air bubbling device, 100 parts of isostearyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), p- 0.22 part of methoxyphenol and 192 parts of ethylene glycol monobutyl ether were added and stirred at room temperature.
Next, a solution prepared by dissolving 64 parts of sodium bisulfite and 12.3 parts of sodium hydroxide in 192 parts of deionized water was added to the flask over 30 minutes. Thereafter, air was bubbled through the reaction solution in the flask, and the mixture was maintained at 100 ° C. for 2 hours with vigorous stirring to obtain a compound. As a result of 1H-NMR measurement analysis, the obtained compound was antifouling agent K (Note 15) having the following structural formula.

It was antifouling agent K (Note 15) having the following structural formula.
(Note 15) Antifouling agent K:

  Example 1 Coating composition no. Production of polyester resin solution No. 1 obtained in Production Example 1 1 (80 parts (solid content), Cymel 303 (note 3) 20 parts (solid content), antifouling agent A (note 5) 6 parts (solid content) obtained in Production Example 10 and Typeke CR-95 ( Note 21) An organic solvent (a mixed solvent of cyclohexanone / swazol 1500 = 40/60 (mass ratio)) is added to 120 parts and 0.5 part of dodecylbenzenesulfonic acid for dilution, and the viscosity is 80 seconds (Ford Cup # 4, 25 ° C.) coating composition No. 1 was obtained.

  Examples 2-40 Coating composition No. 2-No. Production of No. 40 In the same manner as in Example 1 except that the contents shown in Tables 3 to 4 were used, the coating composition No. 2-No. 40 was obtained.

Comparative Example 1 Paint composition No. Production of polyester resin No. 41 obtained in Production Example 1 1 part 100 parts (solid content), antifouling agent A (Note 5) 6 parts (solid content), Type C CR-95 (Note 21) 120 parts, dodecylbenzenesulfonic acid 0.5 part, organic solvent (cyclohexanone / The mixture was diluted by adding a mixed solvent of SWAZOL 1500 and 40/60), and the coating composition No. having a viscosity of 80 seconds (Ford Cup # 4, 25 ° C.) 41 was obtained.

Comparative Examples 2 to 17 Coating composition No. 42-No. Manufacture of 57
Except for the contents shown in Table 5, the coating composition No. 42-No. 57 was obtained.

(Note 3) Cymel 303: Daicel Ornex Co., Ltd., trade name, methyl etherified melamine resin (Note 4) Sumijour BL3175: Sumika Bayer Urethane Co., Ltd., trade name, methyl ethyl ketoxime blocked, hexamethylene diisocyanate nurate (Note 16) New Coal 271-A: Nippon Emulsifier Co., Ltd., trade name, alkyl diphenyl ether disulfonic acid anionic surfactant (d1)
(Note 17) New Coal 707SN: manufactured by Nippon Emulsifier Co., Ltd., trade name, polyoxyethylene alkyl ether sulfate-based anionic surfactant (d2)
(Note 18) New Coal 210: Nippon Emulsifier Co., Ltd., trade name, alkylbenzene sulfonate anionic surfactant (d3)
(Note 19) New Coal 290-A: Nippon Emulsifier Co., Ltd., trade name, sulfosuccinic acid anionic surfactant (d4)
(Note 20) Amino ion AS100: manufactured by Nippon Emulsifier Co., Ltd., trade name, ionic liquid (f)
(Note 21) Taipei CR-95: Ishihara Sangyo Co., Ltd., trade name, titanium white
(Note 22) MKC silicate MS56S: Mitsubishi Chemical Corporation, trade name, methyl esterified silicate which is a condensate of tetramethoxysilane (Note 23) MKC silicate MS58B30: Mitsubishi Chemical Corporation, trade name, condensate of tetraalkoxysilane A methyl / butyl mixed esterified silicate.

Preparation of test plates Paint compositions obtained in the above examples and comparative examples on a zinc-aluminum alloy plated steel plate (GL material, plate thickness 0.35 mm) on which a primer coating film having a dry film thickness of 3 μm was formed using a roll coater Item No. 1-No. 57 were each coated to a dry film thickness of 18 μm, and baked for 40 seconds under the condition that the maximum material arrival temperature was 220 ° C. to obtain each test plate. Tables 3 to 5 show the results of testing using each test plate according to the test conditions described below.

(Note 24) Fume generation: Using the test set of the model diagram shown in FIG. 1, fume generated from the coated plate was evaluated by the following process.
Step 1: The test plate (1) is preheated at 140 ° C. for 3 minutes.
Step 2: Next, a preheated test plate (1) is placed on a hot plate (3) that has been set to 230 ° C., and the test plate (1) is mounted with a vacuum (2) for preventing fumes coming out of the painted plate from escaping. Enclose.
Step 3: Place a steel plate (4) on the back plate (2) to collect fumes from the paint plate, and put a 4 liter round can (5) with ice water on the steel plate (4). Put it on and leave it for 40 seconds to cool the generated fumes immediately.
Step 4: The test plate (1) was renewed and the operations of Steps 1 to 3 were repeated 10 times. Thereafter, the steel plate (4) was taken out and the appearance was evaluated according to the following criteria.
Shows slight interference of fume on steel plate (4) but no interference. ○ shows that fume adheres to steel plate (4).
For Δ, fume adheres to the steel plate (4), a sense of interference is observed, and adhesion of spear is observed.
In x, fume adheres to the steel plate (4), and it is cloudy or the adhesion of spear is remarkably observed.

  (Note 25) Appearance of the initial coating surface: ○ indicates no coating surface abnormality or cloudiness such as repellency, dents, or irregularities on the coating surface. Δ indicates no coating surface abnormality such as repellency, dents, or irregularities, but clouding is observed on the coating surface. In x, an abnormality in the paint surface such as repellency, dents, or irregularities is observed on the paint surface.

(Note 26) Pencil hardness:
About the coating film of a test board, the pencil scratch test prescribed | regulated to JISK5600-5-4 (1999) was done, and the evaluation by the tearing of a coating film was performed. Higher hardness is preferred.

(Note 27) Outdoor exposure test:
Attach an outdoor exposure test piece (test plate cut to a size of 100 x 300 mm) at an angle of 4 degrees from the vertical so that the coating film faces the north side on a mounting table that models the eaves. An exposure test was conducted on the rooftop of Kansai Paint Co., Ltd. in Ota-ku, Tokyo, and the color difference (ΔE) from the initial coated plate in “2 months after the start of exposure” and “24 months after the start of exposure” was based on JIS Z8370. It was measured using a multi-light source spectrocolorimeter MSC-5N manufactured by Suga Test Instruments Co., Ltd. and evaluated according to the following criteria. ◎: △ E is less than 1 ○: △ E is 1 or more and less than 2 △: ΔE is 2 or more and less than 5, ×: ΔE is 5 or more.

(Note 28) Workability:
In a room at 20 ° C., the test plate was bent 180 degrees with a vise with the coating surface on the outside, and the T number at which no crack occurred at the bent portion was displayed. The T number is 0T when bending 180 degrees without anything inside the bent part, 1T, 2 when a sheet of the same thickness as the test plate is folded. In the case of a sheet, 2T,... (The same applies hereinafter)... The results were determined by: ◎: No cracking is observed in 2T folding process ○: Cracking is recognized in 2T folding process, but cracking is not observed in 4T folding process △: Cracking is recognized in 4T folding process However, cracks are not recognized in the 6T folding process. × indicates cracks in the 6T folding process.

  (Note 29) 60 degree specular gloss: 60 degree specular reflectivity was measured according to the 60 degree specular gloss specified in JIS Z 8741 (1997).

  It is possible to reduce the amount of fumes generated during baking, maintain a stain resistance over a long period of time when exposed outdoors, and provide a coated plate with good workability.

1. 1. Waku not to let the fumes from the paint plate escape. 2. Paint plate 3. Hot plate 4. Steel plate for collecting fumes from the painted plate. 4 liter round cans with ice water to cool generated fumes immediately

Claims (5)

A coating composition containing a hydroxyl group-containing resin (a), a crosslinking agent (b) and a stain resistance agent (c) represented by the following formula (1), wherein the hydroxyl group-containing resin (a) and the crosslinking agent (b) The coating composition contains 0.1 to 10 parts by mass of the antifouling agent (c) with respect to 100 parts by mass of the total solid content.
Antifouling agent (c):

Formula (1)
(In Formula (1), X represents a group selected from a sulfonic acid group, a sulfonic acid group, a carboxyl group, and a carboxylic acid group, and Y has a sulfur atom, an oxygen atom, and a linear or branched nitrogen atom. Represents an atom or group selected from a group, R ¹ represents a group selected from an alkylene group, a phenylene group and a phenylalkylene group having 1 to 8 carbon atoms, and R ² represents an alkylene group having 1 to 8 carbon atoms. And R ³ represents a group selected from an alkyl group, a fluorinated alkyl group, a phenyl group, and an aralkyl group having 6 to 24 carbon atoms. The anionic surfactant (d) described below is contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the hydroxyl group-containing resin (a) and the crosslinking agent (b). Paint composition.
Anionic surfactant (d):
Alkyldiphenyl ether disulfonate-based anionic surfactant (d1), polyoxyethylene alkyl ether sulfate-based anionic surfactant (d2), alkylbenzenesulfonate-based anionic surfactant (d3) and At least one anionic surfactant selected from sulfosuccinate-based anionic surfactants (d4) The amount of the nitrogen atom-containing resin (e) having the following characteristics is 0.1 to 20 parts by mass with respect to 100 parts by mass of the solid content of the hydroxyl group-containing resin (a) and the crosslinking agent (b). The coating composition as described.
Nitrogen atom-containing resin (e):
An amino group or a quaternary ammonium base-containing polymerizable unsaturated monomer (e11), a polymerizable unsaturated monomer having a nitrogen atom-containing heterocyclic ring (e12) and N-substituted with respect to the total amount of all the constituent monomers. 5 to 70% by mass of at least one nitrogen atom-containing polymerizable unsaturated monomer (e1) selected from the (meth) acrylamide compound (e13), and 30 to 95% by mass of other polymerizable unsaturated monomer (e2). % Monomer mixture copolymer resin In any one of Claims 1-3 which contain 0.1-20 mass parts of ionic liquids (f) with respect to 100 mass parts of solid content total of hydroxyl-containing resin (a) and a crosslinking agent (b). The coating composition as described. The manufacturing method of a coating metal plate including the process of coating the coating composition as described in any one of Claims 1-4.

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