JP5273335B2 - Resin composition for paint and paint - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for coating, obtaining the coating exhibiting each of the characteristics (corrosion resistance of coated film, processability, etc.) of an epoxy resin and a polyester resin. <P>SOLUTION: This resin composition for coating contains an amine-modified epoxy resin (A) and the polyester resin (B). <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

The present invention relates to a resin composition for paint and a paint using the resin composition for paint.

The paint is used for the purpose of protecting the substrate from wind and rain, chemicals, heat, impact, etc., and imparting aesthetics such as color, luster, and pattern to it. There are various types of resin compositions used in paints. For example, when a bisphenol type epoxy resin is used, a coating film excellent in chemical resistance, corrosion resistance, and adhesion to a metal material can be obtained. In addition, when a polyester resin is used, a coating film having excellent hardness and processability can be obtained, and thick coating can be achieved.

However, the bisphenol-type epoxy resin alone tends to make the coating film brittle, and it may be difficult to mold and process the coated substrate. In addition, the polyester resin alone may not have sufficient corrosion resistance and chemical resistance. Therefore, in the industry, in order to obtain a paint utilizing each feature, both resins are sometimes mixed and used (see, for example, Patent Document 1).

However, a paint obtained by mixing both resins is likely to have a trade-off relationship between the features described above. For example, it is difficult to achieve both the corrosion resistance and workability of the coating film. When the coated substrate is exposed to wind and rain, the coated film may float or peel off, and when the coated substrate is molded, the coating film will crack or crack. May occur. Further, when such a mixed resin is used as a solvent-type paint, the appearance may become turbid. .
JP-A-6-220355

The present invention provides a coating resin composition capable of obtaining a coating material having good corrosion resistance and workability of a coating film and having a good appearance, and a coating material using the resin composition. The task is to do.

As a result of intensive studies, the present inventor has found that the above-mentioned problems can be solved by using a resin composition for coatings in which an amine-modified epoxy resin obtained by modifying a bisphenol-type epoxy resin with an amine and a polyester resin are mixed. That is, the present invention

1. One primary aliphatic amine selected from the group consisting of methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, stearylamine, icosylamine and 2-ethylhexylamine and / or diethanolamine One alkanolamine (a1) selected from the group consisting of diisopropanolamine, di-2-hydroxybutylamine, N-methylethanolamine, N-ethylethanolamine and N-benzylethanolamine and bisphenol-type epoxy and a resin (a2) the reaction components with the amine-modified epoxy resin (a) and alicyclic diols (b1) and the polyester resin to alicyclic dicarboxylic acid (b2) the reaction components (B), both solid matter Heavy Coating resin composition ratio [(A) / (B)] contains within an amount of 0.4 to 2.2,

2. The amount of the (a1) component and the (a2) component used is such that the amino group concentration of the (a1) component is 80 to 120 (eq / g) with respect to the epoxy group concentration of 100 (eq / g) of the (a2) component. The above-mentioned 1. Resin composition for paints,

3. The amines (a1) are amines having one or more alkyl groups having 3 to 30 carbon atoms in the molecule. Or 2. Coating resin composition,

4). The amine-modified epoxy resin (A) further comprises polyisocyanate (a3) as a reaction component. ~ 3. Either coating resin composition,

5. The amount of the component (a3) used is usually 0.1% of the isocyanate group concentration of the component (a3) with respect to the total hydroxyl group concentration 100 (eq / g) of the reaction product of the components (a1) and (a2). a range of the 5~50 (eq / g), the 4. Any of the resin compositions for paints,

6). (A) The resin composition for paints in any one of said 1-5 whose weight average molecular weights of component are 2000-100000 ,
7). (A) The resin composition for paints according to any one of 1 to 6 above, wherein the amine value of the component is 10 to 100 mgKOH / g

8). The use ratio of the component (b1) and the component (b2) is such that [the hydroxyl group concentration of the component (b1) (eq / g) / the carboxyl group concentration of the component (b2) (eq / g)] is 1/2 to 2/1. The resin composition for paints according to any one of claims 1 to 7 ,

9. (B) The resin composition for coatings in any one of said 1-8 whose weight average molecular weights are 3000-100000 ,
10. (B) The resin composition for paints according to any one of 1 to 9 above, wherein the acid value of the component is 0.1 to 10 mgKOH / g,
11. (B) The resin composition for paints according to any one of 1 to 10 above, wherein the hydroxyl value of the component is 3 to 30 mg KOH / g,

12 . 1 above. ~ 11 . A paint comprising the paint resin composition according to any one of the above and a curing agent,

13 . The coating material according to 12 above, wherein the curing agent is a melamine resin;

14 . Furthermore, the said 12 containing a solvent. Or 13 paints.

According to the coating resin composition of the present invention, it is possible to obtain a coating film having excellent adhesion to a substrate (particularly a metal material), chemical resistance, weather resistance, hardness, particularly corrosion resistance and workability. In addition to these effects, the compatibility of the composition is particularly good when a polyester resin, which is a component of the resin composition for paints, has a alicyclic skeleton in the molecule. . Moreover, the resin composition for coatings according to the present invention is suitable for coatings for metals, particularly coatings for pre-coated metals that are subjected to molding after being applied.

The resin composition for coatings of the present invention contains a predetermined amine-modified epoxy resin (A) (hereinafter referred to as component (A)) and a polyester resin (B) (hereinafter referred to as component (B)) in a predetermined weight ratio . It is a composition.

The component (A) includes a predetermined amine (a1) (hereinafter referred to as component (a1)) and a bisphenol type epoxy resin (a2) (hereinafter referred to as component (a2)) as reaction components, and component (a2) This is a modified epoxy resin into which an amino group is introduced, which is obtained by ring-opening reaction of the epoxy group of (a1). In the present invention, by using the component (A), the corrosion resistance and adhesion of the coating film are improved as compared with the paint using the component (a2) alone (that is, an epoxy resin having no amino group introduced).

As the component (a1), one primary aliphatic amine selected from the group consisting of methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, stearylamine, icosylamine and 2-ethylhexylamine And / or one alkanolamine selected from the group consisting of diethanolamine, diisopropanolamine, di-2-hydroxybutylamine, N-methylethanolamine, N-ethylethanolamine and N-benzylethanolamine Is mentioned.

  Among the components (a1), when amines having one or more alkyl groups (about 3 to 30 carbon atoms, preferably 4 to 20 carbon atoms) in the molecule are used, the components (A) and (B) Compatibility with the components is improved, and turbidity, phase separation, changes in viscosity with time, etc. hardly occur in the resulting resin composition for coatings. The alkyl group may be linear or branched. From this point of view, the amount of amines having one or more alkyl groups in the molecule is usually such that the amino group concentration is 50 to the total amino group concentration (eq / g) of the component (a1). The range is preferably about 100%.

In the present specification, the term “˜group concentration (eq / g)” refers to the number of functional groups (eq) per gram formula amount (g) of the compound.

The component (a2) is not particularly limited, and various known bisphenol type epoxy resins can be used. Specifically, for example, bisphenols [reaction products of phenols (phenol, 2,6-dihalophenol, etc.) and aldehydes (formaldehyde, acetaldehyde, etc.); the phenols and ketones (acetone, acetophenone, cyclohexanone, etc.) , Benzophenone, etc.); reaction products of the bisphenols and haloepoxides (epichlorohydrin, β-methylepichlorohydrin, etc.), and the like. These may be used alone or in combination of two or more. Can be used.

In addition, although the usage-amount of (a1) component and (a2) component is not specifically limited, Preferably, the amino group density | concentration of (a1) component is with respect to the epoxy group density | concentration 100 (eq / g) of (a2) component. Usually, it is good to use it so that it may become about 80-120 (eq / g), More preferably, it is 90-110 (eq / g). If it is less than 80, the corrosion resistance of the coating film tends to decrease, and if it exceeds 120, when the coating film is formed, many free amino groups remain in the coating film and the water resistance tends to decrease. is there.

Moreover, in this invention, when polyisocyanate (a3) (henceforth (a3) component) is further used as a reaction component of (A) component, the workability of a coating film will improve further. The component (a3) is not particularly limited as long as it is a polyisocyanate having two or more isocyanate groups in the molecule, and various known ones can be used. Specifically, for example, diisocyanates [1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexa Methylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, etc.], triisocyanates [triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, etc.], and these may be used alone or in combination. A combination of the above can be used.

The amount of the component (a3) used is not particularly limited, but preferably, the isocyanate group concentration of the component (a3) is usually compared to the total hydroxyl group concentration 100 (eq / g) of the component (A). It is good to make it about 0.5 to 50 (eq / g), more preferably 1 to 40 (eq / g). If it is less than 0.5, the molecular weight of the component (A) is difficult to increase, and the processability of the coating film may not be sufficiently improved. On the other hand, if it exceeds 50, the reaction system may be gelled during the production of the component (A).

Various physical properties of the component (A) are not particularly limited, and can be determined as appropriate. For example, the weight average molecular weight (referred to polystyrene conversion value by gel permeation chromatography, hereinafter the same) is usually about 2000 to 100,000 in consideration of the coating property of the paint and the corrosion resistance / workability of the coating film. It is preferable to do this. In consideration of the corrosion resistance and the like of the coating film, the amine value (JIS K 7237) is usually preferably about 10 to 100 mgKOH / g.

The component (A) can be produced by various known methods. For example, the above-described amounts of the (a1) component and the (a2) component may be subjected to an epoxy ring-opening reaction usually at about 80 to 150 ° C. for about 3 to 10 hours. If the reaction temperature is less than 80 ° C., the reaction rate becomes low and the efficiency becomes low. On the other hand, if the reaction temperature exceeds 250 ° C., it is opened between the epoxy groups in the component (a2) or between the epoxy group and the hydroxyl group. A ring reaction occurs, and the reaction product is easily gelled.

When the component (a3) is used, it is added to the same reaction system after the epoxy ring-opening reaction is completed, and the urethanization reaction is usually performed at about 50 to 150 ° C. for about 3 to 10 hours. Just do it. If the reaction temperature is less than 50 ° C., the reaction rate is low, which is not efficient. On the other hand, if the reaction temperature exceeds 150 ° C., the reaction system may gel.

Various known solvents can be used during the epoxy ring-opening reaction or urethanization reaction. Specifically, for example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, methyl cellosolve acetate, cellosolve acetate, Solvesso # 100 (made by Exxon), Solvesso # 150 (made by Exxon), etc. These may be used alone or in combination of two or more.

In addition, if it is for diluting the obtained (A) component, various well-known alcohols can also be used as another solvent. Specific examples include cellosolves such as methyl cellosolve and ethyl cellosolve, isopropyl alcohol, n-butyl alcohol and the like, and these can be used alone or in combination of two or more. In the case of using a solvent, the resin solid content concentration of the component (A) to be obtained is usually about 20 to 70% by weight, preferably 30 to 60, in consideration of workability during coating, coating film thickness, and the like. It is good to adjust to weight%. When the resin solid content concentration is less than 20% by weight, when the component (A) and the component (B) are mixed,

As the component (B), alicyclic diols (b1) (hereinafter, (b1) of component) and alicyclic dicarboxylic acids (b2) (hereinafter, (b2) that component) using a polyester resin as a reaction component . In this invention, the hardness of a coating film and the workability of a coating base material improve by using (B) component.

As the component (b1), various known alicyclic polyhydric alcohols can be used. Specifically, for example, 1,4-cyclohexanedimethanol, tricyclodecane-4,8-dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol as alicyclic dihydric alcohols S, tricyclodecane dimethanol, bishydroxymethylcyclohexane, bishydroxyethylbenzene, hydrogenated bisphenol A alkylene oxide adduct, and the like . Incidentally, (b1) with component [dihydric alcohols such as bisphenol A, further bisphenol A] an aromatic polyhydric alcohols as a and aliphatic polyhydric alcohols, aliphatic dihydric alcohol Ethylene glycol, diethylene glycol , Triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol 2,2,4-trimethyl-1,3-pentanediol, octanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, etc.], fat Group trihydric alcohols [trimethylolpropane, glycerin, etc.] can be used in combination.

Examples of the component (b2) include various known alicyclic polyvalent carboxylic acids such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, cyclohexane-1,4-dicarboxylic acid and the like as alicyclic divalent carboxylic acids. And the corresponding anhydrides and lower alkyl esters of these. In addition to the component (b2), aromatic divalent carboxylic acids [phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, maleic acid, succinic acid, oxalic acid, fumaric acid, malonic acid, Glutaric acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, dimer acid, etc.), aromatic trivalent carboxylic acids (trimellitic acid, pyromellitic acid, etc.), anhydrides corresponding to these, lower alkyl esters, etc. and, as the said aliphatic polycarboxylic acids, aliphatic divalent carboxylic acids [adipic acid, azelaic acid, sebacic acid, fumaric acid, itaconic acid, glutaric acid, maleic acid] it may be used in combination.

The use ratio of the component (b1) and the component (b2) is not particularly limited, but considering the adhesion between the coating film and the substrate, the functional group concentration ratio between them, that is, the hydroxyl group concentration of the component (b1) ( eq / g) / (b2) component carboxyl group concentration (eq / g)] is preferably about 1/2 to 2/1. .

Also, (B) when the component is one having a cyclohexane skeleton (-C6H10-) as alicyclic structure in the molecule, (A) component and (B) workability of compatibility and a coating film of a component Is preferable. In order to introduce the alicyclic structure into the molecule of the component (B), the alicyclic dihydric alcohol (particularly 1,4-cyclohexanedimethanol) is used as the component (b1), or the component as the component (b2). preferably used both alicyclic divalent carboxylic acids (in particular hexahydrophthalic anhydride and / or cyclohexane-1,4-dicarboxylic acid). In this case, when only the alicyclic dihydric alcohol is used, the hydroxyl group concentration is usually 50 to 100% with respect to the total hydroxyl group concentration (eq / g) of the component (b1). It is preferred to use. Moreover, when using only this alicyclic divalent carboxylic acid, it uses in the range from which the carboxyl group density | concentration will be 50-100% normally with respect to the total carboxyl group density | concentration (eq / g) of (b2) component. It is preferable to do this. When both are used, the total hydroxyl group concentration of the alicyclic dihydric alcohol and the alicyclic divalent carboxylic acid is usually 50 with respect to the total hydroxyl group concentration (eq / g) of the component (b1). It is preferable to use in a range of ˜100%.

Various physical properties of the component (B) are not particularly limited and can be determined as appropriate. For example, it is preferable that the weight average molecular weight is usually about 3000 to 100,000 in consideration of workability at the time of manufacture, coating property of the paint, and the like. In consideration of the adhesion and hardness of the coating film, the acid value (JIS K 0070) is usually preferably about 0.1 to 10 mgKOH / g. In consideration of the hardness and workability of the coating film, the hydroxyl value (JIS K 0070) is usually preferably about 3 to 30 mgKOH / g.

The component (B) can be produced by various known esterification methods such as transesterification, dehydration polycondensation reaction, and the like, and the reaction can be performed at normal pressure or reduced pressure. For example, the components (b1) and (b2) in the amounts described above are usually subjected to a dehydration polycondensation reaction at about 170 to 270 ° C. for about 5 to 10 hours, and further at about 200 to 270 ° C. Usually, the reduced pressure polycondensation reaction may be performed for about 2 to 10 hours. In the esterification reaction, a solvent capable of dissolving a polyester resin can be used among various known catalysts and the solvent. The molecular weight of the component (B) can be adjusted by appropriately adjusting the reduced pressure state. Moreover, when using a solvent, the resin solid content density | concentration at the time of manufacture of (B) component is about 20 to 70 weight% normally, Preferably it is good to set it as 30 to 60 weight%. When the resin solid content concentration exceeds 70% by weight, handling becomes difficult due to high viscosity. Moreover, when this is less than 20 weight%, when it mixes with (A) component, it exists in the tendency for the viscosity of a resin composition to become low too much.

The resin composition for coatings of the present invention can be obtained by mixing the component (A) and the component (B) by various known means. The mixing ratio of the both, both the weight ratio between solids [(A) / (B)] is usually about 0.25 to 4.5, in the range preferably to be 0.4 to 2.2, coated The workability of the film, the corrosion resistance, and the compatibility of the resin composition for paints are expressed in a well-balanced manner .

The coating resin composition of the present invention includes various additives such as curing agents (alkyl etherified aminoformaldehyde resins, polyisocyanates, blocked isocyanates, melamine resins, etc.), leveling agents, ultraviolet absorption. An agent or the like can be used. In addition, as a hardening | curing agent, a melamine resin is preferable.

The paint according to the present invention comprises such a resin composition for paint and a curing agent, and is particularly suitable as a solvent-type paint. When the amine-modified epoxy resin (A) or the polyester resin (B) is produced in a solvent, the obtained coating composition containing each resin is used as it is as a solvent-type coating composition. sell. The solvent is the same as described above.

Further, when the paint is used as a solvent-type paint, the solid content concentration can be appropriately adjusted according to purposes such as improvement of workability and adjustment of the coating thickness. Usually, the component (A) is used. And (B) total solid content weight [(A) + (B)] is about 5 to 50% by weight, preferably 10 to 30% by weight. Moreover, when using a hardening | curing agent, the usage-amount is about 5-50 weight% normally with respect to the total solid content weight of (A) component and (B) component, Preferably it is 15-30 weight%. .

  Examples of the base material include metal base materials [non-ferrous metals such as aluminum, zinc, stainless steel, manganese, magnesium, and iron] and non-metallic materials [plastics, wood, fiber materials, etc.]. Moreover, the metal base material (especially aluminum base material) coated with the coating material which concerns on this invention is suitable as a precoat metal. In addition, although the thickness of a coating film changes with uses of a coating material, it is about 3-50 micrometers normally.

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

Production Example 1
In a reaction vessel equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas introduction tube, 38.3 g of stearylamine, 7.7 g of diethanolamine, a bisphenol A type epoxy resin (trade name “Epototo YD-014”; Toto Kasei Co., Ltd.) (Product: Epoxy group concentration 950) 350 g and xylene 303 g were charged, and these were reacted at 100 ° C. for 5 hours under a nitrogen stream to obtain component (A1). The physical properties of this resin are shown in Table 1.

Production Example 2
In the same reaction vessel as in Production Example 1, stearylamine 38.3 g, diethanolamine 7.7 g, bisphenol A type epoxy resin (trade name “Epototo YD-014”; manufactured by Toto Kasei Co., Ltd .: epoxy group concentration 950), Xylene (303 g) was charged, and these were reacted at 100 ° C. for 5 hours under a nitrogen stream to obtain a modified epoxy resin. Next, 8.3 g of isophorone diisocyanate and 303 g of cyclohexanone were charged into the same reaction vessel, and these were reacted at 100 ° C. for 5 hours under a nitrogen stream to obtain component (A2). The physical properties of this resin are shown in Table 1.

Production Examples 3-5
In Production Example 2, components (A3) to (A5) were obtained in the same manner as in Production Example 1, except that the type of amine component (the weight used in parentheses) was changed as shown in Table 1. Each physical property value is shown in Table 1.

Production Example 6
A reaction vessel similar to Production Example 1 was charged with 68 g of cyclohexanedimethanol, 54 g of ethylene glycol, 68 g of neopentyl glycol, 52 g of hexahydrophthalic anhydride, and 231 g of cyclohexane-1,4-dicarboxylic acid, and the reaction system was heated with stirring. These raw materials were melted and then gradually heated from 170 ° C. to 220 ° C. over 3 hours while removing methanol and water produced by the condensation reaction, and further kept at 220 ° C. for 1 hour. Next, 0.10 g of antimony trioxide was charged into the reaction system, and a vacuum decompression apparatus was connected to the reaction vessel, and a reduced pressure polycondensation reaction was performed at 260 ° C. and 0.13 kPa for 2 hours. Next, the reduced pressure state was released and the reaction system was cooled to 150 ° C., and 300 parts of Solvesso # 100 (manufactured by Exxon) and 300 parts of butyl cellosolve were added to the reaction system to obtain component (B1). The physical properties of this resin are shown in Table 2.

Production Example 7
A component (B2) was obtained in the same manner as in Production Example 6 except that the types of the alcohol component and the acid component (the used weight in parentheses) were changed as shown in Table 2. The physical properties of this resin are shown in Table 2.

Each symbol in Tables 1 and 2 has the following meaning.
SA: Stearylamine 2-EHA: 2-ethylhexylamine DEA: Diethanolamine MEA: N-methylethanolamine YD014: “Epototo YD-014”
IPDI: isophorone diisocyanate CHDM: 1,4-cyclohexanedimethanol EG: ethylene glycol NPG: neopentyl glycol 1,4BG: 1,4-butanediol HHPA: hexahydrophthalic anhydride CHDA: cyclohexane-1,4-dicarboxylic acid DMT : Dimethyl terephthalate IPA: isophthalic acid SBA: sebacic acid Nv (%): solid content concentration Mw: weight average molecular weight AV: amine value OHV: hydroxyl value

Example 1
70 ml each of the component (A1) and the component (B1) were collected in a sample bottle, mixed thoroughly with a spatula, and allowed to stand until the bubbles disappeared. Next, a melamine resin (trade name “Cymel 303”, manufactured by Nippon Cytec Industries Co., Ltd.) in an amount of 20% by weight based on the total solid weight of the components (A1) and (B1) is added as a curing agent. The mixture was similarly mixed and allowed to stand. The obtained composition is used as a paint.

Examples 2-8 , Reference Examples 1-5
In the same manner as in Example 1, paint resin compositions having the combinations shown in Table 3 were obtained. Next, a crosslinking agent was added and mixed in the same manner as in Example 1. The obtained composition is used as a paint.

Comparative Examples 1-2
The bisphenol A type epoxy resin (Epototo YD-014) and the component (B1) were mixed so as to have the proportion (solid content weight ratio) shown in Table 3 to obtain a comparative resin composition for paint. Next, a crosslinking agent was added and mixed in the same manner as in Example 1. The obtained composition is used as a paint. In the same manner for the component (B2), a comparative resin composition for paint was obtained, and the paint was similarly used.

Comparative Examples 3-9
The components (A1) to (A5) and the components (B1) to (B2) were used alone as paints.

Each paint was applied to an aluminum alloy plate (JIS-H-400A5052P) to a thickness of 30 μm and dried at 150 ° C. for 20 minutes to obtain a coated plate. Each coated plate was left at 20 ° C. for 5 days to prepare a test plate.

(1) Evaluation of corrosion resistance A salt spray test was conducted according to JIS-K-5400 using the test plate, and a coating film peeling test was conducted using an adhesive tape (approximately 24 mm width) after 20 days. Corrosion resistance was evaluated according to the following criteria according to the peel width of the coating film. The results are shown in Table 3.
◎: Less than 2 mm ○: 2 mm or more and less than -3 mm Δ: 3 mm or more and less than -6 mm x: 6 mm or more

(2) Evaluation of workability A four-piece can was punched using the test plate, and the degree of peeling of the coating film was visually evaluated according to the following criteria. The results are shown in Table 3.
A: Particularly excellent (no cracking or cracking in the coating film)
○ to ○ △: Excellent (the cracks and cracks of the coating are 1 to 2 places)
Δ to Δ ×: Slightly poor (coating or cracking of the coating occurs in 3 to 4 places)
X: Defect (the crack or crack occurs in the coating film at 5 or more locations)

(3) Evaluation of compatibility About Examples 1-14 and Comparative Examples 1-2, the compatibility of the resin composition for coating materials was visually evaluated on the following references | standards. The results are shown in Table 3.
○: Clear Δ: Slightly turbid ×: Cloudy The state between each evaluation is expressed as, for example, ○ △.

Claims (14)

One primary aliphatic amine selected from the group consisting of methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, stearylamine, icosylamine and 2-ethylhexylamine and / or diethanolamine One alkanolamine (a1) selected from the group consisting of diisopropanolamine, di-2-hydroxybutylamine, N-methylethanolamine, N-ethylethanolamine and N-benzylethanolamine and bisphenol-type epoxy and a resin (a2) the reaction components with the amine-modified epoxy resin (a) and alicyclic diols (b1) and the polyester resin to alicyclic dicarboxylic acid (b2) the reaction components (B), both solid matter Heavy Coating resin composition ratio [(A) / (B)] contains within an amount of 0.4 to 2.2. The amount of the (a1) component and the (a2) component used is such that the amino group concentration of the (a1) component is 80 to 120 (eq / g) with respect to the epoxy group concentration of 100 (eq / g) of the (a2) component. The resin composition for paints of Claim 1 which is the range which becomes. The resin composition for paint according to claim 1 or 2, wherein the amine (a1) is an amine having one or more alkyl groups having 3 to 30 carbon atoms in the molecule. The resin composition for paint according to any one of claims 1 to 3, wherein the amine-modified epoxy resin (A) further comprises a polyisocyanate (a3) as a reaction component. The amount of the component (a3) used is usually 0.1% of the isocyanate group concentration of the component (a3) with respect to the total hydroxyl group concentration 100 (eq / g) of the reaction product of the components (a1) and (a2). The resin composition for paints of Claim 4 which is the range used as 5-50 (eq / g). (A) The weight average molecular weight of a component is 2000-100000, The resin composition for coating materials in any one of Claims 1-5. (A) The amine value of a component is 10-100 mgKOH / g, The resin composition for coating materials in any one of Claims 1-6. The use ratio of the component (b1) and the component (b2) is such that [the hydroxyl group concentration of the component (b1) (eq / g) / the carboxyl group concentration of the component (b2) (eq / g)] is 1/2 to 2/1. The resin composition for paints according to any one of claims 1 to 7, which is in a range. (B) The resin composition for coating materials in any one of Claims 1-8 whose weight average molecular weights of component are 3000-100000. (B) The resin composition for coating materials in any one of Claims 1-9 whose acid value of a component is 0.1-10 mgKOH / g. (B) Resin composition for coating materials in any one of Claims 1-10 whose hydroxyl value of component is 3-30 mgKOH / g. The coating material containing the resin composition for coating materials in any one of Claims 1-11, and a hardening | curing agent. The paint according to claim 12, wherein the curing agent is a melamine resin. Furthermore, the coating material of Claim 12 or 13 containing a solvent.