JP3218345B2 - Cured resin composition for paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION The Michael addition reaction in which an active methylene group or a hydroxyl group is added to a polarized double bond such as an α, β-unsaturated carbonyl group does not generate a reaction by-product and is newly formed. Since the formed bond is a chemically stable bond, it is applied to a crosslinking reaction of a curable resin composition such as a paint. Representative prior art includes the following patent documents. U.S. Pat. No. 4,408,018 U.S. Pat. No. 5,017,649 U.S. Pat. No. 5,084,536 JP-A-1-121341 (corresponding to EP0310011) JP-A-1-204919 (corresponding to EP0326723) EP0448154 JP-A-1-167117 JP-A-1-167355 JP-A-1-167356 JP-A-1-29019

Generally, in a Michael addition reaction, a strong base is used to generate a carbanion from an active hydrogen site. Most of the prior art utilizing the Michael addition reaction for crosslinking of resins also uses strong bases as catalysts. As strong base catalysts, alkali metal hydroxides and alkoxides, quaternary ammonium hydroxides and carbonates, tertiary amines, guanidines, amidines and tertiary phosphines are used.

[0003] Strongly basic catalysts generally have to be two-packed due to their strong catalytic activity. In addition, they degrade the resin by hydrolysis and the like, and if the base remains in the coating film, they cause deterioration. For example, an amine catalyst causes yellowing of a coating film. Alkali metal catalysts are hardly soluble in organic solvents for coatings, and it is difficult to uniformly disperse them in the composition.

Japanese Patent Application Laid-Open No. 1-167356 discloses the use of a quaternary ammonium organic carboxylate as a catalyst. However, quaternary ammonium organic carboxylate has low activity and does not substantially accelerate the crosslinking reaction by itself. Halides and other quaternary ammonium salts likewise show no or little catalytic activity alone.

JP-A-1-204919 discloses crosslinking Michael reaction components using a tertiary amine and an epoxide which have catalytic activity per se. In this case, unlike the case where a tertiary amine and an epoxide are reacted in the absence of a Michael reaction component, if an activated methylene component is present, a weakly acidic methylene component and a quaternary ammonium salt are reacted after the amine and epoxide have reacted. And activates the methylene component to cause a reaction with the alkene component. This means that when the tertiary amine is quaternized by reaction with the epoxide, hydrogen of the active methylene is extracted to form a carbanion. Therefore, it is clear that the quaternary ammonium salt which has already formed a stable salt has no such ability.

According to the present invention, an onium salt such as a quaternary ammonium salt which exhibits no or little catalytic activity by itself is suitable for a crosslinking reaction of a resin based on a Michael type addition reaction in the presence of an epoxy group. Is based on the new knowledge that Therefore, the composition according to the present invention has appropriate curability at room temperature or when heated, and has a long pot life even as a one-part type. Quaternary ammonium salts do not yellow the coating film as compared with amines. Further, by appropriately selecting the hydrocarbon substituent of the quaternary ammonium salt, the solubility in the organic solvent for coating can be improved, and therefore, it can be dissolved in the composition.

DISCLOSURE OF THE INVENTION The curable resin composition for paints of the present invention comprises: (a) a component having a plurality of α, β-ethylenically unsaturated carbonyl groups in a molecule; and (b) a plurality of active components in a molecule. Methylene group, active methine group,
And a component having at least one active hydrogen-containing group selected from hydroxyl groups, and (c) a halide anion selected from the group consisting of chloride, bromide and iodide, or salicylic acid, polybasic carboxylic acid, nitric acid, An anion derived from sulfonic acid, sulfuric acid, acid sulfate, sulfurous acid, phosphoric acid or acid phosphate;
An onium salt selected from the group consisting of a quaternary ammonium salt, a quaternary phosphonium salt and a tertiary sulfonium salt; and (d) an epoxy compound covalently bonded to the component (a) or (b) or an independent epoxy compound. I have.

Preferred Embodiment (a) Component (a) The component (a) is a compound or polymer having a plurality of alkenecarbonyl bonds having a double bond between α and β carbons in the molecule. Typical examples of such compounds are (meth) acrylates of polyhydric alcohols, such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, peritaerythritol tetra (meth) acrylate and polyester acrylate resins.

Α, β- such as fumaric acid and maleic acid
Unsaturated polyesters containing unsaturated dicarboxylic acids can also be used as component (a). Unsaturated polyesters are used in large quantities as molding resins such as FRP, and as is well known, α, β-unsaturated dicarboxylic acids such as maleic anhydride and fumaric acid, and optionally phthalic anhydride, isophthalic acid, terephthalic acid and the like. Acid components consisting of other polycarboxylic acids such as acid, adipic acid, sebacic acid and trimellitic acid, and ethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, neopentyl glycol, It is synthesized by a polycondensation reaction with a polyhydric alcohol such as methylolpropane, glycerin, and pentaerythritol.

An example of another resin that can be used as the component (a) is an epoxy acrylate resin. This can be synthesized by, for example, ring-opening addition of an epoxy ring of an epoxy resin such as a bisphenol type or a novolak type by reaction with (meth) acrylic acid. As another example, a hydroxy group-containing acrylic resin is obtained by an addition reaction of a polyisocyanate compound such as isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate or a urethane prepolymer thereof with 2-hydroxyethyl (meth) acrylate. There is a urethane acrylate resin.

The α, β-unsaturated carbonyl group-containing acrylic resin is obtained by ring-opening an epoxy ring with (meth) acrylic acid,
It can be synthesized using a reaction such as acylation of a hydroxyl group with (meth) acrylic acid. For example, an epoxy group-containing acrylic resin obtained by copolymerization of an epoxy group-containing acrylic monomer such as glycidyl (meth) acrylate with another acrylic monomer and / or a non-acrylic ethylenically unsaturated monomer may be used as (meth) It can be synthesized by reacting acrylic acid. Acrylic monomers that can be used for copolymerization include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, 2-ethylhexyl, lauryl, phenyl, benzyl and 2-hydroxyethyl of acrylic acid or methacrylic acid. Acrylamide, methylenebisacrylamide, acrylonitrile, and the like, and non-acrylic-based acrylates, 2-hydroxypropyl ester, Praxel FM-1 (adduct of 2-hydroxyethyl methacrylate and polycaprolactone, manufactured by Daicel Chemical Industries, Ltd.), and acrylonitrile. Examples of the monomer include styrene, α-methylstyrene, itaconic acid, maleic acid, and vinyl acetate.

The carboxy group-containing acrylic resin may be reacted with an epoxy group-containing acrylic monomer such as glycidyl (meth) acrylate. The carboxy group-containing acrylic resin can be synthesized by copolymerizing a carboxyl group-containing monomer such as acrylic acid, methacrylic acid, and itaconic acid with the above-mentioned acrylic monomer and, if necessary, a non-acrylic monomer.

Acrylic polyols can be α, β-acrylated by acylation with acrylic acid or methacrylic acid or a reactive derivative thereof (such as chloride), or by transesterification with a lower alkyl ester of acrylic acid or methacrylic acid such as methyl ester. Unsaturated carbonyl groups can be introduced. Acrylic polyol is
Hydroxy group-containing acrylic monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and Plaxel FM-1 can be used as other acrylic monomers and / or It can be synthesized by copolymerizing with an acrylic monomer.

Other components (a) that can be used include polyether acrylate resins such as polyethylene glycol di (meth) acrylate, and polydiorganosiloxanes having a 3-methacryloyloxypropyl group at both ends. There are (meth) acryloyl group-containing silicone oligomers.

When the above resin is used as the component (a), the molecular weight is 400 to 100,000, preferably 60.
0 to 10,000, the double bond equivalent is 100 to 10,000,
Preferably it is 100-1000. In addition, in this specification, equivalent means the molecular weight per functional group.

Component (b) As the component (b), a component having a plurality of active methylene groups or active methine groups in a molecule is exemplified. As compounds having an active methylene group, acetoacetic acid, malonic acid, cyanoacetic acid and derivatives thereof are known. The compound having a plurality of active methylene groups used in the component (b) of the present invention has a structure derived from the above-mentioned active methylene group-containing carboxylic acid compound. For example, those obtained by esterifying a polyhydric alcohol or polyol with an active methylene group-containing carboxylic acid compound can be mentioned.
As the polyhydric alcohol, those described for the polyester used for the component (a) can be used. As the polyol, acrylic polyol, polyester polyol,
Examples include polyether polyols, epoxy polyols, polyurethane polyols and silicone polyols. Examples of the active methylene group-containing carboxylic acid compound include acetoacetate, malonate and cyanoacetate. In addition, a polyester resin having a plurality of active methylene groups in a molecule can be obtained by polycondensation of a polyhydric alcohol and a malonic ester.

Also, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexanediamine, 1,12-diaminododecane, 1,2-diaminocyclohexane, phenylenediamine, piperazine, 2,6 -Diaminotoluene, diethyltoluenediamine, N, N-bis (2-aminopropyl) ethylenediamine, N, N'-bis (3-aminopropyl) -1,
By reacting diketene with a polyamine compound such as 3-propanediamine, a compound having a plurality of active methylene groups in the molecule can be obtained.

In addition, an acrylic monomer having an active methylene group in the molecule is copolymerized with the acrylic monomer and / or a non-acrylic monomer described above for the acrylic resin of the component (a) to form an active methylene group. Acrylic resins having a plurality in the molecule can also be synthesized. Acrylic monomers having an active methylene group in the molecule include 2-acetoacetoxyethyl or 2-cyanoacetoxyethyl ester of acrylic acid or methacrylic acid, N- (2-cyanoacetoxyethyl) acrylamide, N- (2-propionylacetoxy) Butyl) acrylamide, N-4- (acetoacetoxymethyl) benzylacrylamide, N- (2-acetoacetamidoethyl) acrylamide, N- (2-acetoacetamidoethyl) methacrylamide and the like.

On the other hand, those having a plurality of active methine groups in the molecule include, for example, a transesterification reaction between a trialkyl methanetricarboxylate and a polyhydric alcohol or polyol, or an isocyanate compound as described in EP0310011. And an active methylene group-containing compound. In the reaction between the isocyanate and the active methylene group, one is polyfunctional and the other is monofunctional. For example, in the case of a polyisocyanate in which the polyol terminal is modified with diisocyanate, a compound such as a malonic ester is used as the active methylene group-containing compound. Conversely, a compound having a plurality of active methylene groups shown above in the molecule can be obtained by reacting it with a monofunctional isocyanate compound.

As the component (b), those having a plurality of hydroxyl groups in the molecule can also be used. Such materials include polyhydric alcohols, acrylic polyols, polyester polyols, polyether polyols, epoxy polyols, polyurethane polyols and silicone polyols. Among them, the polyhydric alcohols and acrylic polyols described above can be used. Examples of the polyester polyol include a polyester having a hydroxyl group at a terminal and a polycaprolactone polyol. The polyether polyol is produced by addition-polymerizing an alkylene oxide such as ethylene oxide or propylene oxide in the presence of a basic catalyst using a polyhydric alcohol as an initiator. Epoxy polyols are produced by reacting an epoxy resin such as a bisphenol A type epoxy resin with an amino alcohol such as diethanolamine. Polyurethane polyol is obtained by converting polyhydric alcohol and diisocyanate into NCO.
It is produced by reacting at a / OH ratio of less than 1. In addition, silicone polyols can be used.

The component (b) includes active methylene,
Two or more active methine and hydroxyl groups may be used together. In this case, a single component may be mixed, or a polymer having two or more functional groups may be used. Examples of such a polymer include a copolymer of an acrylic monomer having each functional group and a polyester polyol obtained from malonic ester as a raw material.

When the above resin is used as the component (b), it has a molecular weight of 1,000 to 100,000, preferably 1,000 to 10,000, and an active hydrogen equivalent of 40 to 10,000.
000, preferably 80-5000.

(C) Component As the component (c), quaternary ammonium salts having various cationic moieties can be used, but tetraalkylammonium salts and trialkylaralkylammonium salts are easily available. A quaternary ammonium salt of a nitrogen-containing heterocyclic compound such as pyridine, piperidine, piperazine, and morpholine may be used. Specifically, tetrabutylammonium, tetramethylammonium, tetraethylammonium, trimethylbenzylammonium, tetrapropylammonium, tetrahexylammonium, tetraoctylammonium, tetradecylammonium, tetrahexadecylammonium, triethylhexylammonium, 2-hydroxyethyltrimethylammonium (Choline), methyltrioctylammonium, cetyltrimethylammonium, 2-chloroethyltrimethylammonium, methylpyridinium and the like.

The counter anion of the ammonium salt is selected from those which form a stable salt with the cation moiety,
Chloride, bromide, iodide, salicylate, polycarboxylate, sulfonate, sulfate, phosphate and the like. Specific examples include salicylate, maleate, phthalate, chloride, bromide, iodide, methanesulfonate, p-toluenesulfonate, dodecylbenzenesulfonate, triflate, nitrate, sulfate, metsulfate, phosphate, di-t-butyl phosphate, and the like. .

Quaternary phosphonium salts such as tetrabutylphosphonium bromide, and tertiary sulfonium salts such as trimethylsulfonium iodide can be used as well as quaternary ammonium salts.

Among these onium salts, aromatic carboxylic acids whose anions have a phenolic hydroxyl group such as salicylic acid, polybasic carboxylic acids such as oxalic acid, maleic acid, fumaric acid and phthalic acid, nitric acid, phosphoric acid, Onium salts that are anions of sulfurous acid, acidic phosphoric acid ester, or sulfonic acid alone do not have catalytic activity for the Michael addition reaction, but are satisfactory by heating under baking conditions usually used in the presence of an epoxy group. Exhibits catalytic activity. On the other hand, it has excellent storage stability.

Component (d) When added as an independent compound, preferred components (d) are glycidyl ethers (eg, phenylglycidyl ether, bisphenol-type epoxy resin, reaction product of epichlorohydrin and polyhydric alcohol), glycidyl esters (E.g., glycidyl benzoate, glycidyl (meth) acrylate and polymers), alicyclic epoxy compounds (e.g., 4- (3,4-epoxycyclohexyl) methoxycarbonyl-1,2-epoxycyclohexane, 3,4-epoxycyclohexane) (Meth) acrylate of methanol and its polymer), and α
-Olefin epoxides (e.g. epoxy hexadecane).

When the above resin is used as the component (d), the molecular weight is 400 to 100,000, particularly 400 to 100,000.
000, epoxy equivalent of 200 to 100,000, especially 2
It is preferably from 00 to 5000.

As a method of supporting the component (d) on the component (a) or the component (b) by a covalent bond, the epoxy resin or the epoxy group-containing acrylic resin of the component (a) is less than the stoichiometric value (meth ) A method of reacting acrylic acid to leave a part of the epoxy group. In synthesizing the acrylic resin as the component (b), glycidyl (meth) acrylate and β-methylglycidyl (meth) are used as copolymerized monomers.
There is a method using (meth) acrylate of acrylate and 3,4-epoxycyclohexanemethanol.

Curable Resin Composition The curable resin component of the present invention relates to a double bond and an active hydrogen atom to be added thereto, and the components (a) and (b) are preferably 2: 1 to 1: 2, more preferably 2: 1 to 1: 2. Are 1.5: 1 to 1: 1.
Should be included in an equivalent ratio of 5. Component (c) is 0.1 to 10.0 equivalent% based on the total of components (a) and (b),
Preferably, 0.2 to 5.0 equivalent% is added. Component (d) is 0.5 to 1 with respect to the total of components (a) and (b).
00 equivalent%, preferably 5.0 to 40 equivalent% is used.

When the composition of the present invention is prepared into a paint, it may contain a conventional paint additive such as a conventional paint solvent, an extender, a coloring pigment, an anti-sagging agent, and an ultraviolet absorber. The coating material is cured by a crosslinking reaction when the coating film is left at room temperature after application or when the coating film is heated to 100 to 200 ° C, particularly 120 to 150 ° C, to form a hard coating film.

The curable resin composition of the present invention is suitably used as a clear coating composition applied on a base coating. In this case, a color pigment-containing aqueous paint or a color pigment-containing organic solvent-type paint is preferably used as the base paint. In coating, a two-coat, one-bake curing method in which a clear coating containing the curable resin composition of the present invention is applied (wet-on-wet) to the surface of the base coating without curing the base coating, and then both coating films are cured. Is preferably used.

However, when an aqueous paint is used,
It is preferable to heat the base coat at 60 to 100 ° C. for 2 to 10 minutes before applying the clear paint in order to obtain a coating film having a good finish. US Pat. Nos. 5,151,125 and 5,183,5 as base paints
No. 04 or the like can be used. In particular, the aqueous coating composition described in Example 1 of U.S. Pat. No. 5,183,504 is most suitable in terms of finish, appearance and performance.

In this application, especially in a composite coating applied to an automobile body, it is important that the top coat does not deteriorate due to scratch resistance and acid rain which has recently become a problem. The composition of the present invention is clearly superior in these performances to a conventional acryl-based clear coating composition using a melamine resin as a curing agent.

The present invention will be illustrated below by way of Synthesis Examples, Examples and Comparative Examples. In these, "part" and "%"
Is based on weight.

Synthesis Example 1 The monomers and initiators shown in Table 1 were mixed, and dropwise added over 3 hours at 110 ° C. while 360 parts of xylene was charged in a four-necked flask. Thereafter, aging was performed at 110 ° C. for 0.5 hour. Further, 2 parts of Kayaester O (t-butylperoxyoctate) and 40 parts of xylene were mixed, added dropwise at 110 ° C. over 0.5 hours, and then aged for 1.5 hours. The resulting acrylic resin solution had a nonvolatile content of 49.4%, a number average molecular weight of about 4,300 as measured by GPC, and an active methylene equivalent of 200.
And an epoxy equivalent of 1002.

Synthesis Examples 2 to 10 Synthesis Example 1 except that the monomers and initiators shown in Table 1 were used.
An acrylic resin was synthesized in the same manner as described above. Table 1 shows the nonvolatile content of the obtained acrylic resin solution, the number average molecular weight determined by GPC, the active hydrogen equivalent, and the epoxy equivalent.

Synthesis Example 11 394 parts of the resin solution obtained in Synthesis Example 10 (resin solid content 2
00 parts), 24 parts of methacrylic acid and 0.1 part of hydroquinone.
And 1.0 part of tetrabutylammonium bromide, and reacted at 120 ° C. until the acid value became 1 or less. The obtained resin solution had a double bond equivalent of 790, an epoxy equivalent of 3300 and a nonvolatile content of 52.8%.

Synthesis Example 12 394 parts of the resin solution obtained in Synthesis Example 10 (resin solid content 2
00 parts) to 30 parts of methacrylic acid and 0.1 part of hydroquinone.
And 1.0 part of tetrabutylammonium bromide, and reacted at 120 ° C. until the acid value became 1 or less. The obtained resin solution had a double bond equivalent of 630 and a nonvolatile content of 53.0%.

Synthesis Example 13 A reaction vessel was charged with 236 parts of 1,6-hexanediol, 78 parts of dimethyl phthalate, 230 parts of dimethyl maleate, 1 part of dibutyltin oxide, and heated to 120 ° C. to convert methanol distilled out by transesterification. The temperature was gradually raised to 200 ° C. while distilling off. Heating was continued at 200 ° C. until no methanol was distilled off, followed by cooling, and 250 parts of xylene was added. The obtained resin solution had a nonvolatile content of 61.4%, a number average molecular weight by GPC of about 1700 and a double bond equivalent of 264.

Synthesis Example 14 A reaction vessel was charged with 236 parts of 1,6-hexanediol, 264 parts of dimethyl malonate and 1 part of dibutyltin oxide. The temperature was raised to 120 ° C., and the methanol distilled off by transesterification was gradually distilled off. To 200 ° C. Heating was continued at 200 ° C. until no methanol was distilled off, followed by cooling, and 250 parts of xylene was added. The resulting resin solution had a nonvolatile content of 58.8%, a number average molecular weight by GPC of about 1800, and an active hydrogen equivalent of 91.

Synthesis Example 15 A reaction vessel was charged with 118 parts of 1,6-hexanediol, 148 parts of isophorone diisocyanate and 266 parts of methyl isobutyl ketone, and reacted at 80 ° C. until the NCO value became 1 or less. The obtained resin solution had a nonvolatile content of 49.7% and GPC
Number average molecular weight of about 800, hydroxyl equivalent of 40
It was 0.

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[Table 1]

Example 1 405 parts of the resin solution synthesized in Synthesis Example 1 (resin solid content 20
0 parts), 100 parts of pentaerythritol triacrylate (hereinafter abbreviated as PETA), and 2 parts of tetrabutylammonium nitrate (TBANO) were mixed and uniformly dissolved. This solution was applied on a tin plate using a # 40 bar coater, and cured at 140 ° C. for 20 minutes in a drier. The gel fraction was calculated from the weight change before and after immersion when the obtained coating film was immersed in a mixed solvent of acetone / methanol = 1/1 at room temperature for 48 hours. Table 2 shows the results.
The mixture was stable during storage at 40 ° C. for 10 days.

Example 2 The procedure of Example 1 was repeated, except that 1 part of tetrabutylammonium methanesulfonate (TBAMS) was used in place of TBANO, mixed, coated and cured at 140 ° C. for 20 minutes. Table 2 shows the results. The mixture was stable during storage at 40 ° C. for 10 days.

Example 3 The procedure of Example 1 was repeated, except that 2 parts of tetrabutylammonium di-t-butyl phosphate (TBAP) were used in place of TBANO, mixed and coated, and cured at 140 ° C. for 20 minutes. . Table 2 shows the results. The mixture was stable during storage at 40 ° C. for 10 days.

Example 4 405 parts of the resin solution synthesized in Synthesis Example 1 (resin solid content 20
0 parts), trimethylolpropane triacrylate (T
(MPTA) 50 parts and tetrabutylphosphonium bromide (TBPBr) 3 parts were mixed, applied, and cured at 20 ° C. for 6 hours. Table 2 shows the results. The mixture is 4
It gelled after 2 days at 0 ° C.

Example 5 The procedure of Example 4 was repeated, except that 2 parts of trimethylbenzylammonium acetate (TMBAAc) was used instead of TBPBr as the onium salt, and the mixture was applied and cured at 20 ° C. for 6 hours. Table 2 shows the results. The mixture is 4
It gelled after 1 day at 0 ° C.

Comparative Examples 1-3 405 parts of the resin solution synthesized in Synthesis Example 4 (resin solid content 20
0 parts), mixed and coated in the same manner as in Examples 1 to 3, and cured at 140 ° C. for 20 minutes. Table 3 shows the results.

Comparative Examples 4 and 5 405 parts of the resin solution synthesized in Synthesis Example 4 (resin solid content 20
0)), mixed and coated in the same manner as in Examples 4 and 5, and cured at 20 ° C for 6 hours. Table 3 shows the results.

Example 6 393 parts of the resin solution synthesized in Synthesis Example 5 (resin solid content 20
0 parts), KAYARAD DPCA- manufactured by Nippon Kayaku Co., Ltd.
120 (1 mol of dipentaerythritol / 12 mol of caprolactone, hexaacrylate of ring-opened adduct) 150
Part, tetrabutylammonium chloride (TBAC
I) 2 parts were mixed, applied and cured at 160 ° C. for 20 minutes. Table 4 shows the results.

Example 7 395 parts (resin solid content 20) of the resin solution synthesized in Synthesis Example 6
0 parts), 50 parts of PETA, and 2 parts of tetrabutylammonium acetate (TBAAc), and then mixed and applied at 140 ° C.
For 20 minutes. Table 4 shows the results.

Comparative Example 6 396 parts of the resin solution synthesized in Synthesis Example 7 (resin solid content 20
0 part), mixed and coated in the same manner as in Example 6, except that
Cured at 160 ° C. for 20 minutes. Table 4 shows the results.

Comparative Example 7 396 parts of the resin solution synthesized in Synthesis Example 7 (resin solid content 20
0 part), mixed and coated in the same manner as in Example 7, except that
Cured at 140 ° C. for 20 minutes. Table 4 shows the results.

Example 8 396 parts of the resin solution synthesized in Synthesis Example 7 (resin solid content 20
0 parts), UA-306H manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.
(Adduct of 1 mol of hexamethylene diisocyanate and 2 mol of pentaerythritol triacrylate) 95
, 15 parts of Epicoat 825 (bisphenol A diglycidyl ether) manufactured by Yuka Shell Epoxy Co., Ltd. and 2 parts of tetrabutylammonium salicylate (TBASA) were mixed, applied, and cured at 140 ° C for 20 minutes. Table 4 shows the results.

Example 9 393 parts of the resin solution synthesized in Synthesis Example 8 (resin solid content 20
0), KAYARAD DPCA-120 200
Part, tetrabutylammonium bromide (TBAB
r) 3 parts were mixed, applied and cured at 140 ° C. for 20 minutes. Table 5 shows the results.

Example 10 394 parts of the resin solution synthesized in Synthesis Example 9 (resin solid content 20
0), KAYARAD DPCA-120 200
Was mixed with 30 parts of Showain 508 (diglycidyl phthalate) manufactured by Showa Denko Co., Ltd. and 3 parts of TBABr, and the mixture was cured at 140 ° C. for 20 minutes. Table 5 shows the results.

Comparative Example 8 394 parts of the resin solution synthesized in Synthesis Example 9 (resin solution 200
Part) was mixed and coated in the same manner as in Example 10 except that
Cured at 140 ° C. for 20 minutes. Table 5 shows the results.

Example 11 405 parts of the resin solution synthesized in Synthesis Example 1 (resin solid content 20
0 parts), 75 parts of PETA, and 4 parts of trimethylsulfonium iodide (TMSI) were mixed, applied, and cured at 160 ° C. for 20 minutes. Table 5 shows the results.

Example 12 Instead of TMSI, cetylpyridinium bromide (C
PBr) mixed in the same manner as in Example 11 except for using 4 parts,
Coated and cured at 160 ° C. for 20 minutes. Table 5 shows the results.

Example 13 400 parts of the resin solution synthesized in Synthesis Example 2 (resin solid content 20
0 parts), diacrylate of polyethylene glycol (degree of polymerization 9) (NK Ester A-40 manufactured by Shin-Nakamura Chemical Co., Ltd.)
0) 200 parts and trimethylbenzylammonium chloride (TMBAC1) 2 parts were mixed and applied, and 140 ° C.
For 20 minutes. Table 6 shows the results.

Example 14 411 parts of the resin solution synthesized in Synthesis Example 3 (resin solid content 20
0 parts), 200 parts of Kyoeisha Yushi Kagaku Kogyo Co., Ltd. epoxy ester 3002A (the epoxy ring of diglycidyl ether of 1 mol of bisphenol A / 2 mol of propylene oxide adduct opened with acrylic acid), and tetrabutylammonium ion Three parts of Dyed (TBAI) were mixed, applied and cured at 140 ° C. for 2 hours. Table 6 shows the results.

Example 15 379 parts of the resin solution synthesized in Synthesis Example 11 (resin solid content 2
00 parts), 25 parts of ditrimethylolpropane tetraacetoacetate (DTMPTA), and 2 parts of TBABr were mixed, applied, and cured at 140 ° C. for 20 minutes. Table 6 shows the results.

Example 16 377 parts of the resin solution synthesized in Synthesis Example 12 (resin solid content 2
00 parts), 30 parts of DTMPTA, Epicoat 825 1
5 parts and 2 parts of TBABr were mixed, applied, and cured in a dryer at 140 ° C. for 20 minutes. Table 6 shows the results.

Comparative Example 9 377 parts (resin solid content 2) of the resin solution synthesized in Synthesis Example 12
00 parts), 30 parts of DTMPTA and 2 parts of TBABr were mixed, applied, and cured at 140 ° C. for 20 minutes. Table 6 shows the results.

Example 17 379 parts of the resin solution synthesized in Synthesis Example 11 (resin solid content 2
00 parts), polyethylene glycol (average molecular weight 20)
0) 25 parts and 2 parts of TBASA are mixed and applied, and 140 ° C.
For 20 minutes. Table 7 shows the results.

Example 18 Mixing and coating were performed in the same manner as in Example 17, except that 105 parts of Praxel # 308 (trifunctional polycaprolactone polyol, number average molecular weight 850) manufactured by Daicel Chemical Industries, Ltd. were used instead of polyethylene glycol. 2 at 140 ° C
Cured for 0 minutes. Table 7 shows the results.

Example 19 The procedure of Example 17 was repeated, except that 120 parts of KR-2001 manufactured by Shin-Etsu Chemical Co., Ltd. having the following average composition formula were used instead of polyethylene glycol, mixed, coated, and cured at 140 ° C. for 20 minutes. Was. Table 7 shows the results.

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Example 20 379 parts of the resin solution synthesized in Synthesis Example 11 (resin solid content 2
00 parts), 101 parts of the resin solution synthesized in Synthesis Example 15 (50 parts of resin solids), 4 parts of glycerin, and 2 parts of TBASA were mixed, applied, and cured at 140 ° C. for 20 minutes. Table 7 shows the results.

Example 21 326 parts (resin solid content 2) of the resin solution synthesized in Synthesis Example 13
00 parts), 70 parts of DTMPTA, 20 parts of Celloxide 2021 (4- (3,4-epoxycyclohexyl) methoxycarbonyl-1,2-epoxycyclohexane) manufactured by Daicel Chemical Industries, Ltd., and 5 parts of TBAC1 were mixed and coated, and 140 parts were mixed. Cured at 200C for 20 minutes. Table 7 shows the results.

Example 22 340 parts of the resin solution synthesized in Synthesis Example 14 (resin solid content 2
00 parts), 150 parts of PETA, epoxy hexadecane 3
0 parts and 5 parts of TBAC1 were mixed and applied.
Cured for 0 minutes. Table 8 shows the results.

Example 23 379 parts of the resin solution synthesized in Synthesis Example 11, 127 parts of MACRYNAL LH437 (polyfunctional methanetricarboxylate) manufactured by Hoechst, and 3 parts of tetrabutylammonium phthalate (TBAPA) were mixed and applied.
Cured at 200C for 20 minutes. Table 8 shows the results.

Example 24 405 parts of the resin solution synthesized in Synthesis Example 1 (resin solid content 20
0 parts), 80 parts of PETA, 40 parts of a polysiloxane having a 3-methacryloyloxypropyl group at both terminals (X-22-164B manufactured by Shin-Etsu Chemical Co., Ltd.) and 3 parts of TBAPA are mixed, applied, and cured at 140 ° C. for 20 minutes. Was. Table 8 shows the results.

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[Table 2]

[0076]

[Table 3]

[0077]

[Table 4]

[0078]

[Table 5]

[0079]

[Table 6]

[0080]

[Table 7]

[0081]

[Table 8]

Synthesis Example 16 The procedure of Synthesis Example 1 was repeated except that the amount of Kayaester O in the monomer and the initiator was changed to 36 parts and the polymerization temperature was changed to 130 ° C. %, G
An acrylic resin varnish having a number average molecular weight of about 2500 by PC was obtained.

EXAMPLE 25 A 0.8 mm-thick dull steel plate treated with zinc phosphate was coated with a cationic electrodeposition paint (Powertop PU manufactured by Nippon Paint Co., Ltd.).
-50) is electrodeposited to a dry film thickness of about 25 μm, and an intermediate coating (Nippon Paint Co., Ltd. Olga P-2 sealer) is applied by air spray coating to a dry film thickness of about 40 μm.
Bake at 40 ° C. for 30 minutes. Next, a high solid base paint having the following composition was applied by air spraying so as to have a dry film thickness of about 16 μm, and set for about 7 minutes.

[0084] formulation of the base paint ALPASTE 7160N (manufactured by Toyo Aluminum Co., Ltd. 10 parts of aluminum flake paste, an aluminum flake containing 65 percent) acrylic resin varnish ^* 50 parts Cymel 202 (Mitsui Cyanamide Co., Ltd. Melamine resin, 10 parts of non-volatile 80%) Cymel 327 (same as above, non-volatile content 90%) 10 parts Isopropyl alcohol 7 parts * Non-volatile content 80%, hydroxyl value 100, acid value 30,
Number average molecular weight 1800

Next, a clear paint having the following composition was applied to Ford Cup No. 4, the viscosity was adjusted to 30 seconds, and electrostatic coating was performed so that the dry film thickness became about 40 μm. After setting for about 7 minutes, baking was performed at 140 ° C. for 25 minutes.

Mixture of clear paint 405 parts of acrylic resin varnish of Synthesis Example 16 PETA 80 parts TBANO 2 parts Tinuvin 900 ¹⁾ 6 parts Sanol LS-292 ²⁾ 3 parts 1) UV absorber made by Ciba Geigy ²⁾ Sankyokisei Hindered amine

After curing, the properties of the topcoat coating were tested and the results shown in Table 9 were obtained.

Test Method 1) Paint nonvolatile vo1 (SVS) After unifying at 30 seconds / 20 ° C. with 0.5, 0.5 g of the paint was precisely weighed, diluted with 3 ml of toluene, baked at 110 ° C. for 1 hour, measured for paint non-volatile content (wt), and converted to vo1. 2) Pencil hardness This was performed in accordance with JIS K5400 8, 4, and 2. 3) Scratch resistance A 2 × 2 cm flannel cloth coated with 1 g of a 50% aqueous dispersion of a cleanser (New Homing Cleanser manufactured by Kao) was adhered to a Gakushin-type dyeing friction fastness tester (Daiei Kagaku Seiki Co., Ltd.). . After a load of 500 g was applied and the sliding head was reciprocated 20 times, the 20 ° gloss of the test portion was measured, and the gloss retention was calculated. The evaluation was performed according to the following criteria. ◎: 85% or more ○: 70% or more and less than 85% △: 40% or more and less than 70% ×: less than 40% 4) Acid resistance

After the obtained cured coating film was contacted with 0.5 ml of a 0.1N sulfuric acid aqueous solution at 75 ° C. for 30 minutes, the coating film surface was visually evaluated according to the following criteria. ◎: No abnormality ○: Slight trace △: Large trace ×: Abnormal coating film

Comparative Example 10 A top coat was applied on a base coat by wet-on-wet so as to have a dry film thickness of about 40 μm in the same manner as in Example 25 except that a clear paint having the following composition was used as the top coat. A composite coating was formed with one coat of bake. Evaluation of the cured coating film was performed in the same manner as in Example 25, and the results shown in Table 9 were obtained.

A top coat compound part of the comparative example, Dianal HR-554 (58.3 thermosetting acrylic resin varnish manufactured by Mitsubishi Rayon Co., Ltd., solid content 60%) ACR-461 (Nippon Paint Co., Ltd. 63.6) Thermosetting acrylic resin varnish, solid content 55%) Uban 20N-60 ^* 50.0 Tinuvin 900 2.0 Sanol LS-292 1.0 n-Butanol 1.3 Solvesso 100 5.0 * Mitsui Toatsu Chemical Co., Ltd. ) Melamine resin, 60% non-volatile content

[0092]

Continuation of front page (72) Inventor Hiroto Yoneda 19-17 Ikedanakamachi, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (56) References JP-A-1-204919 (JP, A) JP-A-49-51384 JP, A) JP-A-61-228068 (JP, A) JP-A-1-152117 (JP, A) JP-A-1-167355 (JP, A) JP-A-1-167356 (JP, A) JP-A 1-229019 (JP, A) JP-A-2-84469 (JP, A) JP-A 1-182376 (JP, A) JP-A 1-182377 (JP, A) (58) Fields investigated (Int .Cl. ⁷ , DB name) C08G 59/40 C08G 81/00-81/02 C09D 163/00-163/10 C09D 187/00 C08F 299/00-299/08

Claims (9)

(57) [Claims] (1) a component having a plurality of α, β-ethylenically unsaturated carbonyl groups in the molecule; and (b) at least one selected from a plurality of active methylene groups, active methine groups and hydroxyl groups in the molecule. A component having one kind of active hydrogen-containing group, (c) the anion is chloride, bromide or
Halide anion selected from the group consisting of dyed,
Is salicylic acid, polybasic carboxylic acid, nitric acid, sulfone
Acid, sulfuric acid, acid sulfate, sulfurous acid, phosphoric acid or
An anion derived from an acidic phosphate ester, 4
An onium salt selected from the group consisting of a quaternary ammonium salt, a quaternary phosphonium salt and a tertiary sulfonium salt; and (d) an epoxy compound covalently bonded to the component (a) or (b) or an independent epoxy compound. A curable resin composition for a paint, comprising: 2. The method according to claim 1, wherein the component (a) is a (meth) acrylate ester of a polyhydric alcohol, an unsaturated polyester resin,
The composition according to claim 1, which is a polyester acrylate resin, an epoxy acrylate resin, a urethane acrylate resin, an α, β-unsaturated carbonyl group-containing acrylic resin, a polyether acrylate resin, or a (meth) acryloyl group-containing silicone oligomer. 3. The component (b) comprises an esterification reaction product of a polyhydric alcohol or polyol with an active methylene group or an active methine group-containing carboxylic acid compound, a reaction product of a polyamine compound and diketene, and an active methylene group-containing product. 2. The composition according to claim 1, which is a polymer of an acrylic monomer or an addition reaction product of an isocyanate compound and an active methylene group-containing compound. 4. The composition according to claim 1, wherein said component (b) is a polyhydric alcohol, acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, polyurethane polyol or silicone polyol. 5. The composition according to claim 1, wherein the cation of the component (c) is a tetraalkylammonium, trialkylaralkylammonium, alkylpyridinium, tetraalkylphosphonium or trialkylsulfonium cation. 6. The anion of the component (c) is an anion derived from salicylic acid, polybasic carboxylic acid, nitric acid, phosphoric acid, acidic phosphoric acid ester, sulfonic acid or sulfurous acid, and the composition is composed of one component. The composition of claim 1 which is thermosetting. 7. The composition according to claim 1, wherein the epoxy group of the epoxy compound as the component (d) is a glycidyl group, an alicyclic epoxy group, or an α-olefin epoxide. 8. A cured film obtained by curing the composition according to claim 1. 9. A multi-layer coating film forming method comprising: coating a base coat composition containing a pigment on an object to be coated; coating a transparent top coat composition thereon by wet-on-wet; and curing both at the same time. A method for forming a multilayer coating film, comprising using the composition according to any one of claims 1 to 7 as a transparent topcoat composition.