WO2019240216A1 - Composition de résine thermodurcissable et film durci - Google Patents

Composition de résine thermodurcissable et film durci Download PDF

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WO2019240216A1
WO2019240216A1 PCT/JP2019/023459 JP2019023459W WO2019240216A1 WO 2019240216 A1 WO2019240216 A1 WO 2019240216A1 JP 2019023459 W JP2019023459 W JP 2019023459W WO 2019240216 A1 WO2019240216 A1 WO 2019240216A1
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acid
meth
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acrylate
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PCT/JP2019/023459
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Japanese (ja)
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佑也 森脇
耕資 浅田
克 呑海
直巳 竹中
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共栄社化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • C08G12/32—Melamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen

Definitions

  • the present invention relates to a thermosetting resin composition having a transesterification reaction as a curing reaction in addition to various curing reactions.
  • thermosetting resin compositions are used in applications such as paints and adhesives. Many of such thermosetting resin compositions use a resin having two or more hydroxyl groups in combination with a curing agent, and cure the resin by a crosslinking reaction between the curing agent and the hydroxyl group.
  • melamine resins and polyisocyanate compounds are widely used. These curing agents are widely used because of their good thermal reactivity and excellent properties of the resulting cured resin.
  • the melamine resin is a cause of sick house syndrome because it generates formaldehyde during the curing reaction, its use may be limited in recent years.
  • acid resistance of melamine resin is not sufficient, improvement in acid resistance is also required.
  • a polyisocyanate compound has a high curing reaction, it is not easy to handle due to its toxicity and is expensive. It is also known to use an alkoxysilane compound as an auxiliary agent for improving physical properties, but it is expensive.
  • Patent Document 1 describes a powder coating material having a transesterification reaction as a curing reaction. However, it is only described for use in powder coatings, and is not disclosed for use in general solvent-based or water-based compositions. Moreover, when using as a coating material or an adhesive agent, water resistance is calculated
  • Patent Document 2 discloses a resin composition for solvent-based paints having a transesterification reaction as a curing reaction. However, although the use of an epoxy compound is disclosed, it is not disclosed that an isocyanate compound or a melamine resin is blended.
  • silane coupling agents are widely used for the purpose of improving adhesion to substrates and improving physical properties of coating films in the paint field.
  • it is not publicly known to use this together with a curing reaction by transesterification.
  • thermosetting resin composition having a conventional transesterification reaction as a curing reaction has room for improvement, and an improvement in reaction rate is required.
  • examination is not made about making it harden
  • the present invention is inexpensive and has good curability and has a curing performance equivalent to that of the prior art by using a transesterification reaction that can be used in various applications as part of the curing reaction.
  • an object of the present invention is to provide a thermosetting resin composition that can achieve cost reduction and can easily control physical properties.
  • the present invention provides at least one curing agent component (A) selected from the group consisting of polyisocyanate compounds, melamine resins, epoxy compounds and alkoxysilane compounds.
  • the resin component (B) having an alkyl ester group and a hydroxyl group is preferably a compound (X) having an alkyl ester group and a hydroxyl group.
  • the resin component (B) having an alkyl ester group and a hydroxyl group may be a mixed composition of the alkyl ester group-containing compound (Y) and the hydroxyl group-containing compound (Z).
  • the resin component (B) having an alkyl ester group and a hydroxyl group may be a mixed composition of the compound (X) having an alkyl ester group and a hydroxyl group, the alkyl ester group-containing compound (Y) and the hydroxyl group-containing compound (Z).
  • the present invention is also a thermosetting film formed by a curing reaction of the thermosetting resin composition.
  • thermosetting resin composition of the present invention can achieve cost reduction, toxicity reduction, improved cured film properties, etc. while having high curing reactivity. Furthermore, since the same effect can be acquired even if it reduces the usage-amount of a melamine resin, an isocyanate resin, an epoxy compound, and an alkoxysilane compound, the problem by use of each hardening agent mentioned above can be improved.
  • thermosetting resin composition has been widely and generally performed by using a melamine resin, an isocyanate resin, an epoxy compound, and an alkoxysilane compound in combination with a hydroxyl group-containing compound. And the problems as described above have been known.
  • the use of the transesterification reaction as a curing reaction of a thermosetting resin has been described in some literatures, but has not been commercialized industrially. This seems to be because the curing rate by the transesterification reaction is often slower than polyisocyanate compounds, melamine resins, epoxy compounds, alkoxysilane compounds, etc., which are commonly used curing agents. It is.
  • the present inventors have studied based on such a background, and in a system in which a polyisocyanate compound, a melamine resin, an epoxy compound, and an alkoxysilane compound are present, a curing reaction by a transesterification reaction is further caused. Is. In the case of such a curing system by a plurality of reactions, it is considered that the reaction rate tends to increase because a cross-linked network is constructed mutually.
  • an ester group formed by an ester exchange reaction between an alkyl ester and a hydroxyl group is preferable in that it has good acid stability and low toxicity.
  • thermosetting resin composition using an alkoxysilane compound can also be improved from the viewpoint of having a synergistic effect because it has a structure that forms a crosslinked structure with alkoxysilane.
  • the transesterification reaction is used as a curing reaction of a thermosetting resin, it is possible to greatly improve problems such as a slow reaction rate.
  • the effect mentioned above is that the polyisocyanate compound, the melamine resin, the epoxy compound, and the alkoxysilane compound are mixed, the reactivity of the transesterification reaction is improved, and the polyisocyanate compound, the melamine resin, the epoxy compound, and the alkoxysilane compound are used. It has been completed by finding that a curing reaction equivalent to that of the cured system can be produced.
  • the thermosetting resin composition characterized in that the functional group that functions as a curing agent is present in the same molecule in the resin composition that causes a transesterification reaction.
  • Hardener component (A) in the present invention, at least one curing agent component (A) selected from the group consisting of a polyisocyanate compound, a melamine resin, an epoxy compound, and an alkoxysilane compound is essential.
  • a curing agent component (A) is not particularly limited, and is a polyisocyanate compound, a melamine resin, an epoxy compound, and an alkoxysilane compound, and is known as a curing agent that reacts with a hydroxyl group and / or a carboxyl group. Can be used. More specifically, the following can be mentioned.
  • Polyisocyanate compound (A-1) The polyisocyanate compound is a compound having at least two isocyanate groups in one molecule, such as aliphatic polyisocyanate, alicyclic polyisocyanate, araliphatic polyisocyanate, aromatic polyisocyanate, Derivatives and the like can be mentioned.
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3.
  • Aliphatic diisocyanates such as butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer diisocyanate, methyl 2,6-diisocyanatohexanoate (common name: lysine diisocyanate); 2 , 6-Diisocyanatohexanoic acid 2-isocyanatoethyl, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6,6 1-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyl Examples thereof include aliphatic triisocyanates such as octane.
  • alicyclic polyisocyanate examples include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name) : Isophorone diisocyanate), 4-methyl-1,3-cyclohexylene diisocyanate (common name: hydrogenated TDI), 2-methyl-1,3-cyclohexylene diisocyanate, 1,3- or 1,4-bis (isocyanato) Methyl) cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, alicyclic diisocyanate such as methylenebis (4,1-cyclohexanediyl) diisocyanate (common name: hydrogenated MDI), norbornane diisocyanate 1,3,5-triis
  • araliphatic polyisocyanate examples include methylene bis (4,1-phenylene) diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ⁇ , ⁇ ′-diisocyanato- Aromatic aliphatic diisocyanates such as 1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or mixtures thereof; 1,3 And araliphatic triisocyanates such as 5-triisocyanatomethylbenzene.
  • MDI methylene bis (4,1-phenylene) diisocyanate
  • 1,3- or 1,4-xylylene diisocyanate or a mixture thereof ⁇ , ⁇ ′-diisocyanato- Aromatic aliphatic diisocyanates
  • aromatic polyisocyanate examples include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4-tolylene diisocyanate (common name: 2,4- TDI) or 2,6-tolylene diisocyanate (common name: 2,6-TDI) or a mixture thereof, aromatic diisocyanates such as 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate; , 4 ′, 4 ′′ -triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene and the like; 4,4′-diphenylmethane-2,2 ′ , 5,5'-tetraisocyanate and other aromatics Mention may be made of the tiger isocyanate.
  • polyisocyanate derivatives examples include dimers, trimers, biurets, allophanates, uretdiones, uretimines, isocyanurates, oxadiazine triones, polymethylene polyphenyl polyisocyanates (crude MDI, polymeric MDI). And Crude TDI.
  • the above aliphatic diisocyanate, alicyclic diisocyanate, and derivatives thereof can be suitably used from the viewpoints of adhesion to a substrate and resistance to cold and heat load.
  • polyisocyanate compound a prepolymer obtained by reacting the polyisocyanate and its derivative with a compound capable of reacting with the polyisocyanate under the condition of excess isocyanate group may be used.
  • the compound capable of reacting with the polyisocyanate include compounds having an active hydrogen group such as a hydroxyl group and an amino group.
  • polyhydric alcohol, low molecular weight polyester resin, amine, water, etc. Can be used.
  • the polyisocyanate compound includes a polymer of an isocyanate group-containing polymerizable unsaturated monomer, or a polymerizable unsaturated monomer other than the isocyanate group-containing polymerizable unsaturated monomer and the isocyanate group-containing polymerizable unsaturated monomer.
  • a copolymer may be used.
  • the polyisocyanate compound may be a polyisocyanate compound in which an isocyanate group is blocked with a blocking agent, a so-called blocked polyisocyanate compound.
  • the blocking agent examples include phenols such as phenol, cresol, xylenol, nitrophenol, ethylphenol, hydroxydiphenyl, butylphenol, isopropylphenol, nonylphenol, octylphenol, and hydroxybenzoic acid methyl; ⁇ -caprolactam, ⁇ -valerolactam, Lactams such as ⁇ -butyrolactam and ⁇ -propiolactam; aliphatic alcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol, lauryl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene Ethers such as glycol monomethyl ether and methoxymethanol; benzyl alcohol, glycolic acid, methyl glycolate, ethyl glycolate, butyl glyco
  • azole compounds examples include pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3, Pyrazole or pyrazole derivatives such as 5-dimethylpyrazole and 3-methyl-5-phenylpyrazole; Imidazole or imidazole derivatives such as imidazole, benzimidazole, 2-methylimidazole, 2-ethylimidazole and 2-phenylimidazole; 2-methylimidazoline And imidazoline derivatives such as 2-phenylimidazoline.
  • preferred blocking agents include oxime blocking agents, active methylene blocking agents, pyrazoles or pyrazole derivatives.
  • solvents used for the blocking reaction are preferably those that are not reactive with isocyanate groups.
  • ketones such as acetone and methyl ethyl ketone
  • esters such as ethyl acetate
  • NMP N-methyl-2-pyrrolidone
  • Melamine resin (A-2) It does not specifically limit as a melamine resin which can be used in this invention, The arbitrary thing generally used as a hardening
  • curing agent can be used.
  • Alkyl etherified melamine resins such as methyl-butyl mixed etherified melamine resins partially or fully etherified with are preferred. Such an alkyl etherified melamine resin is particularly preferable in terms of excellent curing performance.
  • Epoxy compound (A-3) The epoxy compound that can be used in the present invention is not particularly limited, and examples thereof include known arbitrary epoxy compounds such as an epoxy group-containing acrylic resin, a bisphenol type epoxy resin, and an alicyclic epoxy compound.
  • the epoxy group-containing acrylic resin is preferably an epoxy group-containing acrylic resin having an epoxy group equivalent of 50 to 700.
  • one molecule has an average of 2 or more, preferably 2 to 10, more preferably 3 to 8 epoxy groups in one molecule.
  • the epoxy group-containing acrylic resin preferably has a number average molecular weight of 200 to 10,000. More preferably, it is 500 to 8000, more preferably 800 to 5000. A larger number average molecular weight is preferable in view of sufficient curability of the coating film, and a smaller number average molecular weight is preferable in order to increase the solid content of the resulting coating.
  • the epoxy group equivalent is 50 to 700, preferably 80 to 600, and more preferably 100 to 500.
  • the epoxy group equivalent is preferably smaller in view of sufficient curability of the coating film, and is preferably larger in consideration of the brittleness of the coating film.
  • the epoxy group-containing acrylic resin (B) is an epoxy group-containing ethylenically unsaturated monomer of 10 to 60% by mass, preferably 15 to 50% by mass, and an ethylenically unsaturated monomer having no epoxy group of 40 to 90% by mass, preferably Is preferably an acrylic polyepoxide obtained by copolymerizing 50 to 85% by mass.
  • the amount of the epoxy group-containing ethylenically unsaturated monomer is preferably large in consideration of sufficient curability of the coating film, and is preferably small in consideration of the weather resistance of the coating film.
  • Examples of the epoxy group-containing ethylenically unsaturated monomer include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, and 3,4-epoxycyclohexanyl (meth) acrylate. In order to prepare a paint exhibiting balanced curability and storage stability, it is preferable to use glycidyl (meth) acrylate.
  • Examples of the ethylenically unsaturated monomer having no epoxy group include various unsaturated group-containing monomers described in detail below.
  • a hydroxyl group-containing monomer when used in combination with the epoxy group-containing ethylenically unsaturated monomer, the hydroxyl group can participate in the transesterification described in detail below. Therefore, it is preferable in that a high crosslinking density can be obtained more suitably. Furthermore, since an epoxy group can react with a hydroxyl group, it is also preferable in terms of obtaining a good crosslinking density.
  • the hydroxyl group-containing monomer that can be used here is a hydroxyl group-containing monomer exemplified in “resin component (B)” described in detail below.
  • the body can be mentioned.
  • the epoxy group-containing acrylic resin has a hydroxyl group
  • the epoxy group-containing acrylic resin has a hydroxyl value of 5 to 300 mgKOH / g, preferably 10 to 200 mgKOH / g, more preferably 15 to 150 mgKOH / g.
  • the hydroxyl value exceeds 300, the solid content of the paint is lowered or the water resistance of the cured coating film is insufficient, and when it is less than 5, the adhesion is inferior.
  • Particularly preferred epoxy group-containing acrylic resins include 5 to 70% by mass of a hydroxyl group-containing ethylenically unsaturated monomer, (ii) 10 to 60% by mass of an epoxy group-containing ethylenically unsaturated monomer, and (iii) a hydroxyl group as required. It can be obtained by copolymerizing with 0 to 85% by mass of an ethylenically unsaturated monomer that does not have both epoxy groups.
  • the epoxy group-containing acrylic resin preferably has an average of 2 to 12, more preferably 3 to 10, and preferably an average of 0.5 to 10, more preferably hydroxyl groups in one molecule. Have 1-8.
  • the hydroxyl-containing monomer illustrated in "resin component (B)" explained in full detail below can be used for the hydroxyl-containing monomer which can be used here.
  • epoxy group-containing resin other than the above-mentioned epoxy group-containing acrylic resin novolak type polyepoxy, epichlorohydrin-bisphenol type polyepoxy, butanediol diglycidyl ether, 1.6-hexanesiodiol diglycidyl ether
  • Polyglycol ether type such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether Epoxidation of polycarboxylic acid esters such as epoxy compounds and diglycidyl phthalate Products, isocyanurate type epoxy compounds such as triglycidyl isocyanurate, epoxidized fatty acid esters such as
  • curing agent component (A) When using an epoxy compound as said hardening
  • the compound having a carboxylic acid that can be used here include an acid group-containing acrylic resin containing a carboxyl group and a carboxylic acid ester group having an acid value of 50 to 300 mgKOH / g (solid content).
  • the above-described compound containing an epoxy group may be a compound having a carboxyl group. Further, it may contain a hydroxyl group.
  • the acid group-containing acrylic resin is not particularly limited as long as it has an acid group, and examples thereof include an acrylic resin having a structural unit derived from (meth) acrylic acid and itaconic acid.
  • the acid group-containing acrylic resin may be obtained by reacting an acrylic resin having an acid anhydride group with a monoalcohol.
  • the acrylic resin having an acid anhydride group includes, for example, an acid anhydride group-containing ethylenically unsaturated monomer, preferably 15 to 40% by mass, more preferably 15 to 35% by mass, and an ethylenic group having no acid anhydride group. It is obtained by copolymerizing a saturated monomer, preferably 60 to 85% by mass, more preferably 65 to 85% by mass.
  • the amount of the acid anhydride group-containing ethylenically unsaturated monomer is less than 15% by mass, the curability is insufficient, and when it exceeds 40% by mass, the resulting coating film becomes too brittle and the weather resistance tends to be insufficient.
  • the acid anhydride group-containing ethylenically unsaturated monomer include itaconic anhydride, maleic anhydride, and citraconic anhydride.
  • the ethylenically unsaturated monomer having no acid anhydride group is not particularly limited as long as it does not adversely affect the acid anhydride group, and has 3 to 15, particularly 3 to 12 carbon atoms having one ethylenically unsaturated bond. It is preferable that it is a monomer. Specific examples include styrene, ⁇ -methylstyrene, pt-butylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, normal butyl (meth) acrylate, (meth) acrylic acid.
  • (Meth) acrylic acid esters such as isobutyl, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate,
  • VeoVa-9 and VeoVa-10 manufactured by Shell are listed.
  • the monomer which has a carboxyl group like acrylic acid, methacrylic acid, itaconic acid, and maleic acid is also mentioned.
  • ⁇ -caprolactone 2 mol-modified acrylic acid such as about 5 to 20 carbon atoms between the ethylenically unsaturated group and the carboxyl group.
  • ⁇ -caprolactone 2 mol-modified acrylic acid such as about 5 to 20 carbon atoms between the ethylenically unsaturated group and the carboxyl group.
  • Use of a long-chain carboxylic acid monomer having a minute spacer portion improves the scratch resistance of the coating film, which is particularly preferable.
  • This acid anhydride group-containing acrylic resin includes, for example, a hydroxyl group-containing monomer and an acid anhydride group-containing compound, and a hydroxyl group and an acid anhydride group in a molar ratio of 1 / 0.5 to 1 / 1.0, Preferably, a carboxyl group-containing ethylenically unsaturated monomer obtained by a half esterification reaction in an amount of 1 / 0.8 to 1 / 1.0, and an ethylenically unsaturated monomer having no acid anhydride group Are copolymerized with each other.
  • the molar ratio of the hydroxyl group to the acid anhydride group exceeds 1 / 0.5, the polymer viscosity becomes high, resulting in poor workability.
  • the ratio is less than 1 / 1.0, an excessive acid anhydride group-containing compound remains, and the water resistance of the coating film is lowered.
  • the acid anhydride group-containing compound used here examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trimellitic anhydride, succinic anhydride, and the like. It can also be used together.
  • the half-esterification reaction of the hydroxyl group-containing ethylenically unsaturated monomer and the acid anhydride group-containing compound is performed at a temperature of room temperature to 150 ° C. according to a usual method.
  • Copolymerization of an acid anhydride group-containing ethylenically unsaturated monomer with an ethylenically unsaturated monomer having no acid anhydride group and copolymerization of the above monomer with an ethylenically unsaturated monomer having no acid anhydride group
  • the polymerization can be carried out by a known method such as solution polymerization such as radical polymerization, for example, at normal pressure or under pressure, at a polymerization temperature of 100 to 200 ° C., and a polymerization time of 3 to 8 hours.
  • the initiator an azo-based or peroxide-based initiator is preferably used.
  • Other additives such as chain transfer agents can also be used.
  • the number average molecular weight of the obtained polymer is preferably 500 to 8000, more preferably 800 to 6000, and particularly preferably 1500 to 4000.
  • the number average molecular weight exceeds 8000, the compatibility between the resins decreases, and the appearance deteriorates.
  • the number average molecular weight is less than 500, the curability of the resin composition becomes insufficient.
  • the resulting polymer has an average of at least 2, preferably 2 to 15, acid anhydride groups in one molecule, and when the number of acid anhydride groups contained in one molecule is less than 2, Curability is insufficient. If it exceeds 15, it becomes too brittle and the weather resistance is insufficient.
  • the said number average molecular weight can be obtained as a conversion value by a styrene polymer standard using a gel permeation chromatography (GPC).
  • the obtained acrylic resin having an acid anhydride group has a molar ratio of acid anhydride group to hydroxyl group of 1/10 to 1/1, preferably 1/5 to 1/1, more preferably 1/2.
  • An acid group-containing acrylic resin having a carboxyl group and a carboxylic ester group is prepared by reacting with monoalcohol in an amount of ⁇ 1 / 1. When this molar ratio is less than 1/10, there is too much excess alcohol and causes cracking at the time of curing, and when it exceeds 1/1, unreacted anhydride groups remain, resulting in poor storage stability.
  • the monoalcohol preferably has 1 to 12, particularly 1 to 8 carbon atoms.
  • Preferred monoalcohols include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, n-hexyl alcohol, lauryl alcohol, methyl cellosolve, ethyl cellosolve, methoxypropanol, ethoxypropanol, furfuryl alcohol, dimethyl.
  • Examples include aminoethanol, diethylaminoethanol, acetol, allyl alcohol, and propargyl alcohol, which can be used in combination. Particularly preferred are acetol, furfuryl alcohol, allyl alcohol, propargyl alcohol, ethanol and methanol.
  • the acid value of the obtained acid group-containing acrylic resin is 50 to 300 mgKOH / g, preferably 50 to 250 mgKOH / g.
  • the acid value is less than 50 mgKOH / g, the curability of the coating film becomes insufficient, and when it exceeds 300 mgKOH / g, the storage stability of the intermediate coating becomes poor.
  • the acid group-containing acrylic resin component is thermally cured at a rate of 10 to 70% by mass, preferably 15 to 50% by mass, more preferably 20 to 45% by mass, based on the mass of the total solid content of the thermosetting resin composition. It mix
  • the blending amount is preferably large in consideration of the acid resistance of the coating film, and is preferably small in consideration of the brittleness of the cured product.
  • Alkoxysilane compound (A-4) The alkoxysilane compound that can be used in the present invention is not particularly limited, and examples thereof include compounds having a Si—OR group that can be cross-linked by reacting with a hydroxyl group. More specifically,
  • R a represents an alkyl group having 1 to 50 carbon atoms which may have a substituent.
  • R b represents an alkyl group having 1 to 4 carbon atoms.
  • n represents an integer of 0 to 2)
  • R a represents an alkyl group having 1 to 50 carbon atoms which may have a substituent.
  • R b represents an alkyl group having 1 to 4 carbon atoms.
  • n represents an integer of 0 to 2
  • n represents an integer of 0 to 2
  • the alkoxysilane compound may be a silicon compound having a functional group such as a vinyl group, an epoxy group, an amino group, a (meth) acryloyl group, a carboxyl group, or a mercapto group in addition to the alkoxy group.
  • a functional group such as a vinyl group, an epoxy group, an amino group, a (meth) acryloyl group, a carboxyl group, or a mercapto group in addition to the alkoxy group.
  • These are compounds also called alkoxysilanes, and such compounds can also be suitably used as the alkoxysilane compounds of the present invention.
  • alkoxysilane compounds include, for example, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltriethoxysilane, ⁇ -ureidopropyltriethoxysilane, N- ⁇ - (N-vinylbenzylaminoethyl) ) - ⁇ -aminopropyltrimethoxysilane, ⁇ -anilinopropyltrimethoxysilane and other amino group-containing alkoxysilane compounds; ⁇ -mercaptopropyltrimethoxysilane, ⁇ -
  • alkoxysilane compound having no functional group described above examples include dialkoxysilane, trialkoxysilane, and tetraalkoxysilane.
  • dialkoxysilane examples include dimethoxydimethylsilane, dimethoxydiethylsilane, dimethoxydiphenylsilane, diethoxydimethylsilane, diethoxydiethylsilane, diethoxydiphenylsilane, dipropoxydimethylsilane, dipropoxydiethylsilane, and dipropoxydipropyl.
  • Examples thereof include silane, dipropoxydiphenylsilane, dibutoxydimethylsilane, dibutoxydiethylsilane, dibutoxydibutylsilane, and dibutoxydiphenylsilane.
  • trialkoxysilane examples include trimethoxymethylsilane, trimethoxyethylsilane, trimethoxypropylsilane, trimethoxybutylsilane, trimethoxyphenylsilane, triethoxymethylsilane, triethoxyethylsilane, triethoxybutylsilane, trimethoxybutylsilane, Examples include ethoxyphenylsilane, tripropoxymethylsilane, tripropoxypropylsilane, tripropoxyphenylsilane, and tributoxyphenylsilane.
  • tetraalkoxysilane examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and dimethoxydiethoxysilane.
  • alkoxysilanes trialkoxysilane and tetraalkoxysilane are preferable from the viewpoint of crosslinkability.
  • the alkoxy group of these alkoxysilanes is not particularly limited, and examples thereof include an alkoxy group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably 1 to 2 carbon atoms.
  • At least one low-condensate of di-, tri-, and tetra-alkoxysilanes may be a low-condensate of a single alkoxysilane of mono-, di-, tri-, and tetra-alkoxysilanes.
  • a low condensate of the above alkoxysilane may be used.
  • the low condensate preferably has a degree of polymerization of 10 or less, particularly about 2 to 6.
  • a mono-alkoxysilane may be partially used.
  • curing agent component (A) is a polyisocyanate compound and / or a melamine resin
  • curing agent component (A) namely, (hardening agent amount) / (hardening).
  • the amount of the agent + the amount of the resin component is preferably 0.01 to 50% by weight, so that the curing reaction by the transesterification reaction and the curing reaction by another curing agent can be simultaneously performed. It is preferable in that it is generated.
  • the lower limit is more preferably 0.01% by weight, and still more preferably 1% by weight.
  • the upper limit is more preferably 30% by weight, still more preferably 20% by weight.
  • the (hardening agent amount) / (hardening agent amount + resin component amount) is preferably 0.001 to 10% by weight.
  • Such a range of the blending amount is preferable in that a curing reaction by the transesterification reaction and a curing reaction by another curing agent are caused simultaneously.
  • the blending ratio of the curing agent component (A) is a case where (curing agent amount) / (curing agent amount + resin component amount) is used at a relatively low ratio of 1 to 20% by weight.
  • sufficient curing performance is produced. This is presumably because curing by the resin component (B) proceeds preferentially, and the curing reaction by the curing agent component (A) proceeds auxiliary, thereby promoting the curing reaction.
  • the curing agent component (A) may be a combination of two or more of the aforementioned polyisocyanate compound, melamine resin, epoxy compound and alkoxysilane compound.
  • the resin component (B) having an alkyl ester group and a hydroxyl group is used. That is, the presence of such a resin component (B) and a transesterification catalyst (C) causes a transesterification reaction at the time of curing, thereby causing curing of the resin. Furthermore, the hydroxyl group in the resin component (B) reacts with both the curing agent component (A) and the carboxy ester group in the resin component (B), thereby causing curing by a plurality of reaction systems, and producing a good cured product. Obtainable. Furthermore, good results can be obtained at the curing temperature and the curing time.
  • the alkyl ester group and the hydroxyl group exist in the compound composition, and if the alkyl ester group and the hydroxyl group exist,
  • the specific chemical structure and the like are not particularly limited. The specific structure is described in detail below, but the resin component (B) of the present invention is not limited to these.
  • the alkyl ester group of the present invention is The curing reaction of the thermosetting resin composition of the present invention is a crosslinking reaction by a reaction between an alkyl ester group and a hydroxyl group.
  • the alkyl ester group of the general formula R 2 is not limited. Those having a known ester group such as methyl ester group, ethyl ester group, n-propyl ester group, isopropyl ester group, n-butyl ester group, isobutyl ester group, sec-butyl ester group, t-butyl ester group Can be used.
  • the alkyl group can have 50 or less carbon atoms. Since the alkyl group is preferably volatilized after the curing reaction, the alkyl group preferably has 20 or less carbon atoms, and more preferably 10 or less. In addition, the boiling point of the corresponding alcohol that volatilizes in the curing reaction is preferably 300 ° C. or less, and more preferably 200 ° C. or less.
  • the resin component (B) having an alkyl ester group and a hydroxyl group in the present invention may be a compound in which both an alkyl ester group and a hydroxyl group are present in one compound, or a compound having an alkyl ester group and a hydroxyl group. It may be a mixture with the compound that it has.
  • the resin component (B) for example, (I) Compound (X) having an alkyl ester group and a hydroxyl group, (II) a composition containing an alkyl ester group-containing compound (Y) and a hydroxyl group-containing compound (Z); (III) A composition containing an alkyl ester group and a hydroxyl group-containing compound (X), and an alkyl ester group-containing compound (Y) and / or a hydroxyl group-containing compound (Z) can be mentioned.
  • the clear coating used in the present invention may contain a component having both an alkyl ester group and a hydroxyl group. Although it does not specifically limit as such a thing, The acrylic resin which has these functional groups, a vinyl polymer, a polyester resin, ester of a hydroxycarboxylic acid compound, etc. can be mentioned.
  • the acrylic resin having both an alkyl ester group and a hydroxyl group is easy to control its composition, and since it is easy to introduce a necessary amount of functional groups or to control viscosity, Particularly preferred.
  • An acrylic resin having both an alkyl ester group and a hydroxyl group is polymerized by mixing a monomer having an alkyl ester group and a monomer having a hydroxyl group at a predetermined ratio and copolymerizing them by a general method. Can be obtained at
  • R 1 , R 2 and R 3 represent hydrogen, an alkyl group, a carboxyl group, and an alkyl ester group, R 4 represents an alkyl group
  • Examples of the compound represented by the general formula (1) include ester derivatives of known unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid.
  • the alkyl group represented by R 4 is most preferably a t-butyl group.
  • the most typical monomer having an alkyl ester group represented by the general formula (1) is an ester of (meth) acrylic acid and alcohol, and examples thereof include t-butyl (meth) acrylate. be able to.
  • tertiary alkyl esters such as t-butyl (meth) acrylate are most preferable from the viewpoint of crosslinking reactivity.
  • t-Butyl (meth) acrylate is particularly preferable in that it is a raw material that easily causes a transesterification reaction and is inexpensive and easily available.
  • the alkylester monomer which has a chemical structure represented by following General formula (2) may be used as a monomer which has an alkylester group.
  • the alkylester monomer which has a chemical structure represented by following General formula (2) may be used.
  • an alkyl ester monomer having a structure represented by the following general formula (2) is used, even if one using a primary or secondary alkyl ester is used, a good transesterification reaction occurs. Is preferable.
  • R 4 has 50 or less main chain atoms, and may have one or more functional groups selected from the group consisting of ester groups, ether groups, amide groups, and urethanes in the main chain.
  • An aliphatic, alicyclic or aromatic alkylene group which may have a side chain.
  • R 5 is an alkyl group having 50 or less carbon atoms
  • the monomer represented by the general formula (2) preferably has a chemical structure represented by the following general formula (3).
  • R 6 is H or a methyl group.
  • R 7 is an alkylene group having 48 or less atoms in the main chain, and may have an ester group, an ether group and / or an amide group in the main chain, and may have a side chain.
  • R 8 is an alkyl group having 50 or less carbon atoms.
  • Such a compound is a derivative of (meth) acrylic acid, and can be obtained by a known synthesis method using (meth) acrylic acid or a derivative thereof as a raw material.
  • the number of atoms in the main chain of R 7 is more preferably 40 or less, further preferably 30 or less, and further preferably 20 or less.
  • the atoms that may be contained in the main chain of R 7 are not particularly limited, and may include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, etc. in addition to carbon atoms. More specifically, the main chain of R 7 has an ether group, an ester group, an amino group, an amide group, a thioether group, a sulfonic acid ester group, a thioester group, a siloxane group, etc. in addition to the alkyl group. There may be.
  • examples of the structure represented by the general formula (3) include compounds represented by the following general formula (4).
  • R 9 is an alkyl group having 1 to 50 carbon atoms.
  • R 10 is an alkylene group having 44 or less atoms in the main chain, and may have an ester group, an ether group and / or an amide group in the main chain, and may have a side chain.
  • R 11 is H or a methyl group.
  • R 12 is an alkyl group having 50 or less carbon atoms.
  • R 13 is H or a methyl group.
  • n 3 is 0 or 1.
  • n 4 is 1 or 2.
  • the compound represented by the general formula (3) is synthesized by reacting a compound that generates an active anion such as a malonic acid ester or acetoacetic acid ester having an unsaturated bond in the molecule with an unsaturated compound having an alkyl ester group.
  • malonic acid ester and acetoacetic acid ester have a methylene group sandwiched between carboxy carbons, and this methylene group is easily anionized and is widely known to easily generate an anionic reaction.
  • Such a compound having an unsaturated bond in the alkyl group of malonic acid ester or acetoacetic acid ester for example, malonic acid or acetoacetic acid and an unsaturated single molecule having a hydroxyl group described in detail as “hydroxyl vinyl monomer” below).
  • hydroxyl vinyl monomer By reacting an ester compound with a monomer with an alkyl ester compound having an unsaturated group, a compound having both an unsaturated group and an alkyl ester group can be synthesized.
  • the compound having such a structure can easily change only the alkyl ester group by using widely used raw materials, and as a result, the curing reactivity can be easily adjusted. Further, it is particularly preferable in that the curing reactivity can be adjusted by changing the reaction rate to the active methylene group.
  • the compound that can be used as the “alkyl ester compound having an unsaturated group” used in the above reaction is not particularly limited, and is a (meth) acrylic acid alkyl ester, methylene malonic acid alkyl ester, a lactone compound having an unsaturated group (for example, ⁇ -Crotonolactone, 5,6-dihydro-2H-pyran-2-one) and the like.
  • the reaction can be performed under basic conditions, for example, by a reaction in an organic solvent in the presence of a crown ether of an alkali metal salt.
  • An example of such a synthesis reaction is shown below.
  • n 1 : 1-10 (Wherein, R 1, R 2, R 3 are the same or different, hydrogen, an alkyl group, a carboxyl group, an alkyl ester group or the following R 4 - represents a [COOH] structure represented by n 1.
  • R 4 has 50 or less main chain atoms, and may have one or more functional groups selected from the group consisting of ester groups, ether groups, amide groups, and urethanes in the main chain.
  • An aliphatic, alicyclic or aromatic alkylene group which may have a side chain.
  • Such a known compound can be made into an unsaturated group-containing ester compound of the present invention by carrying out a normal esterification reaction (for example, reaction with an alcohol corresponding to the alkyl group of the target alkyl ester). .
  • R represents an alkyl group.
  • Such a compound is preferable in that it can be cured at a low temperature because of its high transesterification reactivity.
  • the structural unit having an alkyl ester as a skeleton preferably occupies 1% by weight or more in the polymer. If it is less than 1% by weight, the amount of the crosslinkable functional group is small, which is not preferable in that the curing reaction does not proceed sufficiently.
  • the content is more preferably 5% by weight or more, and still more preferably 10% by weight or more.
  • a hydroxyl group-containing vinyl monomer for introducing the hydroxyl group.
  • Typical examples of the hydroxyl group-containing vinyl monomer are shown below.
  • Various hydroxyl group-containing vinyl ethers such as vinyl ethers; or addition reaction products of these various vinyl ethers with ⁇ -caprolactone; 2-hydroxyethyl (meth) allyl ether, 3-hydroxypropyl (meth) allyl ether, 2-hydroxypropyl (meth) allyl ether, 4-hydroxybutyl (meth) allyl ether, 3-hydroxybutyl (meth) allyl ether, Various hydroxyl group-containing vinyl ethers such as vinyl ethers; or addition reaction
  • the structural unit having the hydroxyl vinyl monomer as a skeleton preferably occupies 1% by weight or more in the polymer. If it is less than 1% by weight, the amount of the crosslinkable functional group is small, which is not preferable in that the curing reaction does not proceed sufficiently.
  • the content is more preferably 5% by weight or more, and still more preferably 10% by weight or more.
  • the acrylic resin may have a part of a structural unit having a monomer other than an alkyl group-containing monomer and a hydroxyl vinyl monomer as a skeleton.
  • a structural unit having a skeleton other than the alkyl group-containing monomer and the hydroxyl vinyl monomer in the acrylic resin and examples include the monomers described in detail below. Can do.
  • ⁇ -olefins such as ethylene, propylene or butene-1; Various halogenated olefins, except fluoroolefins, such as vinyl chloride or vinylidene chloride;
  • alkyl (meth) acrylates having 1 to 18 carbon atoms various cycloalkyl (meth) acrylates, aralkyl (meth) acrylates, phenyl (meth) acrylates or (meta) having a substituted phenyl group ) Acrylate;
  • aromatic vinyl compounds such as styrene, ⁇ -methylstyrene or vinyltoluene; N-dimethylaminoethyl (meth) acrylamide, N-diethylaminoethyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide or N -Various amino group-containing amide unsaturated monomers, such as diethyla
  • the content of such other components is not particularly limited, but is preferably 70% by weight or less.
  • the acrylic resin having both the alkyl ester group and the hydroxyl group preferably has a glass transition temperature of 80 ° C. or lower.
  • the monomer has a relatively high glass transition temperature among various acrylates. For this reason, a glass transition temperature can be made into 80 degrees C or less by using together the structural unit based on another monomer.
  • the glass transition temperature is more preferably 50 ° C. or lower.
  • the clear paint is an organic solvent system
  • the glass transition temperature exceeds 80 ° C. in the acrylic resin
  • transesterification reactivity is slow, and it becomes difficult to form a coating film by low-temperature curing.
  • Cheap even in the obtained coating film, sufficient crosslinking may not be obtained, and the performance as a coating film may not be sufficiently secured.
  • the alkyl ester group and hydroxyl which are reaction points by lowering Tg. It is thought that the group becomes easy to move and the reaction proceeds. Moreover, when an ester group is added to the end having a longer side chain, the reactivity is improved by increasing the degree of freedom of the reaction point. Further, it is also preferable that the glass transition temperature is 80 ° C. or less, in that the leveling property, crosslinkability, and film properties are improved.
  • Tg represents the glass transition temperature of the polymer portion
  • Tg 1 , Tg 2 ,..., Tg m represent the glass transition temperature of each polymerization monomer
  • W 1 , W 2 ,..., W m represent the weight ratio of each polymerization monomer.
  • a polymer monomer having a low glass transition temperature in combination with an alkyl (meth) acrylate is preferable.
  • Such monomers include 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, alkyl (C12-13) methacrylate, isoamyl acrylate, lauryl acrylate, ethoxydiethylene glycol acrylate, 2-ethylhexyl glycol acrylate, methoxyethylene glycol Acrylate, methoxydipropylene glycol acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, m-phenoxybenzyl acrylate, tetrahydrofurfuryl acrylate, 2-acryloyloxyethyl succin
  • t-butyl (meth) acrylate has a high glass transition temperature. Therefore, when t-butyl (meth) acrylate is used as the alkyl (meth) acrylate, the content in the resin should be 80% by weight or less in order to make the glass transition point 80 ° C. or less. Preferably, it is more preferably 50% by weight or less, and most preferably 30% by weight or less.
  • the acrylic resin having both the alkyl ester group and the hydroxyl group preferably has a number average molecular weight of 1,000 to 100,000.
  • the said number average molecular weight is a value of polystyrene conversion molecular weight measured by gel permeation chromatography (GPC).
  • the acrylic resin having both the alkyl ester group and the hydroxyl group is not particularly limited in its production method, and can be produced by polymerization by a known method. More specifically, polymerization methods such as solution polymerization methods in organic solvents, emulsion polymerization methods in water, miniemulsion polymerization methods in water, aqueous solution polymerization methods, suspension polymerization methods, UV curing methods, etc. Can do.
  • solution polymerization in an organic solvent it may be water-dispersed by water dispersion or a resin obtained by polymerizing in water dissolved in an organic solvent. Good.
  • alkyl esters of various hydroxycarboxylic acids can be used. Specific examples include compounds obtained by alkylating carboxyl groups such as lactic acid, 3-hydroxybutanoic acid, 3-hydroxy-4-ethoxybenzoic acid, tartaric acid, citric acid, and amino acids.
  • the resin composition of the present invention may be a mixture of an alkyl ester group-containing component and a hydroxyl group-containing component as a coating film forming component.
  • the alkyl ester group-containing compound that can be used in such a composition is described in detail below.
  • Y-1 (a polymer having a part or all of structural units of a monomer having an alkyl ester group and a polymerizable unsaturated bond)
  • a polymer is a polymer having an ester group and no hydroxyl group.
  • a resin similar to the above-mentioned acrylic resin containing an alkyl ester group and a hydroxyl group can be used except that a hydroxyl group vinyl monomer is not used.
  • Such a compound is preferable in that a compound having two or more alkyl ester groups in the molecule can be obtained at low cost by using a general-purpose material.
  • the monomer having an alkyl ester group and a polymerizable unsaturated bond includes a polymerizable unsaturated bond and an ester group. May be a compound in which is bonded via a linking group.
  • Such a monomer can be used by blending the other monomers exemplified in “component having both ester group and hydroxyl group” in the same ratio.
  • the clear paint of the present invention may be a mixture of an alkyl ester group-containing component and a hydroxyl group-containing component as a coating film forming component.
  • the alkyl ester group-containing compound that can be used in such a composition is described in detail below.
  • A-1 Polymer having a monomer having an alkyl ester group and a polymerizable unsaturated bond as a part or all of the structural unit
  • a polymer is a polymer having an ester group and no hydroxyl group.
  • a resin similar to the above-mentioned acrylic resin containing an alkyl ester group and a hydroxyl group can be used except that a hydroxyl group vinyl monomer is not used.
  • Such a compound is preferable in that a compound having two or more alkyl ester groups in the molecule can be obtained at low cost by using a general-purpose material.
  • Tg may be adjusted by copolymerizing t-butyl (meth) acrylate with other monomers.
  • Tg is preferably 80 ° C. or lower.
  • R 40 represents a primary to tertiary alkyl group having 50 or less carbon atoms.
  • X represents an OR 40 group or a hydrocarbon group having 5 or less carbon atoms. In the case where two R 40 are present in one molecule, these R 40 may be those which differ even in the same. )
  • R 40 is not particularly limited, but is methyl ester group, ethyl ester group, benzyl ester group, n-propyl ester group, isopropyl ester group, n-butyl ester group, isobutyl ester group, sec- Those having a known ester group such as a butyl ester group can be used.
  • Such a compound having an active methylene group include malonic acid esters and acetoacetic acid esters.
  • a compound obtained by adding these compounds to a vinyl compound can be used.
  • a compound having an active methylene group can be added to a double bond by a Michael addition reaction.
  • a general Michael addition reaction by such a compound having an active methylene group is represented by the following formula.
  • a compound represented by the following general formula (6-1) can also be obtained by causing both of the two hydrogen atoms of the active methylene group to undergo a Michael reaction.
  • the compound obtained by such a reaction has a structure represented by the general formula (6) and / or a structure represented by the general formula (6-1), which includes two or more alkyl ester groups. Can be used particularly preferably for the purposes of the present invention.
  • R 40 represents a primary to tertiary alkyl group having 50 or less carbon atoms.
  • R 45 represents hydrogen or a methyl group.
  • R 46 is not particularly limited, and can be any functional group depending on the purpose.
  • a compound represented by the following general formula (8) can also be obtained by causing both of the two hydrogen atoms of the active methylene group to undergo a Michael reaction.
  • the compound represented by the general formula (8) can be obtained by adjusting the molar ratio of (meth) acrylic acid ester and active methylene compound in the blending of raw materials. Furthermore, it can also obtain as a mixture of the compound represented by the said General formula (7), and the compound represented by the said General formula (8) by adjusting these molar ratio.
  • the ester compound obtained by such a reaction is
  • the structural unit represented by the structure is contained in the molecule.
  • the structure represented by the general formula (9) and / or (10) represented by the general formula is a molecule. It can also be set as the ester compound which has 2 or more in. That is, it has the functional group,
  • a compound having a structure represented by the general formula can be suitably used in the present invention.
  • Such a compound is preferable in that it has high transesterification reactivity and has many COOR groups in the molecule, so that good curability can be obtained.
  • n 5 and n 6 are most preferably 2 to 12.
  • L and M are not particularly limited as long as the molecular weight of the compound is 3000 or less, and may have any functional group such as a hydroxyl group, an ester group, and an ether group. Represents a hydrogen group.
  • the above-mentioned “compound obtained by addition reaction between a compound having an active methylene group and a vinyl group” uses a compound having two or more unsaturated bonds in one molecule as a raw material, and the above general formula
  • the structure represented by (11) and / or the structure represented by the general formula (12) may have two or more in one molecule.
  • Such a compound is obtained by performing a Michael addition reaction with a compound having an active methylene group using a raw material of various (meth) acrylic acid derivatives having two or more unsaturated bonds.
  • the “(meth) acrylic acid derivative having one or more unsaturated bonds” is not particularly limited, and examples thereof include the following.
  • Examples of the (meth) acrylate having 1 functional group include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl ( Examples thereof include meth) acrylate and t-butyl (meth) acrylate.
  • Examples of (meth) acrylates having 2 functional groups are 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol Di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 Nonanediol di (meth) acrylate, 1,10-decan
  • bisphenol A PO adduct diacrylate manufactured by Kyoeisha Chemical Co., Ltd .; BP-4PA
  • dimethylol-tricyclodecane di (meth) acrylate DCP-A
  • DCP-A dimethylol-tricyclodecane di (meth) acrylate
  • Examples of the (meth) acrylate having 3 functional groups are trimethylolmethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, trimethylolpropane propylene oxide modified tri ( Meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin propoxytri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate and the like.
  • trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, and the like can be preferably used.
  • Examples of (meth) acrylates having 4 functional groups are dipentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide modified tetra (meth) acrylate, pentaerythritol propylene oxide modified tetra (meth) acrylate. , Ditrimethylolpropane tetra (meth) acrylate and the like. Of these, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like can be preferably used.
  • Examples of (meth) acrylates having 4 or more functional groups include pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide modified tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate, dipenta Examples include polyfunctional (meth) acrylates such as hexa (meth) acrylate of a caprolactone modified product of erythritol.
  • R represents the same or different alkyl groups.
  • n 7 represents 1 to 10;
  • the said compound has a 3 or more alkylester used as a crosslinking point in a molecule
  • the alkyl ester is more preferably 5 or more in the molecule. Note that the compounds described in the section (A-2) can also produce a good transesterification reaction when the alkyl ester group is primary or secondary alkyl.
  • n 31 is preferably an integer of 1 to 10.
  • polyfunctional carboxylic acids are general-purpose raw materials that are widely and inexpensively provided for many uses such as polyester raw materials, polyamide raw materials, neutralizing agents, synthetic raw materials, and the like.
  • a compound obtained by converting such a polyfunctional carboxylic acid into a tertiary alkyl ester by a known method can also be used in the present invention.
  • the esterification can be performed by the above-described tertiary alkyl group having 50 or less carbon atoms.
  • ester compound When such a compound is used as an ester compound, it can be esterified inexpensively by a known method, and a polyvalent ester group can be introduced with a relatively low molecular weight. In addition, esterification improves compatibility with organic solvents and can be used preferably. This is preferable.
  • polyfunctional carboxylic acid used here, For example, a C50 or less thing can be used. More specifically, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, octadecanedioic acid, citric acid, butanetetra Aliphatic polycarboxylic acids such as carboxylic acids; 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 3-methyl-1,2-cyclohexanedicarboxylic acid, 4-methyl -1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,
  • the above-described compounds having two or more alkyl ester groups may be used in combination. Moreover, you may use the acid anhydride of these compounds as a raw material.
  • the alkyl esterified product of a polyfunctional carboxylic acid corresponding to the above (Y-3) preferably has a molecular weight of 10,000 or less. By setting it as such, it is preferable at the point which a molecule
  • the molecular weight can be lower, such as 6000 or less, 4000 or less, or 2000 or less.
  • hydroxyl-containing compound which can be used in the said resin composition
  • An acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol, etc. can be mentioned. Of these, two or more may be used simultaneously. Among these, it is particularly preferable to use an acrylic polyol and / or a polyester polyol.
  • a resin widely used in the paint field can be used. These will be described in detail below.
  • (Z-1) Acrylic polyol An acrylic polyol is prepared by, for example, a hydroxyl group vinyl monomer and other polymerizable unsaturated monomer (c 2 ) copolymerizable with the hydroxyl group vinyl monomer by a known method. Can be produced by copolymerization. More specifically, polymerization methods such as a solution polymerization method in an organic solvent, an emulsion polymerization method in water, a miniemulsion polymerization method in water, and an aqueous solution polymerization method can be exemplified.
  • the hydroxyl group-containing vinyl monomer is a compound having at least one hydroxyl group and one polymerizable unsaturated bond in one molecule. What was mentioned above as such a hydroxyl-containing vinyl monomer can be used.
  • Examples of the other polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing vinyl monomer include the following monomers (i) to (xix) and any combination thereof.
  • Alkyl or cycloalkyl (meth) acrylate For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (Meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate,
  • a polymerizable unsaturated monomer having a fluorinated alkyl group Perfluoroalkyl (meth) acrylates such as perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate; fluoroolefins (viii) polymerizable unsaturated monomers having a photopolymerizable functional group such as maleimide group
  • Carboxyl group-containing polymerizable unsaturated monomer (Meth) acrylic acid, maleic acid, crotonic acid, ⁇ -carboxyethyl acrylate, etc.
  • nitrogen-containing polymerizable unsaturated monomers (Meth) acrylonitrile, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, methylenebis (meth) acrylamide , Ethylene bis (meth) acrylamide, adducts of glycidyl (meth) acrylate and amine compounds, etc.
  • (Xii) a polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule: Allyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, etc.
  • Epoxy group-containing polymerizable unsaturated monomer Glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate , Allyl glycidyl ether, etc.
  • Xiv a polymerizable unsaturated monomer having a (meth) acrylate
  • xv sulfonic acid group having a polyoxyethylene chain whose molecular end is an alkoxy group: 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate, allylsulfonic acid, 4-styrenesulfonic acid, etc .; sodium salts and ammonium salts of these sulfonic acids, etc.
  • a polymerizable unsaturated monomer having a phosphate group Acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, acid phosphooxypoly (oxyethylene) glycol (meth) acrylate, acid phosphooxypoly (oxypropylene) glycol (meth) acrylate, etc.
  • (Xvii) a polymerizable unsaturated monomer having a UV-absorbing functional group: 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2,2′-dihydroxy-4- (3- Methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2′-dihydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H -Benzotriazole, etc.
  • UV-stable polymerizable unsaturated monomer 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4- (meta ) Acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl- 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2, 2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, etc.
  • (Xix) polymerizable unsaturated monomer having a carbonyl group Acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrene, vinyl alkyl ketone having about 4 to about 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), etc.
  • the “polymerizable unsaturated group” means an unsaturated group capable of radical polymerization or ion polymerization.
  • examples of the polymerizable unsaturated group include a vinyl group and a (meth) acryloyl group.
  • the proportion of the hydroxyl group-containing monomer in producing the acrylic polyol is preferably 0.5 to 50% by weight based on the total amount of monomer components. By setting it within such a range, an appropriate crosslinking reaction can be caused, and excellent coating film properties can be obtained.
  • the lower limit is more preferably 1.0% by weight, still more preferably 5% by weight.
  • the upper limit is more preferably 50% by weight, and still more preferably 40% by weight.
  • the hydroxyl value of the acrylic polyol is preferably 1 to 200 mgKOH / g from the viewpoint of the water resistance of the coating film to be formed.
  • the lower limit is more preferably 2 mgKOH / g, still more preferably 5 mgKOH / g.
  • the upper limit is more preferably 180 mgKOH / g, still more preferably 170 mgKOH / g.
  • a commercially available thing can also be used as such an acrylic polyol.
  • Commercially available products are not particularly limited. For example, DIC Corporation's Acridic A-801-P, A-817, A-837, A-848-RN, A-814, 57-773, A-829 55-129, 49-394-IM, A-875-55, A-870, A-871, A-859-B, 52-668-BA, WZU-591, WXU-880, BL-616, CL -1000, CL-408 and the like.
  • polyester polyol can be usually produced by an esterification reaction or an ester exchange reaction between an acid component and an alcohol component.
  • an acid component the compound normally used as an acid component at the time of manufacture of a polyester resin is mentioned.
  • the acid component include aliphatic polybasic acids, alicyclic polybasic acids, aromatic polybasic acids and the like, and anhydrides and esterified products thereof.
  • the aliphatic polybasic acids and their anhydrides and esterified products generally include aliphatic compounds having two or more carboxyl groups in one molecule, acid anhydrides of the aliphatic compounds, and esters of the aliphatic compounds. Fats such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, octadecanedioic acid, citric acid, butanetetracarboxylic acid An aliphatic polycarboxylic acid anhydride; an aliphatic polycarboxylic acid ester of a lower alkyl having about 1 to about 4 carbon atoms; and any combination thereof.
  • the aliphatic polybasic acid is preferably adipic acid and / or adipic anhydride from the viewpoint of the smoothness of the resulting coating film.
  • the alicyclic polybasic acids, and anhydrides and esterified products thereof are generally compounds having one or more alicyclic structures and two or more carboxyl groups in one molecule, and acid anhydrides of the above compounds. And esterified products of the above compounds.
  • the alicyclic structure is mainly a 4-6 membered ring structure.
  • Examples of the alicyclic polybasic acids, and anhydrides and esterified products thereof include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1 , 2-dicarboxylic acid, 3-methyl-1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, etc.
  • An alicyclic polyvalent carboxylic acid anhydride; an anhydride of the alicyclic polyvalent carboxylic acid; an esterified product of a lower alkyl having about 1 to about 4 carbon atoms of the alicyclic polyvalent carboxylic acid; Combinations are listed.
  • Examples of the alicyclic polybasic acids, and anhydrides and esterified products thereof include 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid anhydride, 1, from the viewpoint of smoothness of the resulting coating film.
  • 3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic anhydride are preferred, and 1,2-cyclohexanedicarboxylic acid and / or Alternatively, 1,2-cyclohexanedicarboxylic anhydride is more preferable.
  • aromatic polybasic acids, and anhydrides and esterified products thereof are generally aromatic compounds having two or more carboxyl groups in one molecule, acid anhydrides of the aromatic compounds, and esters of the aromatic compounds.
  • aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, trimellitic acid, pyromellitic acid; Acid anhydride; esterified product of lower alkyl having about 1 to about 4 carbon atoms of the above aromatic polycarboxylic acid, and any combination thereof.
  • aromatic polybasic acids, and anhydrides and esterified products thereof phthalic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and trimellitic anhydride are preferable.
  • acid components other than the aliphatic polybasic acid, alicyclic polybasic acid and aromatic polybasic acid for example, coconut oil fatty acid, cottonseed oil fatty acid, hempseed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid , Fatty acids such as 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 oil fatty acid, safflower oil fatty acid; lauric acid, myristic acid, palmitic acid, stearic acid, olein Monocarboxylic acids such as acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexane acid, 10-phenyloctadecanoic acid; lactic acid, 3-hydroxybutanoic acid, 3-hydroxy-4-e
  • the alcohol component examples include polyhydric alcohols having two or more hydroxyl groups in one molecule, such as 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, 2-methyl-1,3-propanediol, 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, tetra Methylene glycol, 3-methyl-4,3-pentane All, 3-methyl-1,5-pentanediol,
  • polylactone diol obtained by adding a lactone compound such as ⁇ -caprolactone to the above dihydric alcohol
  • ester diol compound such as bis (hydroxyethyl) terephthalate
  • alkylene oxide adduct of bisphenol A polyethylene glycol, polypropylene Polyether diol compounds such as glycerin, polybutylene glycol
  • glycerin, trimethylol ethane trimethylol propane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tris (2-hydroxy Examples thereof include trivalent or higher alcohols such as ethyl) isocyanuric acid, sorbitol, and mannitol
  • fatty acid esterified products of glycerin include trivalent or
  • alcohol components other than the polyhydric alcohol for example, monoalcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, stearyl alcohol, 2-phenoxyethanol; propylene oxide, butylene oxide, “Cardura E10” ( Examples thereof include alcohol compounds obtained by reacting a monoepoxy compound such as a trade name, HEXION Specialty Chemicals, Inc., a glycidyl ester of a synthetic highly branched saturated fatty acid) and an acid.
  • monoalcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, stearyl alcohol, 2-phenoxyethanol
  • propylene oxide butylene oxide
  • Cardura E10 examples thereof include alcohol compounds obtained by reacting a monoepoxy compound such as a trade name, HEXION Specialty Chemicals, Inc., a glycidyl ester of a synthetic highly branched saturated fatty acid
  • the polyester polyol is not particularly limited, and can be produced according to a usual method.
  • the acid component and the alcohol component are heated in a nitrogen stream at about 150 to about 250 ° C. for about 5 to about 10 hours to carry out the esterification reaction or transesterification reaction between the acid component and the alcohol component.
  • a polyester polyol can be produced.
  • the polyol of the present invention may be a combination of both the polyacryl polyol and the polyester polyol described above.
  • (Z-3) Low molecular weight polyol The polyol is not limited to the resin as described above, and a low molecular weight polyol (specifically, a molecular weight of 2,000 or less) can also be used.
  • the low molecular weight polyol 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, 2-methyl-1,3-propanediol, 3-methyl-1,2-butanediol, 1,1,1-trimethylolpropane, 2-butyl-2-ethyl- 1,3-propanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pent
  • Such a low molecular weight polyol is known as a general-purpose product and can be obtained at low cost. Furthermore, the low molecular weight polyol has a strong water solubility, and can be suitably used as a crosslinking agent for the purpose of curing in an aqueous system. In recent years, environmental problems have been screamed, and it can be suitably used as a very important crosslinking agent in promoting the reduction of VOC.
  • the resin composition used in the present invention preferably has an organic solvent type or aqueous type. This is preferable in that thin film coating is possible and low-temperature curing can be performed.
  • the aqueous system may be either water-soluble or water-dispersible, and in addition to water, it can be mixed with ethanol, methanol, alcohol-based, glycol-based, ether-based, ketone-based water, etc. at an arbitrary ratio. It may contain an aqueous solvent.
  • the organic solvent-based resin composition is a composition in which the above components are dissolved or dispersed in various organic solvents.
  • the organic solvent that can be used is not particularly limited. Hydrocarbons such as 1-hexane, 1-octane, 1-decane, 1-tetradecane, cyclohexane, benzene, and xylene, ethers such as dimethyl ether and diethyl ether, acetone, and methyl ethyl ketone Any known compounds such as ketones such as cyclohexanone, chlorinated hydrocarbons such as trichloromethane, carbon tetrachloride, dichloroethane, trichloroethane, and tetrachloroethylene, ethanol, methanol, propanol, butanol, and acetone can be used.
  • Hydrocarbons such as 1-hexane, 1-octane, 1-decane, 1-tetradecane, cyclohex
  • an alkyl ester group-containing component and a hydroxyl group-containing component may be combined and used immediately before use.
  • this invention is not limited to the thing of the state which can isolate
  • thermosetting resin composition having at least one curable functional group selected from the group consisting of a polyisocyanate group, a melamine group, an epoxy group, and an alkoxysilane group, an alkyl ester group, and a hydroxyl group according to the second invention.
  • D And Transesterification catalyst
  • the thermosetting resin composition characterized by containing s also includes those in such a state.
  • the resin composition as a whole has only to have all of a curable functional group, an alkyl ester group, and a hydroxyl group, and any two or more functional groups among these in a single compound. May exist.
  • the curable functional group is an epoxy group or an alkoxysilane group
  • an unsaturated polymerizable monomer having these functional groups is used to form a copolymer with the above-mentioned various acrylic monomers.
  • the second aspect of the present invention described above can be implemented. Examples of the monomer that can be used in the second aspect of the present invention include those described above.
  • the epoxy group is preferably used in combination with an acid group.
  • the compound which has an acid group may also be mix
  • Transesterification catalyst (C) in addition to the resin component which combined each component mentioned above, a transesterification catalyst is used.
  • a functional group having a catalytic action may be introduced into the resin using a monomer having transesterification ability.
  • any compound known to be capable of activating the transesterification reaction can be used.
  • various acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid or sulfonic acid; various basic compounds such as LiOH, KOH or NaOH, amines; PbO, zinc acetate
  • various metal compounds such as lead acetate, antimony trioxide, tetraisopropyl titanate, dibutyltin dilaurate, dibutyltin dioctate or monobutylstannic acid.
  • polyoxyethylene alkyloxymethyl alkyl ether ammonium sulfate and polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate which are reactive emulsifiers, can be used as an emulsifier and a cured transesterification catalyst by introducing them into the molecular chain.
  • fever can also be used.
  • the compound having a sulfonic acid group dodecylbenzenesulfonic acid, phenolsulfonic acid, metasulfonic acid, paratoluenesulfonic acid
  • an alkali of sulfonic acid can be used to sufficiently exhibit the effects of the present invention. It is desirable to use a compound having a group consisting of a metal salt, an amine salt or an ammonium salt.
  • a compound having thermal latent catalytic performance it is a compound that does not have transesterification catalytic ability at the time of production of the composition, but changes to a compound having transesterification catalytic ability by the heat treatment.
  • the composition before heating does not have curing performance, and therefore, the reaction does not proceed during storage of the composition, which is preferable in terms of easy long-term storage.
  • thermal latent catalyst for example, commercially available products such as NACURE 5225, NACURE 5925, NACURE 2500 (above, Enomoto Kasei Co., Ltd.) can be used.
  • the amount of the transesterification catalyst used is preferably 0.01 to 50% by mass with respect to the weight of the resin component having an alkyl ester group and a hydroxyl group. By setting it as such a range, it is preferable at the point which can perform favorable hardening reaction at low temperature.
  • the upper limit is more preferably 30% by weight, and still more preferably 10% by weight.
  • the form of the thermosetting resin composition of the present invention is not particularly limited, but it is particularly preferable to have a form of a powder paint, an organic solvent system or an aqueous composition. This is preferable in that thin film coating is possible and low-temperature curing can be performed.
  • the aqueous system may be either water-soluble or water-dispersible, and in addition to water, it can be mixed with ethanol, methanol, alcohol-based, glycol-based, ether-based, ketone-based water, etc. at an arbitrary ratio. It may contain an aqueous solvent.
  • urethanization reaction catalyst examples include, for example, tin octylate, dibutyltin diacetate, dibutyltin di (2-ethylhexanoate), dibutyltin dilaurate, dioctyltin diacetate, dioctyltin di (2 -Ethylhexanoate), dibutyltin oxide, dibutyltin sulfite, dioctyltin oxide, dibutyltin fatty acid salt, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, zinc fatty acids, bismuth octanoate, 2- Organometallic compounds such as bismuth ethylhexanoate, bismuth ole
  • the catalyst amount is 0.0001 to 0.5 mass%, particularly 0.0005 to 0.1 mass%, based on the total solid content of the thermosetting resin composition. It is preferable to be within the range.
  • thermosetting resin composition of the present invention is not particularly limited, but it is particularly preferable that the thermosetting resin composition has an organic solvent type or aqueous type form. This is preferable in that thin film coating is possible and low-temperature curing can be performed.
  • the aqueous system may be either water-soluble or water-dispersible, and in addition to water, it can be mixed with ethanol, methanol, alcohol-based, glycol-based, ether-based, ketone-based water, etc. at an arbitrary ratio. It may contain an aqueous solvent.
  • the organic solvent-based thermosetting resin composition is a composition in which the above components are dissolved or dispersed in various organic solvents.
  • the organic solvent that can be used is not particularly limited. Hydrocarbons such as 1-hexane, 1-octane, 1-decane, 1-tetradecane, cyclohexane, benzene, and xylene, ethers such as dimethyl ether and diethyl ether, acetone, and methyl ethyl ketone , And the like, chlorine-based hydrocarbons such as trichloromethane, carbon tetrachloride, dichloroethane, trichloroethane, and tetrachloroethylene, and any known ones such as ethanol, methanol, propanol, butanol, acetone, and cyclohexanone can be used.
  • Hydrocarbons such as 1-hexane, 1-octane, 1-decane, 1-tetradecane,
  • the two-component resin composition may be used by mixing just before use. By doing in this way, it is preferable at the point from which storage stability becomes favorable.
  • One or two or more resin components, the above-mentioned curing agent component, and catalyst component are appropriately combined, and each solution is prepared in a combination that does not cause a curing reaction before mixing, so that a curing reaction occurs by mixing. It is preferable to do.
  • it can also be set as a 3 liquid type or more form according to a composition, the objective, etc.
  • thermosetting resin composition such as a powder coating material
  • it can manufacture by drying, mixing, and grind
  • thermosetting resin composition of this invention can be used conveniently in field
  • thermosetting paint When used as a thermosetting paint, in addition to the components described above, additives commonly used in the paint field may be used in combination. For example, color pigments, extender pigments, glitter pigments, etc., and any combination thereof may be used in combination.
  • the pigment When the pigment is used, it is preferably contained in a total range of 1 to 500% by weight based on 100% by weight of the total solid content of the resin component.
  • the lower limit is more preferably 3% by weight, still more preferably 5 parts by weight.
  • the upper limit is more preferably 400% by weight, still more preferably 300% by weight.
  • color pigment examples include titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, selenium pigment, and perylene pigment. , Dioxazine pigments, diketopyrrolopyrrole pigments, etc., and any combination thereof.
  • Examples of the extender pigment include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white. Barium sulfate and / or talc are preferable, and barium sulfate is more preferable.
  • the bright pigment examples include aluminum (including vapor-deposited aluminum), copper, zinc, brass, nickel, aluminum oxide, mica, titanium oxide or iron oxide coated with titanium oxide or iron oxide. Mica, glass flakes, hologram pigments, etc., and any combination thereof.
  • the aluminum pigment includes non-leafing type aluminum and leafing type aluminum.
  • thermosetting paint is optionally added for paints such as thickeners, UV absorbers, light stabilizers, antifoaming agents, plasticizers, organic solvents other than the hydrophobic solvents, surface conditioners, anti-settling agents, etc. It may further contain an agent.
  • the thickener examples include inorganic thickeners such as silicate, metal silicate, montmorillonite, colloidal alumina; copolymer of (meth) acrylic acid and (meth) acrylic ester, poly Polyacrylic acid thickeners such as sodium acrylate; having a hydrophilic part and a hydrophobic part in one molecule, and in the aqueous medium, the hydrophobic part is adsorbed on the surface of pigments and emulsion particles in the paint , An associative thickener exhibiting a thickening action due to the association of the hydrophobic parts; a fibrous derivative thickener such as carboxymethylcellulose, methylcellulose, hydroxyethylcellulose; casein, sodium caseinate, ammonium caseinate, etc.
  • inorganic thickeners such as silicate, metal silicate, montmorillonite, colloidal alumina
  • copolymer of (meth) acrylic acid and (meth) acrylic ester poly Polyacrylic acid thickeners such as sodium acrylate
  • Protein thickeners Alginate thickeners such as sodium alginate; Polyvinyl alcohol, Polyvinylpyrrolidone, Polyvinyl Polyvinyl thickeners such as benzyl ether copolymers; polyether thickeners such as pluronic polyethers, polyether dialkyl esters, polyether dialkyl ethers, polyether epoxy modified products; vinyl methyl ether-maleic anhydride copolymer Examples thereof include maleic anhydride copolymer thickeners such as partial esters of coal; polyamide thickeners such as polyamide amine salts, and any combination thereof.
  • polyacrylic acid thickeners are commercially available.
  • ACRYSOLASE-60 “ACRYSOLTT-615”, “ACRYSOLRM-5” (above, trade name) manufactured by Rohm and Haas, manufactured by San Nopco Examples thereof include “SN thickener 613”, “SN thickener 618”, “SN thickener 630”, “SN thickener 634”, “SN thickener 636” (hereinafter, trade names).
  • the associative thickener is commercially available, for example, “UH-420”, “UH-450”, “UH-462”, “UH-472”, “UH-540” manufactured by ADEKA, “UH-752”, “UH-756VF”, “UH-814N” (named above), “ACRYSOLRM-8W”, “ACRYSOLRM-825”, “ACRYSOLRM-2020NPR”, “ACRYSOLRM” manufactured by Rohm and Haas.
  • thermosetting paint can be applied is not particularly limited, and examples thereof include an outer plate portion of an automobile body such as a passenger car, a truck, a motorcycle, and a bus; an automobile part; a mobile phone, an audio device, and the like.
  • an outer plate portion of an automobile body such as a passenger car, a truck, a motorcycle, and a bus
  • an automobile part such as a mobile phone, an audio device, and the like.
  • Various examples of home appliances, building materials, furniture, adhesives, film and glass coating agents, and the like can be given.
  • it can be used for curing any layer such as an intermediate coating, a base coating, and a clear coating.
  • the object to be coated may be a metal surface of the metal material and a vehicle body formed from the metal material and subjected to a surface treatment such as a phosphate treatment, a chromate treatment, a complex oxide treatment,
  • a surface treatment such as a phosphate treatment, a chromate treatment, a complex oxide treatment
  • the to-be-coated object which has a coating film may be sufficient.
  • Examples of the object to be coated having the coating film include those in which a surface treatment is optionally applied to a substrate and an undercoat coating film is formed thereon.
  • a vehicle body in which an undercoat film is formed with an electrodeposition paint is preferable, and a vehicle body in which an undercoat film is formed with a cationic electrodeposition paint is more preferable.
  • the object to be coated may be obtained by subjecting the plastic surface of the plastic material and an automobile part or the like molded therefrom to surface treatment, primer coating, or the like as desired. Further, a combination of the plastic material and the metal material may be used.
  • thermosetting coating is not particularly limited, and examples thereof include air spray coating, airless spray coating, rotary atomization coating, curtain coat coating, and the like, and air spray coating, rotary atomization coating, and the like are preferable.
  • electrostatic application may be applied if desired.
  • a wet coating film can be formed from the coating composition by the coating method.
  • the wet coating film can be cured by heating.
  • the curing can be performed by a known heating means, for example, a drying furnace such as a hot air furnace, an electric furnace, or an infrared induction heating furnace.
  • the wet coating is preferably at a temperature in the range of about 80 to about 180 ° C., more preferably about 100 to about 170 ° C., and more preferably about 120 to about 160 ° C., preferably about 10 to about 60 minutes, More preferably, it can be cured by heating for about 15 to about 40 minutes. Further, it is preferable in that it can cope with low-temperature curing at 80 to 140 ° C.
  • the present invention is also a thermosetting film obtained by the method described above.
  • Synthesis example 1 n-Butyl methacrylate (Kyoeisha Chemical Co., Ltd. product: Light Ester NB) 245 parts, t-butyl acrylate (Kyoeisha Chemical Co., Ltd. product: Light acrylate TB) 110 parts, Hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. product: Light) Ester HO-250) 115 parts, Styrene 30 parts as monomer mixture, 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemicals V-65) as initiator 25 parts as aromatic hydrocarbon Dissolved in (T-SOL 100) to form an initiator solution.
  • a stirrable flask was charged with 250 parts of aromatic hydrocarbon (T-SOL 100) and 250 parts of propylene glycol monomethyl ether acetate, and the monomer solution and the initiator solution were added dropwise while nitrogen was sealed.
  • the polymerization temperature at this time was 100 ° C.
  • the dropping was performed in 2 hours, and further aging was performed at 100 ° C. for 4 hours to obtain a polymer solution A.
  • Comparative Example 1 A commercially available polyol resin 1 (DIC Corporation, Acridic A-405) and melamine cross-linking agent 1 (Mitsui Chemicals Co., Ltd. Uban 20SB) were mixed, and a 400 ⁇ m coating film was formed by WET using an applicator. Curing was performed at 140 ° C. for 30 minutes. Thereafter, a rigid pendulum test was performed using a gel fraction, a xylene rubbing test, water resistance, acid resistance, and an adjusting solution.
  • Comparative Example 2 Mix the commercially available polyol resin 1 (DIC Co., Ltd., Acridic A-405) and blocked isocyanate cross-linking agent (Asahi Kasei Co., Ltd. product Duranate MF-K60B), and use an applicator to create a 400 ⁇ m coating film with WET And curing at 140 ° C. for 30 minutes. Thereafter, a rigid pendulum test was performed using a gel fraction, a xylene rubbing test, water resistance, acid resistance, and an adjusting solution.
  • Example 1 Resin I was prepared by mixing phenol sulfonic acid (PhS) with the polymer solution A at 3 wt% with respect to the solid content of the polymer solution A.
  • Polyol resin 1 (DIC Co., Ltd., Acridic A-405) and melamine crosslinking agent 1 (Mitsui Chemicals Co., Ltd. Uban 20SB) were mixed at a ratio of 30:70 (solid content weight ratio) to obtain Resin II.
  • Resin I and Resin II were mixed at 30:70 (solid content weight ratio) to prepare a test solution.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 140 ° C. for 30 minutes. Thereafter, a rigid pendulum test was performed using a gel fraction, a xylene rubbing test, water resistance, acid resistance, and an adjusting solution.
  • Example 2 Resin I was prepared by mixing phenol sulfonic acid (PhS) with the polymer solution A at 3 wt% with respect to the solid content of the polymer solution A.
  • Polyol resin 1 (DIC Co., Ltd., Acridic A-405) and melamine crosslinking agent 1 (Mitsui Chemicals Co., Ltd. Uban 20SB) were mixed at a ratio of 30:70 (solid content weight ratio) to obtain Resin II.
  • Resin I and Resin II were mixed at 60:40 (solid content weight ratio) to prepare a test solution.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 140 ° C. for 30 minutes. Thereafter, a rigid pendulum test was performed using a gel fraction, a xylene rubbing test, water resistance, acid resistance, and an adjusting solution.
  • Example 3 Resin I was prepared by mixing phenol sulfonic acid (PhS) with the polymer solution A at 3 wt% with respect to the solid content of the polymer solution A.
  • Polyol resin 1 (DIC Co., Ltd., Acridic A-405) and blocked isocyanate cross-linking agent (Asahi Kasei Co., Ltd. product Duranate MF-K60B) were mixed at a ratio of 30:70 (solid content weight ratio) to obtain Resin II. .
  • Resin I and Resin II were mixed at 30:70 (solid content weight ratio) to prepare a test solution.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 140 ° C. for 30 minutes. Thereafter, a rigid pendulum test was performed using a gel fraction, a xylene rubbing test, water resistance, acid resistance, and an adjusting solution.
  • Example 4 Resin I was prepared by mixing phenol sulfonic acid (PhS) with the polymer solution A at 3 wt% with respect to the solid content of the polymer solution A.
  • Polyol resin 1 (DIC Co., Ltd., Acridic A-405), blocked isocyanate cross-linking agent (Asahi Kasei Co., Ltd. product Duranate MF-K60B) and 60:40 (solid content weight ratio) were mixed to obtain Resin II. .
  • Resin I and Resin II were mixed at 30:70 (solid content weight ratio) to prepare a test solution.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 140 ° C. for 30 minutes. Thereafter, a rigid pendulum test was performed using a gel fraction, a xylene rubbing test, water resistance, acid resistance, and an adjusting solution.
  • Synthesis example 2 250 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester NB), hydroxyethyl acrylate (Kyoeisha Chemical Co., Ltd .: Light Ester HOA (N)) 175 parts, and 75 parts of styrene as a monomer mixture
  • 25 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemicals V-65) was dissolved in an aromatic hydrocarbon (T-SOL 100) to prepare an initiator solution.
  • a stirrable flask was charged with 250 parts of aromatic hydrocarbon (T-SOL 100) and 250 parts of propylene glycol monomethyl ether acetate, and the monomer solution and the initiator solution were added dropwise while nitrogen was sealed.
  • the polymerization temperature at this time was 100 ° C.
  • the dropping was performed in 2 hours, and further aging was performed at 100 ° C. for 4 hours to obtain a polymer solution B.
  • Comparative Example 3 Polymer solution B, melamine cross-linking agent 2 (Sanwa Chemical Co., Ltd. product Nicalac MX-45) and phenolsulfonic acid (PhS) were mixed, and a 400 ⁇ m coating film was formed by WET using an applicator, and 30 ° C. at 30 ° C. Partial curing was performed. Thereafter, a rigid pendulum test was performed using a gel fraction, a xylene rubbing test, water resistance, acid resistance, and an adjusting solution.
  • Example 5 A thermal latent acid catalyst was mixed with the polymer solution A so as to be 3 wt% based on the solid content of the polymer solution A to obtain a resin I.
  • Polymer solution B and melamine crosslinking agent 2 (Sanwa Chemical Co., Ltd. product Nicalak MX-45) were mixed at a ratio of 60:40 (solid content weight ratio), and the thermal latent acid catalyst was further adjusted to 3 wt% with respect to the solid content. It mixed so that it might become resin II.
  • Resin I and Resin II were mixed at 10:90 (solid weight ratio) to prepare a test solution.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 140 ° C. for 30 minutes. Thereafter, a rigid pendulum test was performed using a gel fraction, a xylene rubbing test, water resistance, acid resistance, and an adjusting solution.
  • Example 6 A thermal latent acid catalyst was mixed with the polymer solution A so as to be 3 wt% based on the solid content of the polymer solution A to obtain a resin I.
  • Polymer solution B and melamine crosslinking agent 2 (Sanwa Chemical Co., Ltd. product Nicalak MX-45) were mixed at a ratio of 60:40 (solid content weight ratio), and the thermal latent acid catalyst was further adjusted to 3 wt% with respect to the solid content. It mixed so that it might become resin II.
  • Resin I and Resin II were mixed at 20:80 (solid weight ratio) to prepare a test solution.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 140 ° C. for 30 minutes. Thereafter, a rigid pendulum test was performed using a gel fraction, a xylene rubbing test, water resistance, acid resistance, and an adjusting solution.
  • Example 7 A thermal latent acid catalyst was mixed with the polymer solution A so as to be 3 wt% based on the solid content of the polymer solution A to obtain a resin I.
  • Polymer solution B and melamine crosslinking agent 2 (Sanwa Chemical Co., Ltd. product Nicalak MX-45) were mixed at a ratio of 60:40 (solid content weight ratio), and the thermal latent acid catalyst was further adjusted to 3 wt% with respect to the solid content. It mixed so that it might become resin II.
  • Resin I and Resin II were mixed at 30:70 (solid content weight ratio) to prepare a test solution.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 140 ° C. for 30 minutes. Thereafter, a rigid pendulum test was performed using a gel fraction, a xylene rubbing test, water resistance, acid resistance, and an adjusting solution.
  • Example 8 A thermal latent acid catalyst was mixed with the polymer solution A so as to be 3 wt% based on the solid content of the polymer solution A to obtain a resin I.
  • Polymer solution B and melamine crosslinking agent 2 (Sanwa Chemical Co., Ltd. product Nicalak MX-45) were mixed at a ratio of 60:40 (solid content weight ratio), and the thermal latent acid catalyst was further adjusted to 3 wt% with respect to the solid content. It mixed so that it might become resin II.
  • Resin I and Resin II were mixed at 40:60 (solid content weight ratio) to prepare a test solution.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 140 ° C. for 30 minutes. Thereafter, a rigid pendulum test was performed using a gel fraction, a xylene rubbing test, water resistance, acid resistance, and an adjusting solution.
  • Example 9 A thermal latent acid catalyst was mixed with the polymer solution A so as to be 3 wt% based on the solid content of the polymer solution A to obtain a resin I.
  • Polymer solution B and melamine crosslinking agent 2 (Sanwa Chemical Co., Ltd. product Nicalak MX-45) were mixed at a ratio of 60:40 (solid content weight ratio), and the thermal latent acid catalyst was further adjusted to 3 wt% with respect to the solid content. It mixed so that it might become resin II.
  • Resin I and Resin II were mixed at 50:50 (solid content weight ratio) to prepare a test solution.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 140 ° C. for 30 minutes. Thereafter, a rigid pendulum test was performed using a gel fraction, a xylene rubbing test, water resistance, acid resistance, and an adjusting solution.
  • Example 10 Resin I was prepared by mixing phenol sulfonic acid (PhS) with the polymer solution A so that the solid content of the polymer solution A was 3 wt%.
  • Polymer solution B and melamine cross-linking agent 2 (Sanwa Chemical Co., Ltd. product Nicalac MX-45) were mixed at a ratio of 60:40 (solid content weight ratio), and phenolsulfonic acid (PhS) was added at 3 wt. %
  • Resin II Resin I and Resin II were mixed so as to be 40:60 (solid content weight ratio), and further diluted with methanol to obtain a test solution.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 90 ° C. for 30 minutes. Thereafter, gel fraction, xylene rubbing test, water resistance, and acid resistance test were conducted.
  • NACURE 5225 manufactured by Enomoto Kasei Co., Ltd. was used as the thermal latent acid catalyst.
  • Nikalac MX-45 (alkyl etherified melamine resin) manufactured by Sanwa Chemical Co., Ltd. was used.
  • Synthesis example 3 135 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd. product: light ester NB), 135 parts of t-butyl acrylate (Kyoeisha Chemical Co., Ltd. product: light acrylate TB), hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. product: Light) 135 parts of ester HO-250, 20 parts of methyl methacrylate (Kyoeisha Chemical Co., Ltd. product: Light Ester A) 20, 12 parts of reactive emulsifier (Daiichi Kogyo Seiyaku: AQUALON KH-10) are used as a monomer mixture and as an initiator.
  • Comparative Example 4 Commercially available polyol resin 2 (DIC Co., Ltd. Watersol 2001) and melamine crosslinker 3 (Silm 303LF, manufactured by Allnex) were mixed, and a 400 ⁇ m coating film was formed by WET using an applicator, and at 140 ° C. for 30 minutes. Curing was performed. Thereafter, gel fraction, xylene rubbing test, water resistance, and acid resistance test were conducted.
  • Example 11 Polymer solution C and melamine cross-linking agent 3 (Symel 303LF, manufactured by Allnex) were mixed 4: 6 (solid content weight ratio), and the thermal latent acid catalyst was mixed therewith so as to be 5 wt% with respect to the solid content of polymer solution C. It mixed and it was set as the test liquid.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 140 ° C. for 30 minutes. Thereafter, gel fraction, xylene rubbing test, water resistance and acid resistance test were conducted.
  • Example 12 Polymer solution C and melamine cross-linking agent 3 (Symel 303LF manufactured by Allnex) were mixed at 6: 4 (solid content weight ratio), and the thermal latent acid catalyst was mixed therewith so as to be 5 wt% with respect to the solid content of polymer solution C. It mixed and it was set as the test liquid.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 140 ° C. for 30 minutes. Thereafter, gel fraction, xylene rubbing test, water resistance and acid resistance test were conducted.
  • Example 13 Polymer solution C and melamine cross-linking agent 3 (Symel 303LF, manufactured by Allnex) are mixed 8: 2 (solid content weight ratio), and the thermal latent acid catalyst is adjusted to 5 wt% with respect to the solid content of polymer solution C. It mixed and it was set as the test liquid.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 140 ° C. for 30 minutes. Thereafter, gel fraction, xylene rubbing test, water resistance and acid resistance test were conducted.
  • Example 14 The polymer solution A was mixed with phenolsulfonic acid (PhS) and a silane coupling agent to prepare a test solution.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 140 ° C. for 30 minutes. Thereafter, gel fraction, xylene rubbing test and water resistance test were conducted.
  • KBM-803 (3-mercaptopropyltrimethoxysilane) was used as the silane coupling agent.
  • Synthesis example 4 54 parts of ethylene glycol monoacetoacetate monomethacrylate, 43 parts of methyl acrylate, 33 parts of potassium carbonate, 2 parts of 18-crown-6 ether and 97 parts of tetrahydrofuran were mixed and stirred at 50 ° C. for 3 hours. After completion of the reaction, cyclohexane and water were added and washed with water. The organic layer was neutralized with a saturated aqueous ammonium chloride solution, washed twice with water, and the resulting organic layer was concentrated under reduced pressure to obtain monomer A.
  • Synthesis example 5 100 parts of 2-ethylhexyl methacrylate, 150 parts of monomer A, 120 parts of hydroxyethyl methacrylate (product of Kyoeisha Chemical Co., Ltd .: Light Ester HO-250) and 120 parts of styrene are used as a monomer mixture, and AIBN (azobisiso) is used as an initiator. 25 parts of butyronitrile) was dissolved in an aromatic hydrocarbon (T-SOL100) to form an initiator solution. A stirrable flask was charged with 250 parts of aromatic hydrocarbon (T-SOL 100) and 250 parts of propylene glycol monomethyl ether acetate, and the monomer solution and the initiator solution were added dropwise while nitrogen was sealed. The polymerization temperature at this time was 100 ° C. The dropping was performed in 2 hours, and further aging was performed at 100 ° C. for 4 hours to obtain a polymer solution D.
  • T-SOL100 aromatic hydrocarbon
  • the molecular weight was measured by measuring polystyrene equivalent molecular weight using gel permeation chromatography.
  • Synthesis Example 6 5 parts of acrylic acid, 25 parts of hydroxyethyl acrylate, 10 parts of ethyl acrylate, 30 parts of butyl acrylate and 30 parts of styrene are used as a monomer mixture, and 1 part of 2,2′-azobis (2,4-dimethylvalerontri) as an initiator was dissolved in 3 parts of isopropyl alcohol to obtain an initiator solution. 45 parts of isopropyl alcohol was placed in a stirrable flask, and the monomer solution and the initiator solution were added dropwise while nitrogen was sealed. The polymerization temperature at this time was 80 ° C. The dropwise addition was performed in 3 hours, and further aging was performed at 80 ° C. for 4 hours to obtain a polymer solution E.
  • Comparative Example 5 Polymer solution B and melamine cross-linking agent 4 (Sanwa Chemical Co., Ltd. product Nicalac MX-750) were mixed, a 400 ⁇ m coating film was formed by WET using an applicator, and cured at 150 ° C. for 30 minutes. Thereafter, gel fraction, xylene rubbing test, water resistance and acid resistance test were conducted.
  • Example 15 Resin I was prepared by mixing Neostan U-820 (manufactured by Nitto Kasei Co., Ltd.) with the polymer solution D so that the solid content of the polymer solution D was 3 wt%.
  • Polymer solution B and melamine cross-linking agent 4 (Sanwa Chemical Co., Ltd. product Nicalac MX-750) were mixed at a ratio of 60:40 (solid content weight ratio) to obtain Resin II.
  • Resin I and Resin II were mixed at 40:60 (solid content weight ratio) to prepare a test solution.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 150 ° C. for 30 minutes. Thereafter, gel fraction, xylene rubbing test, water resistance and acid resistance test were conducted.
  • Example 16 Resin I was prepared by mixing Neostan U-820 (Nitto Kasei Co., Ltd.) with the polymer solution D so that the solid content of the polymer solution D was 3 wt%.
  • Polymer solution B and melamine cross-linking agent 4 (Sanwa Chemical Co., Ltd. product Nicalac MX-750) were mixed at a ratio of 60:40 (solid content weight ratio) to obtain Resin II.
  • Resin I and Resin II were mixed at 60:40 (solid content weight ratio) to prepare a test solution.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 150 ° C. for 30 minutes. Thereafter, gel fraction, xylene rubbing test, water resistance and acid resistance test were conducted.
  • Example 17 Resin I was prepared by mixing Neostan U-820 (Nitto Kasei Co., Ltd.) with the polymer solution D so that the solid content of the polymer solution D was 3 wt%.
  • Polyol resin 1 (DIC Co., Ltd., Acridic A-405), blocked isocyanate cross-linking agent (Asahi Kasei Co., Ltd. product Duranate MF-K60B) and 60:40 (solid content weight ratio) were mixed to obtain Resin II. .
  • Resin I and Resin II were mixed at 40:60 (solid content weight ratio) to prepare a test solution.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 150 ° C. for 30 minutes. Thereafter, gel fraction, xylene rubbing test, water resistance and acid resistance test were conducted.
  • Example 18 Resin I was prepared by mixing Neostan U-820 (Nitto Kasei Co., Ltd.) with the polymer solution D so that the solid content of the polymer solution D was 3 wt%.
  • Polyol resin 1 (DIC Co., Ltd., Acridic A-405), blocked isocyanate cross-linking agent (Asahi Kasei Co., Ltd. product Duranate MF-K60B) and 60:40 (solid content weight ratio) were mixed to obtain Resin II. .
  • Resin I and Resin II were mixed at 60:40 (solid content weight ratio) to prepare a test solution.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 150 ° C. for 30 minutes. Thereafter, gel fraction, xylene rubbing test, water resistance and acid resistance test were conducted.
  • Example 19 Resin I was prepared by mixing Neostan U-820 (Nitto Kasei Co., Ltd.) with the polymer solution D so that the solid content of the polymer solution D was 3 wt%. Resin I and acid / epoxy paint (Kansai Paint Co., Ltd.) were mixed at 40:60 (solid content weight ratio) to prepare a test solution. A 400 ⁇ m coating film was prepared by WET using an applicator and cured at 150 ° C. for 30 minutes. Thereafter, gel fraction, xylene rubbing test, water resistance and acid resistance test were conducted.
  • Resin I was prepared by mixing Neostan U-820 (Nitto Kasei Co., Ltd.) with the polymer solution D so that the solid content of the polymer solution D was 3 wt%. Resin I and acid / epoxy paint (Kansai Paint Co., Ltd.) were mixed at 40:60 (solid content weight ratio) to prepare a test solution. A 400 ⁇ m coating film was prepared by WET using an applicator and cured at 150 ° C. for 30 minutes. Thereafter, gel fraction, xylene rubbing test, water resistance and acid resistance test were conducted.
  • Neostan U-820 (Nitto Kasei Co., Ltd.) and a silane coupling agent were mixed with the polymer solution D to prepare a test solution.
  • a 400 ⁇ m coating film was prepared by WET using an applicator and cured at 150 ° C. for 30 minutes. Thereafter, gel fraction, xylene rubbing test and water resistance test were conducted.
  • KBM-803 (3-mercaptopropyltrimethoxysilane) was used as the silane coupling agent.
  • the physical properties in Tables 1 to 7 are measured by the following methods.
  • the gel fraction was measured by dissolving the film obtained in the example in acetone reflux using Soxhlet for 30 minutes, and the remaining weight% of the film was measured as the gel fraction.
  • the gel fraction was 0 to 40%, which was unacceptable for practical use.
  • a gel fraction of 40-80% was marked as ⁇ for practical use.
  • a gel fraction of 80 to 100% was marked as ⁇ with excellent performance.
  • thermosetting resin of the example was coated on a PET film and rubbed 10 times with a medicinal gauze soaked in xylene, and the surface was observed. Evaluation was evaluated as x for those that could not withstand practical use, ⁇ for those that could withstand practical use, and ⁇ for those with superior performance.
  • Pendulum FRB-100 Film thickness (WET): 100 ⁇ m
  • the gel fraction is 40 or more, it is judged that a certain curing reaction occurs, and it is clear that the gel fraction has a function as a curable resin composition.
  • those having excellent properties such as xylene rubbing and water resistance are suitable for use in many applications including paints (particularly paints forming the outermost layer) based on these properties.
  • the curable resin composition of the present invention can be used in the fields of pressure-sensitive adhesives and adhesives, and the inner layer in multilayer coatings. It will be a thing.
  • Comparative Examples 1 to 4 the existing technology is evaluated. As is generally known, the melamine curable resin has poor acid resistance.
  • Examples 1 and 2 it is apparent that acid resistance can be improved without lowering other physical properties by using a transesterification curing system in combination with an existing melamine curing system. Further, excellent results were obtained in the curing performance.
  • the transesterification curing system and the existing isocyanate curing system can be used together to reduce the amount of isocyanate used while maintaining the conventional physical properties. It is clear that there is.
  • Examples 5 to 9 the same effect as in Examples 1 and 2 was obtained, and even in a system using both a fully etherified melamine and an ester exchange curing system that require an acid catalyst for curing, without lowering other physical properties, It is clear that the acid resistance can be improved.
  • Example 10 it was revealed that when the catalyst was changed to phenolsulfonic acid, it was cured even at a low temperature of 90 ° C. and excellent curing performance including acid resistance was obtained.
  • Example 11 to 13 it is apparent that the acid resistance of the water-based melamine coating can be improved by using a transesterification curing system in combination.
  • Example 14 it became clear that the system using the silane coupling agent and the transesterification curing system can proceed without hindering the curing and improve the physical properties.
  • thermosetting resin composition of the present invention can be used in various thermosetting resin compositions, and in particular, various coating compositions (automobile paints, PCM paints, CAN paints, electrodeposition paints) and adhesive compositions. Can be suitably used in film formation, coating film formation, molding material, laminate material, and resist material.
  • various coating compositions automobile paints, PCM paints, CAN paints, electrodeposition paints
  • adhesive compositions can be suitably used in film formation, coating film formation, molding material, laminate material, and resist material.

Abstract

Le problème décrit par la présente invention est de fournir une composition de résine thermodurcissable qui est peu coûteuse, a de bonnes propriétés de durcissement, peut être utilisée dans diverses applications, et qui, suite à l'utilisation d'une réaction de transestérification dans le cadre de la réaction de durcissement, facilite l'ajustement de ses propriétés physiques, et peut permettre de réduire les coûts, tout en maintenant des performances de durcissement équivalentes à l'état de la technique. La solution selon l'invention porte sur une composition de résine thermodurcissable comprenant : au moins un constituant de durcissement (A) choisi dans le groupe constitué par les composés de type polyisocyanate, une résine de mélamine et des composés de type alcoxysilane ; un constituant de type résine (B) comportant un groupe ester alkylique et un groupe hydroxyle ; et un catalyseur de transestérification (C).
PCT/JP2019/023459 2018-06-13 2019-06-13 Composition de résine thermodurcissable et film durci WO2019240216A1 (fr)

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