Thermosetting resin composition and cured film

Abstract

The thermosetting resin composition with ester exchange as a curing reaction, which has curing performance at a lower temperature and can cope with water-borne properties, is obtained. A thermosetting resin composition containing a resin component (A) containing an ester group (a), an epoxy group (b), and a hydroxyl group (c), and a transesterification catalyst (B), the ester group being any one of (a-1) to (a-5).

Description

TECHNICAL FIELD

[0001] The present application relates to a thermosetting resin composition and a cured film. BACKGROUND

[0002] The present inventors have studied a thermosetting resin composition in which transesterification is used as a curing reaction (Patent Documents 1 to 3). According to recent studies, it has been found that, by using transesterification as a curing reaction, it is possible to ensure a curing performance equivalent to that of a curing reaction using a melamine resin or a polyisocyanate compound, which is conventionally known.

[0003] On the other hand, in recent years, from the viewpoint of energy saving, it is desired to achieve curing at a lower temperature than ever before. In the various methods described in Patent Documents 1 to 3, sufficient low-temperature curing can be achieved, but a method that enables curing at an even lower temperature than ever before is preferred. Furthermore, from the viewpoint of VOC, studies on high solid type, water-based, and the like are also widely conducted.

[0004] Patent Document 4 discloses a curable resin composition that uses a compound containing an ester group represented by a specific structure, and undergoes a curing reaction by transesterification. However, detailed studies for obtaining sufficient low-temperature curing performance have not been conducted.

[0005] Patent Document 5 describes mixing an epoxy compound in a resin composition in which transesterification is used as a curing reaction.

[0006] Patent Document 6 describes a dual-curing type curable composition that also has an energy ray curing function, by introducing an unsaturated group into a thermosetting resin composition in which transesterification is used as a curing reaction.

[0007] PRIOR ART DOCUMENTS

[0008] PATENT DOCUMENTS

[0009] Patent Document 1: Japanese Patent No. 6398026

[0010] Patent Document 2: International Publication No. 2019 / 069783

[0011] Patent Document 3: International Publication No. 2019 / 139069

[0012] Patent Document 4: Japanese Patent Application Laid-Open No. 2003-119401

[0013] Patent Document 5: Japanese Patent Application Laid-Open No. Hei 2-147675

[0014] Patent Document 6: International Publication No. 2021 / 006290 SUMMARY

[0015] Problem to be solved by the Invention

[0016] In view of the above, an object of the present invention is to obtain a thermosetting resin composition with a curing performance at a lower temperature and capable of responding to water-based, in which ester exchange is used as a curing reaction, and a cured film obtained using the same.

[0017] Means for solving the problem

[0018] The present invention relates to a thermosetting resin composition characterized by containing: a resin component (A) containing an ester group (a), an epoxy group (b), and a hydroxyl group (c), and an ester exchange catalyst (B), the ester group being any one of the following (a-1) to (a-5).

[0019] (a-1) a compound represented by the following general formula (1)

[0020] [Chemical Formula 1]

[0021]

[0022] n1: 1 to 10

[0023] (In the formula, R4, R5, R6 are the same or different, and are hydrogen, an alkyl group, a carboxyl group, an alkyl ester group, or a structure represented by R7-[COOR8]n1 described below.

[0024] R7 is an aliphatic, alicyclic, or aromatic alkylene group which can have a side chain, and the number of atoms in the main chain is 50 or less, and one or two or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and a urethane group can be present in the main chain.

[0025] R8 is an alkyl group with 50 or less carbon atoms.

[0026] In the compound represented by the above general formula (1), the R7-[COOR8]n1 group can be a lactone structure of the following general formula (1-1).

[0027] [Chemical Formula 2]

[0028]

[0029] (a-2) a compound having the structure represented by the following general formula (2) as a structural unit of the above (a-1).

[0030] [Chemical Formula 3]

[0031]

[0032] n = 0 to 20

[0033] R1 is an alkyl group with 50 or less carbon atoms.

[0034] R3 is hydrogen or an alkyl group having 10 or less carbon atoms.

[0035] (a-4) a compound having a structure represented by General Formula (3) or (4) shown below

[0036] [Chemical Formula 4]

[0037]

[0038] [Chemical Formula 5]

[0039]

[0040] (In any one of the above General Formula (3), General Formula (4), R1 is an alkyl group having 50 or less carbon atoms.

[0041] R2 is an alkylene group having 50 or less carbon atoms, a part of which can include an oxygen atom, a nitrogen atom)

[0042] (a-5) General Formula (5) and / or General Formula (6) shown below

[0043] [Chemical Formula 6]

[0044]

[0045] (R1 represents a primary alkyl group or a secondary alkyl group. R2 represents hydrogen or a methyl group.

[0046] X represents a hydrocarbon group having 5 or less carbon atoms or an -OR1 group.

[0047] The resin component (A) can further include an unsaturated functional group.

[0048] The resin component (A) can further have a carboxyl group.

[0049] The resin component (A) can be an aqueous composition.

[0050] The resin component (A) can be water-based by neutralizing a carboxyl group.

[0051] The present application also relates to a cured film, characterized by being obtained by curing the above thermosetting resin composition.

[0052] Effects of the Invention

[0053] The thermosetting resin composition of the present application has excellent curing properties at a lower temperature, and can also be water-based. In addition, a compound having a carboxyl group is used to improve adhesion and pigment dispersion, and also has the advantage of being able to obtain sufficient curing properties. DETAILED DESCRIPTION

[0054] The present application will be described in detail below.

[0055] The present inventors have studied a thermosetting resin composition in which transesterification is used as a crosslinking reaction. As a result, many insights have been obtained.

[0056] As one of these insights, it can be mentioned that a thermosetting resin composition having an ester group as described in (a-1) to (a-5) above has particularly excellent curing properties at low temperatures.

[0057] Crosslinking based on transesterification can use general exchange catalysts such as acids, bases, and metal catalysts. In the research to date, the use of metal catalysts has been effective in targeting crosslinking at lower temperatures.

[0058] In the case of water-based thermosetting resin compositions, it is common to include a carboxyl group in the resin and make it water-based by neutralization, but in the case of such a composition, the carboxyl group becomes a hindering factor, and thus curing at low temperatures cannot be performed sufficiently.

[0059] The thermosetting resin composition of the present invention has an epoxy group, and thus has higher heat curing properties, and it is presumed that such problems are improved. More specifically, it is presumed that even in the case of a water-based resin, transesterification at low temperatures occurs by causing the carboxylic acid required for water-based treatment to react with the epoxy group at the time of sintering.

[0060] The present invention is a thermosetting resin composition characterized by containing a resin component (A) and a transesterification catalyst (B), the resin component (A) containing an ester group (a), an epoxy group (b), and a hydroxyl group (c) as described in (a-1) to (a-5) above.

[0061] The reason for the ester group (a) as described in (a-1) to (a-5) above is not clear, but the reactivity of transesterification is high. Therefore, by using an ester compound having this functional group as part or all of the resin component (A), a thermosetting resin composition having more excellent curing properties than in the past can be produced.

[0062] In addition, the effect of improving reactivity can be obtained regardless of the catalyst used. That is, as a transesterification catalyst, acid catalysts, basic catalysts, and metal compound catalysts are known, and in the case of using any of these, excellent curing properties can be obtained. Among these, the use of a basic catalyst or a metal compound catalyst is preferred.

[0063] The thermosetting resin composition of the present disclosure can be used in a wide variety of fields such as the field of paints, the field of adhesives, and the field of electronic materials. Therefore, there are problems in that the catalyst that can be used is limited depending on the intended use of each field. Even in such a case, it is preferable in that a catalyst suitable for the purpose can be used.

[0064] Further, in the case where the thermosetting resin composition is used as a coating material and wet-on-wet coating is performed, the thermosetting resin composition of the present application also has a good effect that has not been obtained in the past, and can be suitably used.

[0065] In the field of coating such as automotive coating, a multilayer coating film in which a plurality of coating films are stacked is often formed.

[0066] In the formation of such a multilayer coating film, a coating film formation method in which, after the application of an aqueous base coating material, a solvent-based clear coating material is applied to an uncured coating film that has been subjected only to drying and not to thermal curing, and the coating films of the multilayer system are simultaneously cured is generally performed.

[0067] In such coating, the components of the aqueous base coating film are transferred to the clear coating film. Due to this, the catalytic activity of the solvent-based clear coating material is sometimes deactivated, and the curability of the clear coating material cannot be sufficiently obtained. Therefore, sometimes sufficient curing at low temperature cannot be performed, and the effect of low-temperature curing cannot be sufficiently obtained.

[0068] The thermosetting resin composition of the present application is high in reactivity as described above, and therefore, in the formation of the above-described wet-on-wet multilayer coating film, even in the case where intermixing of the coating films with other layers occurs, it can be cured at a relatively low temperature. Due to this, the multilayer coating film can be efficiently formed by curing at a low temperature.

[0069] Therefore, in the formation of the above-described wet-on-wet multilayer coating film, the thermosetting resin composition of the present application can be used as the aqueous base coating material composition of the lower layer, and can be used as the solvent-based clear coating material composition of the upper layer. In addition, both of them can be the thermosetting resin composition of the present application.

[0070] The ester group-containing compounds having the structure of the ester group (a) represented by (a-1) to (a-5) described above are all well-known compounds, and they will be briefly described below.

[0071] (a-1) a compound represented by the following general formula (1)

[0072] [Chem. 7]

[0073]

[0074] n1: 1 to 10

[0075] (In the formula, R4, R5, and R6 are the same or different and are hydrogen, an alkyl group, a carboxyl group, an alkyl ester group, or a structure represented by R7-[COOR8]n1 described below.

[0076] R7is an aliphatic, alicyclic or aromatic alkylene group which can have a side chain, the number of atoms of the main chain of which is 50 or less, and which can have one or two or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, a urethane group in the main chain.

[0077] R8is an alkyl group having 50 or less carbon atoms.

[0078] In the compound represented by the above general formula (1), the R7-[COOR8]n1group can be a lactone structure of the following general formula (1-1).

[0079] [Chemical Formula 8]

[0080]

[0081] The ester group in such a compound easily undergoes transesterification. Furthermore, since such a compound has an unsaturated group, energy ray curing can also be produced through the unsaturated group. Therefore, a dual-curing type thermosetting resin composition which can be cured by both heat curing and energy ray curing can be produced.

[0082] As the structure represented by the above general formula (1), more specifically, a structure represented by the following general formula can be exemplified.

[0083] [Chemical Formula 9]

[0084]

[0085] n2: 1 to 10

[0086] (In the formula, R9is H or a methyl group.

[0087] R 10 is an alkylene group which can have a side chain, the number of atoms of the main chain of which is 48 or less, and which can have an ester group, an ether group and / or an amide group in the main chain.

[0088] R 11 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 publicly known synthesis method using (meth)acrylic acid or a derivative thereof as a raw material.

[0089] The number of atoms of the main chain of the above R 10 is more preferably 40 or less, further preferably 30 or less, and further preferably 20 or less. As the atoms which can be contained in the main chain of R 10 , there is no particular limitation, and in addition to carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms and the like can be contained. More specifically, in R 10In addition to the alkyl group, the main chain can have an ether group, an ester group, an amino group, an amide group, a sulfide group, a sulfonate group, a thioester group, a siloxane group, or the like.

[0090] More specifically, the structure represented by the above general formula (5) can be, for example, a compound represented by the following general formula (12) or the like.

[0091] [Chemical Formula 10]

[0092]

[0093] (In the formula, R 20 is an alkyl group having 1 to 50 carbon atoms.

[0094] R 21 is an alkyl group having 1 to 50 carbon atoms.

[0095] R 22 is an alkyl group having 1 to 50 carbon atoms.

[0096] R 23 is an alkyl group having 1 to 50 carbon atoms.

[0097] R 24 is an alkyl group having 1 to 50 carbon atoms.

[0098] n7 is 0 or 1.

[0099] n8 is 1 or 2.

[0100] The compound represented by the above general formula (5) can be a compound having a functional group and an unsaturated group represented by the following general formula (31).

[0101] [Chemical Formula 11]

[0102]

[0103] n = 0 to 20

[0104] R1 is an alkyl group having 1 to 50 carbon atoms.

[0105] R3 is hydrogen or an alkyl group having 1 to 10 carbon atoms.

[0106] That is, in the compound represented by general formula (1), the COOR8 group can have the structure represented by the above general formula (31).

[0107] The reason for the ester group represented by the above general formula (31) is not clear, but the reactivity of the transesterification reaction is high. Therefore, by using an ester compound having this functional group as part or all of the resin component, a thermosetting resin composition having more excellent curing properties than conventional ones can be produced.

[0108] Therefore, it is possible to suitably use as a resin for obtaining a thermosetting resin composition satisfying the conditions that the curing start temperature is 130°C or lower and the gel fraction at the time of curing under the conditions of sintering at 150°C for 30 minutes is 80% or more.

[0109] (Structure of General Formula (31))

[0110] The structure of the above General Formula (31) is based on an α-substituted carboxylate skeleton. In General Formula (31), n is 0 to 20.

[0111] The lower limit of n is more preferably 0. The upper limit of n is more preferably 5. Furthermore, it is also possible to use a mixture of a plurality of components in which the value of n in the above General Formula (31) is different. In this case, the average value of n, nav, is preferably 0 to 5. The upper limit of navis more preferably 3. The measurement of navcan be performed by NMR analysis. Furthermore, the value of n can also be measured by NMR analysis. n is most preferably 0.

[0112] In the above General Formula (31), as R1, any alkyl group having 50 or fewer carbon atoms can be used, and it can be any one of primary, secondary, or tertiary.

[0113] The alkyl group in the above alkyl ester group (i.e., R1in the above General Formula) is an alkyl group having 50 or fewer carbon atoms, more preferably in the range of 1 to 20, further preferably in the range of 1 to 10, and further preferably in the range of 1 to 6.

[0114] Most preferably, it is in the range of 1 to 4. By being in such a range, it is preferable in terms of being able to appropriately perform a curing reaction.

[0115] As the above alkyl ester group, specifically, for example, a methyl ester group, an ethyl ester group, a benzyl ester group, a n-propyl ester group, an iso-propyl ester group, a n-butyl ester group, an iso-butyl ester group, a sec-butyl ester group, a t-butyl alkyl group, and the like having a well-known ester group can be used.

[0116] As the compound having the structure represented by the above General Formula (31) and an unsaturated bond, specifically, for example, a compound represented by the following General Formula (36) can be obtained.

[0117] [Chemical Formula 12]

[0118]

[0119] (In the formula, R1is an alkyl group having 50 or fewer carbon atoms.

[0120] R2is hydrogen or a methyl group.

[0121] R3is hydrogen or an alkyl group having 10 or fewer carbon atoms.

[0122] n is 0 to 20)

[0123] R1in the above compound represented by General Formula (36) can be any one of primary, secondary, or tertiary as long as the number of carbon atoms is 50 or less. However, primary or secondary is more preferable, and primary is most preferable.

[0124] The above compound represented by General Formula (5) can be a compound having a functional group represented by General Formula (41) and / or a functional group represented by General Formula (42), and an unsaturated group.

[0125] [Chemical Formula 13]

[0126]

[0127] [Chemical Formula 14]

[0128]

[0129] (R1in any one of the above General Formula (41) and General Formula (42) is an alkyl group having 50 or less carbon atoms.

[0130] R2is an alkylene group having 50 or less carbon atoms, and can contain an oxygen atom and a nitrogen atom as a part thereof

[0131] As such a compound, more specifically, a compound represented by the following general formulae can be given.

[0132] [Chemical Formula 15]

[0133]

[0134] Examples of specific chemical structures of the compound represented by General Formula (1) that can be synthesized by the above exemplified methods are shown below. Note that the present application is not limited to the following exemplified compounds.

[0135] [Chemical Formula 16]

[0136]

[0137] (R1in the above general formula represents an alkyl group having 50 or less carbon atoms.)(a-2) A polymer having the above (a-1) as a structural unit

[0138] The compound of the above (a-1) has an unsaturated group, and thus a polymer can be produced by polymerizing the unsaturated group. Such a polymer can also be suitably used in the present application.

[0139] The polymer used in the present application can be a homopolymer or a copolymer composed of only the above monomer represented by General Formula (1), or a copolymer using other monomers.

[0140] As the other monomer usable in the above polymer, any monomer can be used as long as it is a monomer having a polymerizable unsaturated group, without particular limitation. The following exemplifies the usable monomers.

[0141] various (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, benzyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate;

[0142] various α-olefins such as ethylene, propylene or 1-butene;

[0143] various halogenated olefins other than fluoroolefins such as chloroethylene or vinylidene chloride;

[0144] various aromatic vinyl compounds such as styrene, α-methylstyrene or vinyltoluene; various amido-containing unsaturated monomers such as N-dimethylaminoethyl (meth)acrylamide, N-diethylaminoethyl (meth)acrylamide, N-dimethylaminopropyl (meth)acrylamide or N-diethylaminopropyl (meth)acrylamide; various dialkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate or diethylaminoethyl (meth)acrylate; various amino-containing monomers such as t-butylaminoethyl (meth)acrylate, t-butylaminopropyl (meth)acrylate, aziridinylethyl (meth)acrylate, pyrrolidinylethyl (meth)acrylate or piperidinylethyl (meth)acrylate;

[0145] various carboxyl-containing monomers such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid; various epoxy-containing monomers such as glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate or (meth)allyl glycidyl ether; various monoesters or diesters of α,β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid with monohydric alcohols having 1 to 18 carbon atoms;

[0146] various monomers containing a hydrolyzable silyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldiethoxysilane, vinyltris(β-methoxyethoxy)silane, allyltrimethoxysilane, trimethoxysilyl ethyl vinyl ether, triethoxysilyl ethyl vinyl ether, methyldimethoxysilyl ethyl vinyl ether, trimethoxysilyl propyl vinyl ether, triethoxysilyl propyl vinyl ether, methyldiethoxysilyl propyl vinyl ether, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, or γ-(meth)acryloxypropylmethyldimethoxysilane;

[0147] various fluorine-containing α-olefins such as fluoroethylene, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene, or hexafluoropropylene; or various perfluoroalkyl-perfluorovinyl ethers such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluorovinyl ether, or heptafluoropropyl trifluorovinyl ether, or various (per)fluoroalkyl vinyl ethers (in which the number of carbon atoms of the alkyl group is in the range of 1 to 18) containing a fluorine atom such as trifluoromethyl vinyl ether, pentafluoroethyl vinyl ether, heptafluoropropyl vinyl ether, or the like;

[0148] various alkyl vinyl ethers or substituted alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, chloromethyl vinyl ether, chloroethyl vinyl ether, benzyl vinyl ether, or phenylethyl vinyl ether;

[0149] various cyclic alkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether, or methylcyclohexyl vinyl ether; and vinyl esters of aliphatic carboxylic acids represented by 2,2-dimethylpropionic acid vinyl ester, 2,2-dimethylbutyric acid vinyl ester, 2,2-dimethylvaleric acid vinyl ester, 2,2-dimethylhexanoic acid vinyl ester, 2-ethyl-2-methylbutyric acid vinyl ester, 2-ethyl-2-methylvaleric acid vinyl ester, 3-chloro-2,2-dimethylpropionic acid vinyl ester, and the like, and vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate, or vinyl laurate, vinyl C9 branched aliphatic carboxylate, vinyl C 10 branched aliphatic carboxylate, or vinyl stearate; or vinyl esters of carboxylic acids having a cyclic structure such as vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate, or vinyl p-t-butylbenzoate, and the like. 11 branched aliphatic carboxylate, or vinyl stearate; or vinyl esters of carboxylic acids having a cyclic structure such as vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate, or vinyl p-t-butylbenzoate, and the like.

[0150] As the monomer containing a hydroxyl group, there are no particular limitations, and the following monomers can be cited. Various hydroxyl group-containing vinyl ethers such as 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether, hydroxyethyl acrylamide, or 6-hydroxyhexyl vinyl ether; or addition reaction products of these various vinyl ethers with ε-caprolactone; various hydroxyl group-containing allyl ethers such as 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, 2-hydroxy-2-methylpropyl (meth)allyl ether, 5-hydroxypentyl (meth)allyl ether, or 6-hydroxyhexyl (meth)allyl ether; or addition reaction products of these various allyl ethers with ε-caprolactone;

[0151] or various hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, or polypropylene glycol mono(meth)acrylate; or addition reaction products of these various (meth)acrylates with ε-caprolactone.

[0152] Further, in the case where the monomer containing a hydroxyl group as a monomer does not directly have a hydroxyl group but has a hydroxyl group via a linking chain of 5 or more molecules, it is preferable from the aspect that the hydroxyl group is easily mobile in the resin and easily reacts.

[0153] Further, a compound having both an unsaturated group and an epoxy group such as glycidyl (meth)acrylate described in detail below can also be used as a monomer.

[0154] In the present application, by combining and polymerizing the above various monomers as necessary, a compound having both the structure represented by the above general formula (1) and a hydroxyl group, a structural unit derived from the structure (a) represented by the above general formula (1), a polymer having one or two or more functional groups selected from the group consisting of a hydroxyl group and an epoxy group can be produced. Further, the above functional group necessary for water solubilization can also be introduced into the resin in the necessary proportion according to the purpose.

[0155] The method for producing the above polymer is not particularly limited, and the polymer can be produced by polymerization using a publicly known method. More specifically, there can be mentioned a solution polymerization method in an organic solvent, an emulsion polymerization method in water, a microemulsion polymerization method in water, a water-solution polymerization method, a suspension polymerization method, a UV curing method, and the like.

[0156] In addition, in the case where solution polymerization in an organic solvent is performed, thereafter, water-based treatment can be performed by a publicly known operation, and a form that can be used for the water-based thermosetting resin composition can also be produced.

[0157] In addition, the side chain of the polymer obtained by polymerizing the above composition can also be reacted, and thereby a hydroxyl group and / or the structure (a) represented by the above general formula (1) can be introduced into the side chain. As the reaction to the side chain, there is no particular limitation, and there can be mentioned transesterification, reaction with an isocyanate, reaction with an epoxy, reaction with a silane, reaction with a melamine resin, addition reaction, hydrolysis, dehydration condensation, substitution reaction, and the like.

[0158] Further, an unsaturated group can also be introduced into the side chain by the above reaction. Specifically, an unsaturated group can be introduced into the side chain by a method in which (meth)acrylic acid is copolymerized, and then glycidyl methacrylate is added, and an unsaturated group is introduced into the side chain of the resin by reaction of a carboxyl group with an epoxy group; a method in which hydroxy methacrylate is copolymerized, and then 2-isocyanatoethyl (meth)acrylate is added, and an unsaturated group is introduced by reaction of a hydroxyl group with an isocyanate group; and the like. The thermosetting resin composition of the present application is preferably one having a polymerizable unsaturated group from the viewpoint that a dual-curable curable resin composition capable of both thermal curing and energy ray curing can be produced.

[0159] The molecular weight of the above polymer is not particularly limited, and for example, the weight average molecular weight can be 3,000 to 1,000,000. The upper limit of the above weight average molecular weight is more preferably 300,000, further preferably 100,000, and further preferably 50,000. The lower limit of the above weight average molecular weight is more preferably 3,000, and further preferably 4,000.

[0160] There can be mentioned a water-soluble acrylic resin having a weight average molecular weight of usually 5,000 to 100,000, and preferably 5,000 to 50,000, or a dispersion of an acrylic resin emulsion having a weight average molecular weight of 50,000 or more, and preferably 100,000 or more, that is, an acrylic resin particle.

[0161] The water-based acrylic resin preferably contains a hydroxyl group, and generally preferably has a hydroxyl value in the range of 20 to 200 mgKOH / g, particularly 20 to 150 mgKOH / g, from the viewpoints of water dispersibility or compatibility with other components, the curing property of the formed coating film, and the like. In addition, the water-based acrylic resin generally preferably has an acid value in the range of 1 to 100 mgKOH / g, particularly 10 to 70 mgKOH / g.

[0162] (a-3) a compound having a structure represented by the following general formula (2).

[0163] [Chemical Formula 17]

[0164]

[0165] n = 0 to 20

[0166] R1is an alkyl group having 50 or less carbon atoms.

[0167] R3is hydrogen or an alkyl group having 10 or less carbon atoms.

[0168] As described above, a compound in which a carboxylic acid group of a compound having a carboxylic acid group is converted to a structure represented by the above general formula (1) can also be used. Such a compound can be obtained by reacting a carboxylic acid or a derivative thereof with a compound represented by the above general formula (2). Note that a compound having both a structure represented by general formula (1) and an unsaturated group used in the polymerization of the above (A-1) can also be used as a component of (A-2) in a state in which the compound contains an unsaturated group.

[0169] When used in the thermosetting resin composition of the present application, it is preferable to be a compound having two or more functional groups, and a polycarboxylic acid having two or more carboxyl groups, a hydroxycarboxylic acid having a carboxyl group and a hydroxyl group, and the like can be used.

[0170] Various polycarboxylic acids are general raw materials that are widely and inexpensively provided for a variety of uses such as polyester raw materials, polyamide raw materials, neutralizing agents, synthetic raw materials, and the like. A compound obtained by alkyl esterification of such a polycarboxylic acid by a known method can also be used in the present application.

[0171] When such a compound is used as a compound having an alkyl ester group, it can be esterified inexpensively by a known method, and a polycarboxylic ester group can be introduced at a relatively low molecular weight. In addition, by esterification, the compatibility with organic solvents becomes good, and it can be used as appropriate, which is preferable in this respect.

[0172] As the polycarboxylic acid used herein, there is no particular limitation, and for example, a polycarboxylic acid having 50 or less carbon atoms can be used.

[0173] More specifically, there are aliphatic polycarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, octadecanedioic acid, citric acid, butane tetracarboxylic acid, and the like;

[0174] cycloaliphatic polycarboxylic acids such as 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, and the like;

[0175] aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, trimellitic acid, pyromellitic acid, and the like;

[0176] fatty acids such as coconut oil fatty acid, cottonseed oil fatty acid, rapeseed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, and the like; monocarboxylic acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexanoic acid, 10-phenylstearic acid, and the like; hydroxycarboxylic acids such as lactic acid, 3-hydroxybutyric acid, 3-hydroxy-4-ethoxybenzoic acid, and the like; and the like.

[0177] The molecular weight of the compound in which the carboxylic acid group of the above polycarboxylic acid is replaced by the structure represented by the above general formula (1) is preferably 10,000 or less. By such a compound, the molecule is preferably mobile and curing is facilitated. The molecular weight can also be lower, such as 6,000 or less, 4,000 or less, 2,000 or less, 1,000 or less. The above molecular weight can be determined by chemical analysis means such as NMR to ascertain the chemical structure of the compound. In the case of a mixture of a plurality of compounds having different values of n, it is only necessary that a portion of the components have a molecular weight of 3,000 or less.

[0178] In the present application, as a preferred example of the compound having the structure represented by the general formula (1), there is a compound represented by the following general formula (11).

[0179] [Chemical Formula 18]

[0180]

[0181] (R1is an alkyl group having 50 or fewer carbon atoms.

[0182] R3is hydrogen or an alkyl group having 10 or fewer carbon atoms.

[0183] x is 1 to 8

[0184] n = 0 ~ 20

[0185] Further, the compound having the structure represented by the above general formula (1) is preferably one having a benzene ring. That is, a compound in which the carboxyl group of a compound having 2 or 3 carboxyl groups on a benzene ring is substituted with the structure of the above general formula (1) corresponds thereto.

[0186] If such a compound is used as a curing agent, because of having a benzene ring, a cured product excellent in heat resistance and strength can be produced, and in this respect it is preferred. As such a carboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and the like can be given. Among these, the use of trimellitic acid is particularly preferred. The chemical formula of a compound in which the carboxyl group of trimellitic acid is converted to the structure of general formula (1) is represented by the following general formula (12).

[0187] [Chemical Formula 19]

[0188]

[0189] R1is an alkyl group having 50 or less carbon atoms.

[0190] R3is hydrogen or an alkyl group having 10 or less carbon atoms.

[0191] n = 0 ~ 20

[0192] Further, in the case where the carboxylic acid group in citric acid or a derivative thereof is provided with the structure represented by the above general formula (2), the structure represented by the following general formula is obtained.

[0193] [Chemical Formula 20]

[0194]

[0195] Note that R4is not particularly limited, and can be H or an alkyl group having 20 or less carbon atoms, and can have an ester group, an ether group, an amide group, an amino group, a carbamate group, an aromatic group, or an unsaturated group in the structure.

[0196] (a-4) a compound having a structure represented by the following general formula (3) or (4)

[0197] [Chemical Formula 21]

[0198]

[0199] [Chemical Formula 22]

[0200]

[0201] (In either of the above general formula (3) and general formula (4), R1is an alkyl group having 50 or less carbon atoms.

[0202] R2is a moiety of an alkylene group having 50 or less carbon atoms which can contain an oxygen atom, a nitrogen atom

[0203] As such a compound, there is no particular limitation, and a compound obtained by converting various carboxylic acids to the above-mentioned functional groups by reacting with a compound having an alkyl ester group and a carboxyl group can be used. As the carboxylic acid, there is no particular limitation, and various carboxylic acids exemplified in the above-mentioned (a-3) can be mentioned.

[0204] (a-5) the following general formula (5) and / or general formula (6)

[0205] [Chemical Formula 23]

[0206]

[0207] (R1represents a primary alkyl group or a secondary alkyl group. R2represents hydrogen or a methyl group.

[0208] X represents a hydrocarbon group having 5 or less carbon atoms or an -OR1group.

[0209] (epoxy group)

[0210] The thermosetting resin composition of the present application has an epoxy group.

[0211] The above-mentioned epoxy group can exist in any form in the composition, and any epoxy compound of an aliphatic, alicyclic, aromatic, or the like can be used. In addition, a compound having both the functional group and / or the hydroxyl group and the epoxy group represented by the above-mentioned general formula (1) can also be used. Furthermore, as the polymer, it can also be a polymer in which the epoxy group exists as a polymer having the functional group and / or the hydroxyl group and the epoxy group represented by general formula (1).

[0212] As a representative example of such an epoxy group, an alicyclic epoxy compound having a glycidyl group, a functional group represented by the following general formula (21), and other various epoxy compounds known per se can be mentioned.

[0213] [Chemical Formula 24]

[0214]

[0215] (compound having a glycidyl group)

[0216] As the compound having a glycidyl group, a polymer made using a compound having both a glycidyl group and a polymerizable unsaturated group, a compound having both a glycidyl group and a polymerizable unsaturated group, a bisphenol epoxy resin commonly used as a so-called epoxy resin, a novolak-type epoxy resin, and other arbitrary known compounds can be used.

[0217] As the compound having both a glycidyl group and a polymerizable unsaturated group, for example, a polymerizable unsaturated monomer containing an epoxy group such as glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, 3,4-epoxycyclohexylpropyl (meth)acrylate, and allyl glycidyl ether can be used alone or in combination of two or more. The polymerization method of the polymer using the same as a raw material is not particularly limited, and can be obtained by a publicly known method.

[0218] In the present application, other publicly known epoxy compounds can be used. For example, glycidyl ether compounds represented by the following general formulae, etc. can be mentioned. As such epoxy compounds, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, etc. can be mentioned.

[0219] [Chemical Formula 25]

[0220]

[0221] For example, if an epichlorohydrin is used, an epoxy group can be introduced in a compound having various skeletons by reacting it with a phenol compound, a carboxylic acid compound, a compound containing a hydroxyl group, etc. By subjecting such an arbitrary epoxide to the above reaction, a compound having a functional group represented by the above general formula (41) can be obtained. The general formula of such a reaction is shown below.

[0222] [Chemical Formula 26]

[0223]

[0224] The alicyclic epoxy compounds represented by the above general formula (21) can also be used. As such alicyclic epoxy compounds, there can be mentioned vinylcyclohexene monoxide ("CELLOXIDE 2000 (manufactured by Daicel Chemical Industries, Ltd.)", vinylcyclohexene dioxide ("ERL-4206 (manufactured by Union Carbide Corporation)", limonene dioxide ("CELLOXIDE 3000 (manufactured by Daicel Chemical Industries, Ltd.)", cyclohexene oxide, long-chain epoxy compounds ("UVR-6126 (manufactured by Union Carbide Corporation)", and the like), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate ("CYRACURE UVR-6110 (manufactured by Union Carbide Corporation)", bis(3,4-epoxycyclohexyl) adipate ("CYRACURE UVR-6128 (manufactured by Union Carbide Corporation)", and the like), bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxycyclohexyl) ether, bis(3,4-epoxycyclohexylmethyl) ether, bis(3,4-epoxycyclohexyl) diethyl siloxane, epoxidized tetrahydrobenzyl alcohol ("ETHB (manufactured by Daicel Chemical Industries, Ltd.)", 3,4-epoxycyclohexylmethyl (meth)acrylate and its caprolactone-modified product ("CYCLOMERM 100 (manufactured by Daicel Chemical Industries, Ltd.)", "CYCLOMERM 101 (same)", "CYCLOMERA 200 (same)", and the like), 1,2-bis(3,4-epoxycyclohexylmethyl)-4,5-epoxycyclohexane carboxylate and its caprolactone-modified product ("EPOLEAD GT 301 (manufactured by Daicel Chemical Industries, Ltd.)", "Epolead GT 302 (same)", and the like), 1,2,3,4-(3,4-epoxycyclohexylmethyl) tetracarboxylate and its caprolactone-modified product ("Epolead GT 401 (same)", "Epolead GT 403 (same)", and the like), and the like.

[0225] Further, the following exemplified compounds can also be used.

[0226] As the mono-epoxy compounds, there are not limited to the following compounds, for example, there can be mentioned butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, p-t-butylphenyl glycidyl ether, oxirane, propylene oxide, p-xylyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl hexanoate, glycidyl benzoate, and the like.

[0227] As the polyvalent epoxy compound, for example, there can be mentioned a bisphenol type epoxy resin in which a bisphenol such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetra bromo bisphenol A, tetra chloro bisphenol A, tetra fluoro bisphenol A, or the like is glycidylated; an epoxy resin in which other 2-valent phenol such as biphenol, dihydroxy naphthalene, 9,9-bis(4-hydroxyphenyl)fluorene, or the like is glycidylated; an epoxy resin in which a 3-valent phenol such as 1,1,1-tris(4-hydroxyphenyl)methane, 4,4-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylene)bisphenol, or the like is glycidylated; an epoxy resin in which a 4-valent phenol such as 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, or the like is glycidylated; a novolak type epoxy resin in which a novolak such as phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, or the like is glycidylated; an epoxy resin in which a polyvalent phenol is glycidylated; an aliphatic ether type epoxy resin in which a polyol such as glycerin, polyethylene glycol, or the like is glycidylated; an ether ester type epoxy resin in which a hydroxy carboxylic acid such as p-hydroxy benzoic acid, β-hydroxy naphthoic acid, or the like is glycidylated; an ester type epoxy resin in which a polyvalent carboxylic acid such as phthalic acid, terephthalic acid, or the like is glycidylated; a glycidylated product of an amine compound such as 4,4-diamino diphenyl methane, m-aminophenol, or the like; an amine type epoxy resin such as isocyanuric acid triglycidyl ester, or the like; and an alicyclic epoxy compound such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, or the like. These can be used singly or in combination of two or more. Furthermore, a substance in which these epoxy compounds are emulsified, a substance in which these epoxy compounds are microcapsulated, or the like can also be used.

[0228] (Hydroxyl group-containing compound)

[0229] For the resin component (A) of the present application, a hydroxyl group is essential. Here, the hydroxyl group can be present in a compound having the structure shown by the general formula (1) described above or a compound having an epoxy group, or a hydroxyl group-containing compound other than the compound having the structure shown by the general formula (1) described above can be additionally used.

[0230] Hereinafter, a compound which can be used when a hydroxyl group-containing compound other than the compound having the structure shown by the general formula (1) described above is used will be exemplified.

[0231] (Acrylic polyol)

[0232] The acrylic polymer described above in which a hydroxyl group-containing monomer is used as a part or all of the monomers can be suitably used in the present application. As such an acrylic polyol, any publicly known acrylic polyol can be used.

[0233] (Low molecular weight polyol)

[0234] In addition, as the compound having at least two hydroxyl groups in the molecule, a low molecular weight polyol (specifically, a molecular weight of 2,000 or less) can be used.

[0235] As the low molecular weight polyol (B-3), for example, ethylene glycol, propylene glycol, diethylene glycol, 1,3-propanediol, 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-trishydroxymethylpropane, 2-butyl-2-ethyl-1,3-propanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyl-1,3-propanediol, tetramethylene glycol, 3-methyl-4,3-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, hydroxypivalic acid neopentyl glycol ester, hydrogenated bisphenol A, hydrogenated bisphenol F, dimethylolpropionic acid, and the like 2-valent alcohols; poly-lactone diols obtained by adding a lactone compound such as ε-caprolactone to the above 2-valent alcohols; ester diol compounds such as bis(hydroxyethyl) terephthalate; polyether diol compounds such as an alkylene oxide addition product of bisphenol A, polyethylene glycol, polypropylene glycol, polybutylene glycol, and the like; glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerol, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tris(2-hydroxyethyl) isocyanurate, sorbitol, mannitol, and the like alcohols of 3 or more valences can be exemplified.

[0236] Such a low molecular weight polyol is known as a general-purpose product and can be obtained at low cost. In addition, the low molecular polyol has high water solubility and can be appropriately used as a crosslinking agent in the case of aiming at water-based curing.

[0237] (Polymerizable unsaturated functional group)

[0238] The thermosetting resin composition of the present application can further have a polymerizable unsaturated functional group. If the polymerizable unsaturated functional group is present, a resin composition capable of both heat curing and energy ray curing, so-called dual curing, can be produced. Such dual curing is known per se and is described in, for example, the above-mentioned Patent Document 6 and the like. On the other hand, it is a new invention that the curing system of the functional group represented by General Formula (1), the epoxy group, and the hydroxyl group is dual curing as in the present application.

[0239] As described above, the curing system of the present application having the functional group, the epoxy group, the hydroxyl group represented by General Formula (1) can achieve low-temperature curing. Also, since there is no component that hinders energy ray curing due to polymerization of an unsaturated bond, it is also possible to cope with dual curing.

[0240] Such a compound having a polymerizable unsaturated group can be a compound having a polymerizable unsaturated group in addition to at least one of the functional group, the epoxy group, the hydroxyl group represented by General Formula (1) of the present application, or can be a compound having a polymerizable unsaturated group without these functional groups. The compound having a polymerizable unsaturated group in addition to at least one of the functional group, the epoxy group, the hydroxyl group represented by General Formula (1) described above as a monomer in detail can be directly mixed in the composition in the state of a monomer.

[0241] Further, it is also possible to introduce an unsaturated group in a polymer. Such a compound having a polymerizable unsaturated group is particularly preferably a compound having a (meth)acryloyl group. Such a compound is described in detail below.

[0242] Compound having a (meth)acryloyl group (a)

[0243] As the compound having a (meth)acryloyl group (a), various compounds known as energy ray curable compounds can be used.

[0244] Examples of the (meth)acrylate having a functional group number of 1 can include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, and the like.

[0245] Examples of the (meth)acrylate having a functional group number of 2 include 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-decanediol di(meth)acrylate, glycerol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate (DCP-A), EO adduct of bisphenol A diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.; LIGHT-ACRYLATE BP-4EA, BP-10EA), PO adduct of bisphenol A diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.; BP-4PA, BP-10PA, and the like). Among them, the PO adduct of bisphenol A diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.; BP-4PA), dimethyloltricyclodecane di(meth)acrylate (DCP-A), and the like can be preferably used.

[0246] Examples of the (meth)acrylate having a functional group number of 3 include trimethylolmethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane epoxy ethane-modified tri(meth)acrylate, trimethylolpropane epoxy propane-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol propoxy tri(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, and the like. Among them, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, and the like can be preferably used.

[0247] Examples of the (meth)acrylate having a functional group number of 4 include dipentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol epoxy ethane-modified tetra(meth)acrylate, pentaerythritol epoxy propane-modified tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and the like. Among them, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and the like can be preferably used.

[0248] Examples of the (meth)acrylate having 4 or more functional groups can 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, hexa(meth)acrylate of a caprolactone-modified dipentaerythritol, and the like.

[0249] Further, a compound represented by the following general formula can also be used as the compound having an unsaturated group.

[0250] [Chemical Formula 27]

[0251]

[0252] n1: 1 to 10

[0253] (In the formula, R1, R2, and R3 are the same or different and are hydrogen, an alkyl group, a carboxyl group, an alkyl ester group, or R4-[COOR5] n1 represented by the following structure.

[0254] R4 is an aliphatic, alicyclic, or aromatic alkylene group which can have a side chain, and the number of atoms in the main chain is 50 or less, and the main chain can have one or two or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and a urethane group.

[0255] R5 is an alkyl group having 50 or less carbon atoms.

[0256] In the compound represented by the above general formula (1), R4-[COOR5] n1 may be a lactone structure of the following general formula (1-1).

[0257] [Chemical Formula 28]

[0258]

[0259] (Rx is a hydrocarbon group having 2 to 10 carbon atoms which can have a branched chain)

[0260] The above compound is a compound having both an unsaturated group and an alkyl ester group, and is, for example, a well-known compound described in detail in Patent Document 6 or the like, and they can be used.

[0261] Further, a compound in which an unsaturated bond is introduced by reacting a compound having an isocyanate group and an unsaturated bond with a variety of polyol compounds such as a vinyl polymer having a hydroxyl group can be used.

[0262] Specifically, a compound having an unsaturated group obtained by the following reaction can be used.

[0263] [Chemical Formula 29]

[0264]

[0265] As the compound having an isocyanate group and a polymerizable unsaturated group that can be used in the above reaction, there is no particular limitation, and for example, a compound represented by the following general formula (4) or the like can be mentioned.

[0266] [Chemical Formula 30]

[0267]

[0268] (In the formula, R 32 is a hydrocarbon group having 1 to 20 carbon atoms.

[0269] R 31 is H or a methyl group

[0270] More specifically, 2-isocyanatoethyl acrylate sold by Showa Denko K.K. under the trade name of Karenz AOI (registered trademark) or the like can be mentioned.

[0271] As the above polyol compound, there is no particular limitation, and various compounds having a hydroxyl group such as an acrylic polyol, a polyester polyol, a polycarbonate polyol, a polyurethane polyol, a polymer having a polyvinyl alcohol unit, and the like known in the art can be used.

[0272] Further, a compound having an unsaturated group introduced by reacting a (meth)acrylic acid with a polymer having an epoxy group can also be used. Specifically, a compound having an unsaturated group obtained by the following reaction can be used.

[0273] [Chemical Formula 31]

[0274]

[0275] As the compound having an epoxy group that can be used in the above reaction, there is no particular limitation, and various epoxy resins such as a bisphenol-based epoxy resin, a novolak-based epoxy resin, and the like, and an acrylic polymer having glycidyl (meth)acrylate as a part of the monomers can be mentioned.

[0276] The polymer represented by the above general formula (4) or (5) can further have a hydroxyl group and / or an alkyl ester group.

[0277] (Resin composition)

[0278] The thermosetting resin composition of the present application has the structure (a), the epoxy group (b), and the hydroxyl group (c) shown in the above general formula (1) as a whole of the composition. That is, it can be a compound having all of (a) to (c) in a single polymer, or it can be a mixture of compounds having one or more than two of the functional groups of (a) to (c).

[0279] (Ester exchange catalyst (B))

[0280] The thermosetting resin composition of the present application contains the ester exchange catalyst (B). That is, the ester exchange catalyst (B) is mixed in order to efficiently cause the ester exchange reaction between the ester group and the hydroxyl group and obtain sufficient thermosetting.

[0281] As the above ester exchange catalyst (B), any compound known as a substance capable of activating the ester exchange reaction can be used. Specifically, for example, various acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, or sulfonic acid, heteropoly acid, and the like; various basic compounds such as LiOH, KOH, or NaOH, amines, phosphines, and the like; various metal compounds such as PbO, magnesium oxide, zinc acetate, zinc acrylate, zinc triflate, lead acetate, manganese acetate, copper acetate, nickel acetate, palladium acetate, aluminum isopropoxide, zirconium acetylacetonate, ferric chloride, cobalt chloride, palladium chloride, zinc dithiocarbamate, antimony trioxide, tetraisopropyl titanate, dibutyltin dilaurate, dibutyltin dioctoate, monobutyltin acid, ytterbium triflate, or scandium triflate; quaternary ammonium salts such as tetramethylammonium chloride, dodecyltrimethylammonium bromide, triethylbenzylammonium chloride, tetramethylammonium hydroxide, trimethylbenzylmethylammonium carbonate, and the like; phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium hydroxide; strong bases such as 1,8-diazabicyclo[5.4.0]-7-undecene; and the like. In addition, a light-responsive catalyst that generates an acid by light or heat, a thermal latent catalyst can also be used. Furthermore, a zinc cluster catalyst (for example, ZnTAC24 (trade name) manufactured by Tokyo Chemical Industry Co., Ltd.) and the like can also be used. Furthermore, two or more of the above compounds can also be used together.

[0282] In the thermosetting resin composition of the present application, more preferably at least one compound selected from the group consisting of metal compounds containing metals other than alkali metals and basic catalysts is used as a catalyst. Further, as a part or all of the catalyst, most preferably a metal compound (B-1) containing a metal other than an alkali metal is used. In the thermosetting resin composition of the present application, metal compounds are particularly excellent in view of catalytic activity. In addition, for the water-insoluble catalyst, it can be prepared as a dispersion or dissolved and added to a water-soluble solvent. In particular, in the thermosetting resin composition having a primary alkyl ester group or a secondary alkyl ester group, this tendency is remarkable. In addition to the above metal compound (B-1), it is preferable to further contain at least one compound (B-2) selected from the group consisting of an organic phosphorus compound, urea, an alkylated urea, thiourea, an alkylated thiourea, a sulfoxide compound, a quaternary ammonium compound, a quaternary phosphonium compound, and an amine compound, pyridine, quinoline, isoquinoline, phenanthroline, an imidazole compound, and derivatives thereof. Hereinafter, these compounds are described in detail.

[0283] The organic phosphorus compound is not particularly limited, and examples thereof include phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, organophosphine oxide, organophosphine compounds, and various esters, amides, and salts thereof. The ester can be an alkyl ester, a branched alkyl ester, a substituted alkyl ester, a difunctional alkyl ester, an alkyl ether ester, an aryl ester, and a substituted aryl ester. The amide can be an alkyl amide, a branched alkyl amide, a substituted alkyl amide, a difunctional alkyl amide, an alkyl ether amide, an aryl amide, and a substituted aryl amide.

[0284] Among these, at least one compound selected from the group consisting of a phosphonic acid ester, a phosphoric acid amide, and an organophosphine oxide compound is particularly preferable. When these organic phosphorus compounds are used, transesterification catalytic function is the best. More specifically, organophosphine oxide compounds such as triphenylphosphine oxide, trioctylphosphine oxide, and tricyclohexylphosphine oxide; phosphoric acid amide compounds such as hexamethylphosphoric triamide and tris(N,N-tetramethylene)phosphoric triamide; organophosphine sulfide compounds such as triphenylphosphine sulfide, tributylphosphine sulfide, and trioctylphosphine sulfide; and the like can be preferably used.

[0285] The alkylated urea is not particularly limited, and examples thereof include urea, dimethylurea, dimethylpropyleneurea, and the like. Note that it can have a cyclic structure like dimethylpropyleneurea and the like.

[0286] The alkylated thiourea is not particularly limited, and examples thereof include dimethylthiourea, trimethylthiourea, tetramethylthiourea, diethylthiourea, dibutylthiourea, and the like. The sulfoxide compound is not particularly limited, and examples thereof include dimethyl sulfoxide, diphenyl sulfoxide, and the like.

[0287] The quaternary ammonium compound is preferably a compound represented by the following general formula (i).

[0288] [Chemical Formula 32]

[0289]

[0290] (wherein, in formula (i), R41to R44each independently represent a monovalent hydrocarbon group, or a monovalent hydrocarbon group having a functional group which is inert to the reaction, and Y1represents a monovalent anion.)

[0291] R 41 ~R 44 In the case where R 41 ~R 44 The number of carbon atoms of each of R 41 ~R 44 Each of R

[0292] R 41 ~R 44 The functional group in the case where R

[0293] As the quaternary ammonium (R 41 R 42 R 43 R 44 N + ), tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetra-n-butylammonium, methyltri-n-octylammonium, n-dodecyltrimethylammonium, n-dodecyltri-n-butylammonium, hexadecyltrimethylammonium, trimethylbenzylammonium, triethylbenzylammonium, hexadecylbenzyldimethylammonium, trimethyl-2-hydroxyethaneammonium, hexadecylpyridinium, n-dodecylpyridinium, phenyltrimethylammonium, phenyltriethylammonium, N-benzylmethylpyridinium, pentaalkylquaternary ammonium, hexaalkylquaternary ammonium, and the like can be given.

[0294] As Y 1- , fluoride ion, chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, bisulfate ion, hydroxide ion, acetate ion, benzoate ion, benzenesulfonate ion, p-toluenesulfonate ion, and the like can be given, with fluoride ion, chloride ion, bromide ion, iodide ion, hydroxide ion, acetate ion being preferred, and fluoride ion, chloride ion, bromide ion, iodide ion, hydroxide ion being more preferred, and chloride ion or bromide ion being further preferred.

[0295] As the compound represented by the above general formula (i), from the aspects of versatility and reactivity, the following quaternary ammonium (R 41 R42 R 43 R 44 N + ) and the following Y 1- The combination of .

[0296] Quaternary ammonium (R) 41 R 42 R 43 R 44 N + ): Tetramethylammonium, tetra-n-butylammonium, n-dodecyltrimethylammonium, n-dodecyltri-n-butylammonium, triethylbenzylammonium, trimethyl-2-hydroxyethaneammonium.

[0297] Y 1- Fluoride ions, chloride ions, bromide ions, iodide ions, hydroxide ions, and acetate ions.

[0298] As a quaternary ammonium compound, considering factors such as reactivity, industrial availability, price, and ease of operation, it is preferably selected from at least one of the following groups: tetramethylammonium chloride, tetra-n-butylammonium fluoride, tetra-n-butylammonium iodide, tetra-n-butylammonium hydroxide, tetra-n-butylammonium acetate, n-dodecyltrimethylammonium bromide, n-dodecyltri-n-butylammonium bromide, triethylbenzylammonium chloride, and trimethyl-2-hydroxyethane ammonium chloride (choline chloride).

[0299] Examples of quaternary phosphorus compounds include those represented by the general formula (ii) below.

[0300] [Chemistry 33]

[0301]

[0302] (wherein, in equation (ii), R) 51 ~R 54 Each of the following independently represents a monovalent hydrocarbon group, Y 2- R represents a monovalent anion. 51 ~R 54 They can be the same group or different groups.

[0303] As R 51 ~R 54 Examples of hydrocarbon groups in this text include alkyl, cycloalkyl, alkenyl, cycloalkenyl, and aryl groups, with alkyl and aryl groups being preferred.

[0304] As in the above general formula (ii), quaternary phosphonium (R) 51 R 52 R 53 R 54 P +As the above-mentioned quaternary phosphonium compound, tetraethylphosphonium, tetra-n-butylphosphonium, ethyltri-n-octylphosphonium, hexadecyltriethylphosphonium, hexadecyltri-n-butylphosphonium, n-butyltriphenylphosphonium, n-pentyltriphenylphosphonium, methyltriphenylphosphonium, benzyltriphenylphosphonium, tetraphenylphosphonium, and the like can be given.

[0305] As the above-mentioned quaternary phosphonium compound, at least one selected from the group consisting of tetra-n-butylphosphonium hydroxide, tetra- butylphosphonium bromide, and tetra-butylphosphonium chloride is preferable from the aspects of reactivity and easiness of industrial availability.

[0306] As Y 2- As the above-mentioned anion, chloride ion, fluoride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, bisulfate ion, hydroxide ion, acetate ion, benzoate ion, benzenesulfonate ion, p-toluenesulfonate ion, and the like can be given, and fluoride ion, chloride ion, bromide ion, and hydroxide ion are preferable.

[0307] As the above-mentioned imidazole compound, a compound represented by the following general formula is preferable.

[0308] [Chemical Formula 34]

[0309]

[0310] (In the formula, R is an alkyl group, an alkenyl group, or an aromatic substituent having 10 or less carbon atoms which can have a branched structure or a ring structure.)

[0311] As the above-mentioned compound represented by the general formula, 1-methylimidazole, 1- ethylimidazole, 1-propylimidazole, 1-butylimidazole, 1-vinylimidazole, and the like can be given, and 1-methylimidazole is preferable in terms of manufacturing cost.

[0312] As the above-mentioned pyridine derivative, dimethylaminopyridine, quinoline, isoquinoline, nicotinate, and the like can be given.

[0313] As the above-mentioned quinoline derivative, 8-hydroxyquinoline, 2-methyl-8- hydroxyquinoline, and the like can be given.

[0314] As the above-mentioned amine compound, any one of primary, secondary, and tertiary can be given, and 1,4-piperidine, dimethylethanolamine, diazabicycloundecene, diazabicyclononene, aminopyridine, 4-dimethylaminopyridine, triethylenediamine, dimethyloctylamine, N,N,N-tetramethylethylenediamine, N,N-dimethylcyclohexylamine, 1- azabicyclo[2,2,2]octane, 1-azabicyclo[2,2,2]octan-3-ol, bis(2-dimethylaminoethyl)ether 1,4- diazabicyclo[2.2.2]octan-2-ylmethanol, and the like can be given.

[0315] The transesterification catalyst preferably contains the compound (B-1) and the compound (B-2) in a ratio of (B-1):(B-2) = 100:1 to 1:100 by weight. By mixing them in such a ratio, particularly preferable results can be obtained. The above lower limit is more preferably 50:1, and further preferably 10:1. The above upper limit is more preferably 1:50, and further preferably 1:10.

[0316] The compound (B-1) is preferably contained in an amount of 0.01 to 50% by weight, relative to the amount of the compound participating in the reaction in the reaction system at the time of the reaction. The compound (B-2) is preferably contained in an amount of 0.01 to 50% by weight, relative to the amount of the compound participating in the reaction in the reaction system at the time of the reaction.

[0317] In the resin composition of the present application, as the transesterification catalyst (B), (1) a zirconium compound is used, and (2) the above-mentioned compound (B-1) and the compound (B-2) are used, and by such a method, the above-mentioned physical properties can be particularly suitably obtained, and it is preferred from this aspect. If the above-mentioned (1) and (2) are used as the transesterification catalyst, and a substance having particularly high transesterification reactivity is selected as the resin component, a resin composition having properties of a curing start temperature of 130°C or lower, and a gel fraction of 80% or more when cured under conditions of sintering in 30 minutes at 150°C or lower can be obtained.

[0318] In the resin composition of the present application, as the transesterification catalyst (B), it is also preferred to use a basic compound (B-3). As the basic compound (B-3), there is no particular limitation, and an amine compound or the like can be preferably used.

[0319] The amine compound which can be used as the basic compound (B-3) can be any one of primary, secondary, and tertiary, and 1,4-piperidine, dimethyl ethanolamine, diazabicyloun-decane, diazabicyclononane, aminopyridine, 4-dimethylaminopyridine, triethylenediamine, dimethyloctylamine, N,N,N-tetramethylethylenediamine, N,N-dimethylcyclohexylamine, N,N,N'N'pentamethyldiethylenetriamine, 1,4-diazabicyclo[2.2.2]octan-2-ylmethanol, N,N,N'N'-trimethylhexane-1,6-diamine, bis(2-dimethylaminoethyl)ether, ethyleneglycol bis(3-dimethylaminopropyl ether, 1-azabicyclo[2.2.2]octane, 1-azabicyclo[2,2,2]octan-3-ol, N,N,N'N'N"N"-hexamethyltriazene tetraamine, and the like can be mentioned.

[0320] Among these, a tertiary amine and a quaternary ammonium salt are particularly preferred.

[0321] In the present application, it is clarified that by containing an epoxy compound, the reactivity is remarkably improved in transesterification reaction using a basic catalyst. Therefore, even in the case where the above metal catalyst is not used but only the basic compound (B-3) is used as a catalyst, it is preferable in terms of showing excellent low-temperature curing properties.

[0322] A thermosetting resin composition containing the resin component (A) (B) having -COOR (R is an alkyl group having 50 or less carbon atoms) and a hydroxyl group, and the transesterification catalyst of the above (2) as the transesterification catalyst (B) is also one of the present application.

[0323] Further, if zinc acetylacetonate is used as the transesterification catalyst, and a substance having particularly high transesterification reactivity is selected as the resin component, a resin composition having properties of a gelation rate of 80% or more when cured under conditions of sintering at 100°C or less for 30 minutes with a curing start temperature of 100°C or less can be obtained.

[0324] The amount of the above transesterification catalyst (B) is preferably 0.01 to 50% by weight, relative to the total weight of the resin component (A) (B). By being in such a range, it is preferable in terms of being able to perform a good curing reaction at low temperatures.

[0325] In addition, in the case where the above thermosetting resin composition is made into an aqueous composition, such a catalyst is preferably a water-soluble compound or a water-soluble dispersion or emulsion. From the above viewpoint, as the water-soluble catalyst which can be preferably used in the present application, there are no particular limitations, and examples include tetramethylammonium chloride, dodecyltrimethylammonium bromide, triethylbenzylammonium chloride, tetramethylammonium hydroxide, trimethylbenzylammonium methyl carbonate, zinc acetate, zinc acrylate, 1,8-diazabicyclo[5.4.0]-7-undecene, dibutyltin dilaurate, and the like.

[0326] (Photo-polymerization initiator (B-4))

[0327] In the case where the curable resin composition of the present application has an unsaturated bond, it is preferable to contain a photo-polymerization initiator. Thereby, a composition having both thermal curing properties and energy ray curing properties can be made.

[0328] As the photopolymerization initiator, there are no particular limitations, and examples thereof include acetophenone-based initiators such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-l-phenylpropan-l-one, 2-methyl-l-[4-(methylthio)phenyl]-2-morpholinopropan-l-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-l-propan-l-one, and the like; benzoin-based initiators such as benzoin, 2,2-dimethoxy-l,2-diphenylethan-l-one, and the like; benzophenone-based initiators such as benzophenone, [4-(methylphenylthio)phenyl]phenyl methanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and the like; thioxanthone-based initiators such as 2-chlorothioxanthone, 2,4-diethylthioxanthone, and the like; and the like. As the accelerator, there are no particular limitations, and examples thereof include tertiary amines such as ethyl-p-dimethylaminobenzoate, isoamyl-p-dimethylaminobenzoate, and the like. The content of the above-described photopolymerization initiator (B-2) is not particularly limited, and it is preferably mixed at a proportion of 0.01 to 50% by weight with respect to the solid content of the resin component (A). If the coloring, physical properties, storage stability, and the like of the coating film are taken into consideration, it is more preferably 0.5 to 10% by weight.

[0329] In the thermosetting composition of the present application, in addition to the above-described components (A) and (B), other crosslinking agents that are generally used in the field of paints and adhesives can be further used in combination. As the crosslinking agent that can be used, there are no particular limitations, and examples thereof include isocyanate compounds, blocked isocyanate compounds, melamine resins, epoxy resins, silane compounds, and the like. In addition, vinyl ethers, anionic polymerizable monomers, cationic polymerizable monomers, radical polymerizable monomers, and the like can also be used in combination. A curing agent for promoting the reaction of these combined crosslinking agents can also be used in combination.

[0330] Note that the above-described other crosslinking agent is not essential, and the thermosetting resin composition of the present application can achieve good curability even if the above-described other crosslinking agent is not contained, and it is preferred from this aspect.

[0331] In the case where the above-described crosslinking agent is a polyisocyanate compound and / or a melamine resin, the mixing amount thereof with respect to the total amount of the resin component (A) and the crosslinking agent, that is, the mixing amount of (the amount of the crosslinking agent) / (the amount of the crosslinking agent + the amount of the resin component) is preferably 0.01 to 50% by weight. By being in this range of the mixing amount, both the curing reaction based on the transesterification reaction and the curing reaction based on the other curing agent can occur, and it is preferred from this aspect.

[0332] The above-described lower limit is more preferably 0.01% by weight, and further preferably 1% by weight. The above-described upper limit is more preferably 30% by weight, and further preferably 20% by weight.

[0333] The thermosetting resin composition of the present application can be an aqueous thermosetting resin composition, or a solvent-based thermosetting resin composition. Furthermore, it can also be a thermosetting resin composition having a solid form such as a powder paint.

[0334] When the thermosetting resin composition of the present application is made into an aqueous thermosetting resin composition, it is particularly preferable from the viewpoint of being able to sufficiently obtain low-temperature curing properties. That is, in the case of a known aqueous thermosetting resin composition in which transesterification is used as the curing reaction, when a -COOH group is present, there is a tendency for the reactivity to decrease. Therefore, when the resin is made aqueous by introducing a -COOH group, if the curability is not improved by increasing the curing reaction or the like, sufficient curing reaction cannot occur.

[0335] However, the compound having the alkyl ester group represented by the above general formula (1) is able to perform a curing reaction at a lower temperature even in the presence of a -COOH group. Therefore, it can also be suitably used as an aqueous thermosetting resin composition.

[0336] As such an aqueous thermosetting resin composition, the following methods are generally known:

[0337] (a) A method in which aqueous is performed by using a water-soluble component or a water-dispersible component.

[0338] (b) A method in which aqueous is performed by emulsifying a water-insoluble component in water using an emulsifier.

[0339] Therefore, each of these methods will be described in detail. Note that among the components included in the aqueous thermosetting resin composition, a part of the components can be made aqueous using method (a), and the other components can be made aqueous using method (b).

[0340] (a) A method of water-based by using a water-soluble ingredient or a water-dispersible ingredient.

[0341] Such a method is a method in which the organic component that forms the coating film is made water-soluble or water-dispersible itself. When such a method is used, it is possible to make a coating composition that does not use a surfactant, and this is preferable from this aspect.

[0342] The resin used in the above (a) is not particularly limited, and a resin having at least one acid group selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a sulfuric acid group, and a phosphoric acid group, and being water-solubilized by converting it into a hydrophilic group by neutralization with ammonia and / or an amine compound can be used. In addition, the water-soluble compound described in detail below can also be used. Among these, a carboxylic acid group is preferable from the viewpoint of low cost and the like.

[0343] The resin having an acid group described above can be obtained by performing a known polymerization reaction using at least a part of a monomer having such a functional group in an organic solvent. After that, neutralization can be performed by adding water and an amine and / or ammonia, and water-based can be performed.

[0344] In the case of water-based by neutralizing the acid group like this, among various resins, an acrylic polymer, a polyester resin, a urethane resin can be most suitably used in general. In order to introduce a functional group having the acid group described above in an acrylic resin, it is preferable to perform a polymerization reaction using a polymerizable monomer having an acid group as a part of a raw material.

[0345] In such a method, a monomer that can be used as a monomer having an acid group is not particularly limited, and a monomer that can be used can be selected according to the type of the resin. For example, a carboxylic acid compound containing an unsaturated group such as (meth)acrylic acid, 2-methacryloyloxyethyl succinic acid, maleic acid, crotonic acid, acrylic acid-β-carboxyethyl ester, toluenesulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacryloyloxyethyl acid phosphate, and the like can be exemplified.

[0346] In the above polymer, such an acid group is preferably introduced in a manner that the acid value of the resin is in the range of 0.1 to 100. The lower limit of the above acid value is preferably 0.5, and further preferably 1. The upper limit of the above acid value is preferably 50, and further preferably 30.

[0347] As the amine compound described above, for example, tertiary amines such as triethylamine, tributylamine, dimethylethanolamine, triethanolamine, and the like; secondary amines such as diethylamine, dibutylamine, diethanolamine, morpholine, and the like; primary amines such as propylamine, ethanolamine, dimethylethanolamine, and the like; quaternary ammonium such as ammonia; and the like can be exemplified. In the case of reacting with an epoxy group, primary amines and secondary amines react, and therefore tertiary amines or quaternary amines are preferable.

[0348] As for the amount of use when the amine compound described above is used, it is preferable to be in the range of generally 0.1 to 1.5 molar equivalents with respect to the carboxyl group in the unsaturated carboxylic acid or acid anhydride modified polyolefin (i).

[0349] In the case of water-based by the method described above, a resin can be obtained by a method such as general solution polymerization, and after that, water and an amine compound are added and stirred, and thus water-based can be performed.

[0350] (b) A method of water-based by emulsifying an ingredient in water using an emulsifier.

[0351] Unlike the above method, water-based can be performed by emulsifying the resin using an emulsifier.

[0352] In this case, the resin can be obtained by emulsion polymerization, or a resin obtained by solution polymerization or the like can be emulsified using an emulsifier. Further, the emulsifier can also use a reactive emulsifier.

[0353] As the above-mentioned anionic reactive emulsifier, for example, a sodium salt, an amine salt, an ammonium salt, or the like of a sulfonic acid compound having a (meth)allyl group, a (meth)acryl group, an acryl group, a butenyl group, or the like polymerizable unsaturated group can be exemplified. Of these, an ammonium salt of a sulfonic acid compound having a polymerizable unsaturated group is preferred from the viewpoint of excellent water resistance of the obtained coating film. As a commercial product of the ammonium salt of the sulfonic acid compound, for example, Latemul S-180A (manufactured by Showa Denko K.K., trade name), Aquaron KH10 (manufactured by NOF Corporation, trade name), or the like can be exemplified.

[0354] Further, as a nonionic reactive emulsifier, for example, a reactive emulsifier having a (meth)allyl group, a (meth)acryl group, an acryl group, a butenyl group, or the like polymerizable unsaturated group and obtained by adding ethylene oxide, propylene oxide, or the like can be exemplified.

[0355] Further, of the above-mentioned ammonium salts of sulfonic acid compounds having a polymerizable unsaturated group, an ammonium salt of a sulfate compound having a polymerizable unsaturated group and a polyoxyalkylene group is more preferred. As a commercial product of the above-mentioned ammonium salt of a sulfate compound having a polymerizable unsaturated group and a polyoxyalkylene group, for example, Aquaron KH-10 (manufactured by NOF Corporation, trade name), SR-1025A (manufactured by Asahi Denka Kogyo K.K., trade name), or the like can be exemplified.

[0356] The concentration of the above-mentioned emulsifier is preferably generally in the range of 0.1 to 10% by mass, particularly 1 to 5% by mass, based on the total amount of the radical polymerizable unsaturated monomers used.

[0357] Among the emulsified resins obtained by emulsion polymerization using a reactive emulsifier, since the emulsifier is introduced into the resin, it has the advantage that adverse conditions due to the presence of the emulsifier do not occur. Therefore, in applications where the presence of the emulsifier becomes a problem, it is preferred to use an emulsified resin obtained by such a method.

[0358] As the emulsifier other than the above-mentioned reactive emulsifier, for example, nonionic emulsifiers such as polyoxyethylene monooctyl ether, polyoxyethylene monostearate, polyoxyethylene monolauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, and the like; anionic emulsifiers such as sodium salts, ammonium salts, and the like of alkylsulfonic acids, alkylbenzenesulfonic acids, alkylphosphoric acids, and the like; and the like can be mentioned. In addition, polyoxyalkylene anionic emulsifiers having an anionic group and a polyoxyalkylene group in one molecule, reactive anionic emulsifiers having an anionic group and a polymerizable unsaturated group in one molecule, and the like can be used. In addition, high-molecular emulsifiers, quaternary ammonium salts, and the like can be used. These emulsifiers can be used alone or in combination of two or more.

[0359] The amount of the above-mentioned emulsifier is preferably usually 30 parts by mass or less, particularly 0.5 to 25 parts by mass, relative to 100 parts by mass of the solid content of the above-mentioned unsaturated carboxylic acid or acid anhydride-modified polyolefin (i).

[0360] In addition, in the case of using a resin obtained by emulsion polymerization, the emulsion polymerization method is not particularly limited and can be performed by a publicly known conventional method. In addition, the emulsifier can be the above-mentioned reactive emulsifier or a conventional emulsifier.

[0361] In the case of performing a method of emulsifying a resin obtained by a method such as solution polymerization using a conventional organic solvent using an emulsifier, the specific method is not particularly limited and can be performed by a publicly known conventional method. As the emulsifier that can be used in this case, the above-mentioned emulsifiers that can be used in emulsion polymerization can be mentioned.

[0362] In addition, in the case of using various ester compounds or polyhydric alcohols described in detail below and being a substance that is not soluble in water, water-solubilization can be performed by applying a publicly known method, for example, a method of emulsifying using an emulsifier, a method of solubilizing by using an organic solvent having high miscibility with water in addition to water, and the like. As the organic solvent having high miscibility with water that can be used in such a method, methanol, ethanol, isopropanol, butanol, butyl cellulose, ether-based solvents, ketone-based solvents, and the like can be mentioned.

[0363] The thermosetting resin composition of the present application can be appropriately used in the fields of thermosetting paints, thermosetting adhesives, and the like.

[0364] The thermosetting resin composition of the present application can contain, in addition to water, an aqueous solvent such as ethanol, methanol, an alcohol-based solvent, a glycol-based solvent, an ether-based solvent, a ketone-based solvent, or the like, which can be mixed with water in any ratio.

[0365] In the case of use as a thermosetting paint, an additive generally used in the paint field can be used in combination with the above-described components. For example, a leveling agent, a defoaming agent, a reactive diluent, a non-aqueous dispersion type paint (NAD), a coloring pigment, a body pigment, a luster pigment, and the like, a pigment dispersant, a rheology control agent, an antioxidant, a UV absorber, and any combination thereof can be used in combination.

[0366] In the case of using a pigment, the pigment is preferably contained in a range of 1 to 500% by mass, based on 100% by mass of the total solid content of the resin component. The lower limit of the above range is more preferably 3% by mass, and further preferably 5% by mass. The upper limit of the above range is more preferably 400% by mass, and further preferably 300% by mass.

[0367] As the coloring pigment, for example, titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, an azo-based pigment, a phthalocyanine-based pigment, a quinacridone-based pigment, an isoindoline-based pigment, a sylene-based pigment, a perylene-based pigment, a dioxazine-based pigment, a diketopyrrolopyrrole-based pigment, and the like, and any combination thereof can be given.

[0368] As the body pigment, for example, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, alumina white, and the like can be given, and barium sulfate and / or talc is preferred, and barium sulfate is more preferred.

[0369] As the luster pigment, for example, aluminum (including vapor-deposited aluminum), copper, zinc, brass, nickel, alumina, mica, alumina coated with titanium oxide or iron oxide, mica coated with titanium oxide or iron oxide, glass flake, holographic pigment, and the like, and any combination thereof can be given. The above aluminum pigment includes non-floating aluminum as well as floating aluminum.

[0370] The coloring pigment is preferably mixed in the thermosetting resin composition in a state of being dispersed with a pigment dispersing resin. The amount of the coloring pigment can vary depending on the kind of the pigment, and the like, and is generally preferably in a range of about 0.1 to about 300 parts by mass, and more preferably about 1 to about 150 parts by mass, with respect to 100 parts by mass of the solid content of the resin component contained in the pigment dispersing resin.

[0371] The above thermosetting paint can further contain, as desired, a coating additive such as an organic solvent, a thickening agent, a UV absorber, a light stabilizer, a defoaming agent, a plasticizer, a surface conditioning agent, an anti-settling agent, a dispersant, an anti-blooming agent, a rheology control agent, a leveling agent, a base material wetting agent, a slip agent, and the like.

[0372] As the above-mentioned thickening agent, for example, inorganic thickening agents such as silicates, metal silicates, montmorillonite, colloidal alumina, polyacrylic acid-based thickening agents such as copolymers of (meth)acrylic acid and (meth)acrylate, sodium polyacrylate, associative thickening agents (the associative thickening agent has a hydrophilic portion and a hydrophobic portion in one molecule, and in an aqueous medium, the above-mentioned hydrophobic portion is adsorbed on the surface of pigments or emulsion particles in a paint, and the above-mentioned hydrophobic portions show thickening action by association or the like), cellulose derivative-based thickening agents such as carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, protein-based thickening agents such as casein, sodium caseinate, ammonium caseinate, alginic acid-based thickening agents such as sodium alginate, polyvinyl-based thickening agents such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl benzyl ether copolymer, polyether-based thickening agents such as polyether polyol, polyether dialkyl ester, polyether dialkyl ether, polyether epoxy modifier, maleic anhydride copolymer-based thickening agents such as partial ester of vinyl methyl ether-maleic anhydride copolymer, polyamide-based thickening agents such as polyamide amine salt, and the like, and any combination thereof can be mentioned.

[0373] The above-mentioned polyacrylic acid-based thickening agent is commercially available, and for example, "ACRYSOL LASE-60", "ACRYSOL TT-615", "ACRYSOL RM-5" (trade names), "SN-THICKENER 613", "SN-THICKENER 618", "SN-THICKENER 630", "SN-THICKENER 634", "SN-THICKENER 636" (trade names) manufactured by Rohm and Haas Co., Ltd., SAN NOPCO Co., Ltd., and the like can be mentioned.

[0374] In addition, the above-mentioned associative thickening agent is commercially available, and for example, "UH-420", "UH-450", "UH-462", "UH-472", "UH-540", "UH-752", "UH-756VF", "UH-814N" (trade names) manufactured by ADEKA Co., Ltd., "ACRYSOL RM-8W", "ACRYSOL RM-825", "ACRYSOL RM-2020NPR", "ACRYSOL RM-12W", "ACRYSOL SCT-275" (trade names) manufactured by Rohm and Haas Co., Ltd., "SN-THICKENER 612", "SN-THICKENER 621N", "SN-THICKENER 625N", "SN-THICKENER 627N", "SN-THICKENER 660T" (trade names) manufactured by SAN NOPCO Co., Ltd., and the like can be mentioned.

[0375] As the pigment dispersing resin described above, an acrylic pigment dispersing resin is preferably used. More specifically, for example, an acrylic resin obtained by polymerizing a polymerizable unsaturated monomer using a polymerization initiator in the presence of a hydrophilic organic solvent can be mentioned.

[0376] As the polymerizable unsaturated monomer described above, the compounds exemplified in the synthesis of the resin described above can be used in combination as appropriate.

[0377] The pigment dispersing resin described above is preferably a resin that can be dissolved or dispersed in water, and specifically has a hydroxyl value of preferably 10 to 100 mgKOH / g, more preferably 20 to 70 mgKOH / g, and an acid value of preferably 10 to 80 mgKOH / g, more preferably 20 to 60 mgKOH / g.

[0378] As the hydrophilic organic solvent used in the polymerization described above, for example, alcohol-based organic solvents such as methanol, ethanol, isopropanol, n-butanol, isobutanol, and the like; ether-based organic solvents such as dioxane, tetrahydrofuran, and the like; glycol ether-based organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-tert-butyl ether, and the like; diethylene glycol ether-based organic solvents such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-isopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-isobutyl ether, diethylene glycol mono-tert-butyl ether, and the like; propylene glycol ether-based organic solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, and the like; dipropylene glycol ether-based organic solvents such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-isopropyl ether, and the like; ester-based organic solvents such as ethyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, and the like; and the like, and combinations thereof can be mentioned.

[0379] In the thermosetting resin composition of the present application, the pigment dispersing resin is preferably contained at 5 to 70% by mass, and more preferably 7 to 61% by mass, based on the total of the solid content mass of the resin and the pigment dispersing resin described above. The above range is preferred from the viewpoints of storage stability of the thermosetting resin composition, and finishability, water resistance, polishing property in coating (middle polishing property), and the like of a colored coating film formed using the colored coating composition of the present application.

[0380] As a coated object to which the thermosetting resin composition of the present application can be applied, there are no particular limitations, and various examples such as an outer panel portion of a car body of a passenger car, a truck, a motorcycle, a bus, and the like; an automobile part; a coating agent for a home electric appliance such as a mobile phone, an audio device, and the like; a building material; furniture; an adhesive; a film; and glass can be given. Further, a pre-coated metal in which a coating film is formed by high-temperature short-time curing, and coating on a metal can can also be given. In addition, use in an electrodeposition paint, an adhesive, a particle board, and the like can also be given.

[0381] The thermosetting resin composition of the present application can also be used in the formation of a multilayer coating film. In a multilayer coating film, the thermosetting resin composition of the present application can be appropriately used in the formation of a multilayer coating film based on a wet-on-wet method.

[0382] The wet-on-wet method refers to a method in which, after a first coating film layer is formed, a second coating film layer is directly coated in a state in which the first coating film layer is only dried without being cured, and the plurality of coating film layers are simultaneously heated and cured. A coating film layer of three or more layers can also be formed by such a method.

[0383] In such a formation of a multilayer coating film based on a wet-on-wet method, transfer of coating film components can occur between the layers. Therefore, components contained in a layer can be dissolved into another layer, and this can adversely affect the curability. The thermosetting resin composition of the present application has good reactivity, and is not easily affected by other components, and thus can be appropriately used in the formation of a multilayer coating film based on a wet-on-wet method.

[0384] As a general method of wet-on-wet coating, a method in which an aqueous base coating material is used as a first layer, and a solvent-based clear coating material is used as a second layer can be given. The thermosetting resin composition of the present application can be used in both the first layer and the second layer, and among these, the thermosetting resin composition of the present application can be used in only one layer.

[0385] As described above, the thermosetting resin composition of the present application can achieve appropriate properties when made into an aqueous coating material. In addition, as described above, even in the case in which other coating film layer components are mixed, good curability can be achieved.

[0386] Therefore, even in the case in which the thermosetting resin composition of the present application is used in a second layer solvent-based clear coating material, a problem in which the curability is reduced due to components from a first layer aqueous base coating material is not easily caused, and this is preferable from this aspect.

[0387] The above-described aqueous thermosetting resin composition can also be used as an electrodeposition coating material composition. As an electrodeposition coating material, a cationic electrodeposition coating material and an anionic electrodeposition coating material can be given, and either of these can be used.

[0388] The aforementioned coated object may be a surface treated such as phosphate treatment, chromate treatment, or composite oxide treatment on the metal surface of the aforementioned metal material and the metal body formed therefrom, or it may be a coated object with a coating film.

[0389] Examples of the coated objects described above include: objects on which a substrate is surface-treated as desired and a primer coating is formed. In particular, a vehicle body with a primer coating formed using an electrodeposited coating is preferred, and a vehicle body with a primer coating formed using a cationic electrodeposited coating is more preferred.

[0390] The object to be coated may be an object on which surface treatment and undercoating have been performed as desired on the plastic surface of the aforementioned plastic material or automotive parts molded from the aforementioned plastic material. Alternatively, it may be an object composed of a combination of the aforementioned plastic material and the aforementioned metal material.

[0391] There are no particular limitations on the coating method for the above-mentioned thermosetting resin composition. Examples include air spraying, airless spraying, spin atomization coating, and curtain coating, with air spraying and spin atomization coating being preferred. During coating, static electricity can be applied as desired. Using the above coating method, a wet coating film can be formed from the above-mentioned water-based coating composition.

[0392] The aforementioned wet coating film can be cured by heating. This curing can be carried out using known heating methods, such as hot air furnaces, electric furnaces, infrared induction heating furnaces, and other drying ovens. The aforementioned wet coating film can be cured by heating at a temperature preferably in the range of about 80 to about 180°C, more preferably about 100 to about 170°C, and even more preferably about 120 to about 160°C, for a period of about 10 to about 60 minutes, more preferably about 15 to about 40 minutes. Furthermore, it can also withstand low-temperature curing at 80 to 140°C, which is preferable from this perspective.

[0393] The thermosetting resin composition of the present invention can also be used in a wet-on-wet method for forming a multilayer coating. In this case, methods such as applying a coating made of the thermosetting resin composition of the present invention, applying another coating composition on top of it without curing, and simultaneously firing these two coating layers to form a multilayer coating. Furthermore, in such a coating method, as a multilayer coating with two or more layers, at least one layer can be formed from the thermosetting resin composition of the present invention.

[0394] When using the thermosetting resin composition of the present invention to form such a multilayer coating, the coating used can be aqueous or solvent-based. Furthermore, the curing system can be the transesterification-based curing system described above, or other curing systems such as melamine curing or isocyanate curing.

[0395] Note that, in the case where the thermosetting resin composition of the present application is used in the field of paints, it is necessary to have sufficient curing properties such as smoothness, water resistance / acidity resistance, and the like.

[0396] On the other hand, in the case where it is used in the field of adhesives, adhesives, and the like, it is not necessary to have as high a curing property as required in paints. The thermosetting resin composition of the present application can reach a level that can be used as a paint, but even a composition that does not reach such a level can sometimes be used in the field of adhesives, adhesives, and the like.

[0397] The thermosetting resin composition of the present application can also be made into a normal dry type thermosetting resin composition. That is, it can also be used as a thermosetting resin composition that, after painting, is not cured based on heating, but is left to stand at normal temperature, thereby being cured. This is not simply cured by drying, but refers to three-dimensional crosslinking at normal temperature. The thermosetting composition of the present application is particularly excellent in curing properties at low temperatures, and is thus also suitable for such use

[0398] The present application also relates to a cured film characterized by being formed by three-dimensionally crosslinking the above thermosetting resin composition.

[0399] Such a cured film has sufficient properties that can be used as a paint, an adhesive.

[0400] The above cured film also includes a cured film formed by the above multilayer coating film formation method.

[0401] Examples

[0402] Hereinafter, the present application will be described in more detail based on examples. Note that the present application is not limited to the following examples. Note that, in the present specification, parts refer to parts by weight.

[0403] Synthesis Example 1

[0404] A monomer mixture solution was prepared from 35 parts of n-butyl methacrylate (product of Gohsenol Co., Ltd.: LIGHT ESTER NB), 30 parts of methoxycarbonylmethyl methacrylate (product of Gohsenol: LIGHT BOM-102), 25 parts of 4-hydroxybutyl acrylate, and 10 parts of styrene, and 5 parts of AIBN as an initiator was dissolved in 20 parts of an aromatic hydrocarbon (T-SOL 100) to prepare an initiator solution. An aromatic hydrocarbon (T-SOL 100) was added to a stirrable flask, and the monomer solution and the initiator solution were added dropwise while sealing with nitrogen. The polymerization temperature at this time was set to 100°C. The dropwise addition was performed for 2 hours, and further aging was performed at 100°C for 4 hours to obtain a polymer solution A having a weight average molecular weight of 9400.

[0405] Synthesis Example 2

[0406] A monomer mixture solution was prepared from 60 parts of n-butyl methacrylate (product of Kokai Co., Ltd.: LIGHT ESTER NB), 30 parts of 4-hydroxybutyl acrylate, and 10 parts of styrene. An initiator solution was prepared by dissolving 5 parts of AIBN as an initiator in 20 parts of an aromatic hydrocarbon (T-SOL 100). An aromatic hydrocarbon (T-SOL 100) was added to a stirrable flask, and the monomer solution and the initiator solution were added dropwise while sealing with nitrogen. The polymerization temperature at this time was set to 100°C. The dropwise addition was performed for 2 hours, and further aging was performed at 100°C for 4 hours, thereby obtaining a polymer solution B having a weight average molecular weight of 11200.

[0407] Synthesis Example 3

[0408] A monomer mixture solution was prepared from 30 parts of n-butyl methacrylate (product of Kokai Co., Ltd.: LIGHT ESTER NB), 30 parts of methoxycarbonylmethyl methacrylate (product of Kokai Co., Ltd.: LIGHT BO M-102), 25 parts of 4-hydroxybutyl acrylate, 10 parts of styrene, and 5 parts of methacrylic acid. An initiator solution was prepared by dissolving 3 parts of AIBN as an initiator in 20 parts of propylene glycol monomethyl ether (PGME). PGME was added to a stirrable flask, and the monomer solution and the initiator solution were added dropwise while sealing with nitrogen. The polymerization temperature at this time was set to 100°C. The dropwise addition was performed for 2 hours, and further aging was performed at 100°C for 4 hours, thereby obtaining a polymer solution C having a weight average molecular weight of 18400. The polymer solution can be arbitrarily water-based by neutralization.

[0409] Synthesis Example 4

[0410] A monomer mixture solution was prepared from 60 parts of n-butyl methacrylate (product of Kokai Co., Ltd.: LIGHT ESTER NB), 25 parts of 4-hydroxybutyl acrylate, 10 parts of styrene, and 5 parts of methacrylic acid. An initiator solution was prepared by dissolving 3 parts of AIBN as an initiator in 20 parts of propylene glycol monomethyl ether (PGME). PGME was added to a stirrable flask, and the monomer solution and the initiator solution were added dropwise while sealing with nitrogen. The polymerization temperature at this time was set to 100°C. The dropwise addition was performed for 2 hours, and further aging was performed at 100°C for 4 hours, thereby obtaining a polymer solution D having a weight average molecular weight of 9300. The polymer solution can be arbitrarily water-based by neutralization.

[0411] Synthesis Example 5

[0412] A monomer mixture solution was prepared by mixing n-butyl methacrylate (product of Kokyo Alcohol Co., Ltd.: LIGHT ESTER NB) 10 parts, 4-hydroxybutyl acrylate 25 parts, styrene 5 parts, N-(2-hydroxyethyl) acrylamide 20 parts, and glycidyl methacrylate (product of Kokyo Alcohol Co., Ltd.: LIGHT ESTER G) 40 parts. A solution of 2-ethylhexyl peroxy-2- ethylhexanoate (product of NOF Corporation: Perocta O) 5 parts as an initiator was dissolved in PGME. A butanediol 100 parts was charged in a stirring flask, and the monomer solution and the initiator solution were added dropwise while being sealed with nitrogen. The polymerization temperature at this time was set to 100°C. The dropwise addition was performed for 2 hours, and further aging was performed at 100°C for 4 hours to obtain a polymer solution E having a weight average molecular weight of 12,300.

[0413] Synthesis Example 6

[0414] A monomer mixture solution was prepared by mixing n-butyl methacrylate (product of Kokyo Alcohol Co., Ltd.: LIGHT ESTER NB) 15 parts, methoxycarbonylmethyl methacrylate (product of Kokyo Alcohol Co., Ltd.: LIGHT BO M-102) 35 parts, 4-hydroxybutyl acrylate 15 parts, styrene 15 parts, and glycidyl methacrylate (product of Kokyo Alcohol Co., Ltd.: LIGHT ESTER G) 20 parts. A monomer emulsion was prepared by emulsifying the monomer mixture solution using a homogenizer for 1 hour at room temperature after adding ADEKA REASOAP SR-3025, 12 parts (product of ADEKA Co., Ltd.), ion exchange water 70 parts. A stirring flask was charged with ion exchange water 115 parts, and the monomer emulsion and an initiator were added dropwise while being sealed with nitrogen, and polymerization was performed at the same time. Ammonium persulfate 0.3 parts as an initiator was added. The polymerization temperature at this time was 75°C. The dropwise addition was performed for 3 hours, and further aging was performed at 75°C for 5 hours to obtain a polymer F.

[0415] In the following examples and comparative examples, a thermosetting resin composition was prepared by mixing the composition obtained in the synthesis example in the following table, and applying it on a PET film using an applicator, and sintering it for 30 minutes at each sintering temperature. The film thickness was 30 to 50 μm (dry). Using the obtained coated film, physical property evaluation was performed.

[0416] [Table 1]

[0417] Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 Example 4 Example 5 Polymer A 200 160 Polymer B Polymer C 200 160 160 150 100 Polymer D 160 Polymer E 40 40 40 40 Polymer F 50 100 Water 50 20 DMEA 5 5 5 5 5 5 MI 2 2 2 2 2 2 2 2 Zn(acac)2 3 3 3 3 3 3 3 3 Sintering temperature 80℃ 80℃ 80℃ 70℃ 80℃ 80℃ 80℃ 80℃ Gel rate ◎ × × ◎ ◎ ◎ ◎ ◎ Xy friction ○ △ × ○ ○ ○ ◎ ○

[0418] DMEA: dimethyl ethanol amine, MI: 1-methyl imidazole

[0419] [Table 2]

[0420] Example 6 Example 7 Example 8 Polymer C 180 180 180 Epolight 400E 10 Epolight 80MF 10 CELLOXIDE 2021 10 DMEA 5 5 5 MI 2 2 2 Zn(acac)2 3 3 3 Sintering temperature 80℃ 80℃ 80℃ Gel rate ◎ ◎ ◎ Xy friction ◎ ◎ ○

[0421] Epolight 400E: polyethylene glycol diglycidyl ether product of Showa Denko K.K.

[0422] Epolight 80MF: glycerol diglycidyl ether product of Showa Denko K.K.

[0423] CELLOXIDE 2021: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate product of Daicel Corporation Synthesis Example 7

[0424] In a four-necked flask which can be refluxed, trimellitic anhydride 140 parts, toluene 310 parts, ion-exchanged water 14 parts were stirred at 80°C for 1 hour to synthesize trimellitic acid. Then potassium hydroxide 115 parts was added to synthesize trimellitic acid tripotassium salt. Next, triethylamine 232 parts, methyl chloroacetate 244 parts were added and reacted at 90°C for 10 hours or more. After the reaction, water 210 parts was added to remove the precipitated potassium chloride. The organic layer was washed with water 200 parts three times, and then concentrated under reduced pressure to obtain ester compound A.

[0425] Synthesis Example 8

[0426] In a four-necked flask which can be refluxed, methyl chloroacetate 60 parts, trisodium citrate 40 parts, triethylamine 1.5 parts were stirred at 100°C for 5 hours. After the reaction, toluene 250 parts, water 150 parts were added and washed with water. The organic layer was washed with water 150 parts three times, and then concentrated under reduced pressure to obtain ester compound B.

[0427] (Examples 9 to 11 and Comparative Examples 4 to 7)

[0428] In the following examples, the composition obtained in the synthesis example was mixed as in the following table to prepare a thermosetting resin composition, which was coated on a PET film using an applicator, and sintered at each sintering temperature for 30 minutes. The film thickness was 30 to 50 μm (dry). Using the obtained coating film, physical property evaluation was performed.

[0429] [Table 3]

[0430] Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Example 9 Example 10 Example 11 Polymer B 140 140 Polymer C 40 Polymer D 140 140 120 120 Polymer E 30 30 Polymer F 240 Ester compound A 30 30 30 Ester compound B 30 30 30 Water DMEA 5 5 5 5 2 MI 2 2 2 2 2 2 5 Zn(acac)2 3 3 3 3 3 3 3 Sintering temperature 100℃ 100℃ 100℃ 100℃ 100℃ 100℃ 100℃ Gel rate ◎ ◎ △ △ ◎ ◎ ◎ Xy friction ◎ ◎ × × ◎ ◎ ○

[0431] DMEA: dimethyl ethanol amine neutralization MI: 1-methyl imidazole

[0432] Note that in this example, the weight average molecular weight and the dispersity were values measured by the area ratio of gel permeation chromatography (GPC) and polystyrene conversion molecular weight. The column used was GPC KF-804L, and the solvent used was tetrahydrofuran. The gel ratio and xylene rub were measured based on the following standards.

[0433] (Gel ratio)

[0434] As for the gel fraction, the coating film obtained in the examples was dissolved in acetone reflux for 30 minutes using a Soxhlet extractor, and was measured as the residual weight % of the coating film.

[0435] A gel fraction of 0 to 40% is not practical, and is marked as X.

[0436] A gel fraction of 40 to 60% is confirmed to be somewhat cured, and is marked as Δ.

[0437] A gel fraction of 60 to 80% is practical, and is marked as O.

[0438] A gel fraction of 80 to 100% is excellent in performance, and is marked as.

[0439] (Xylene Rubbing)

[0440] The coating film obtained in the comparative example and the examples was rubbed 10 times with medical gauze impregnated with xylene. After drying the xylene, the surface state was observed visually.

[0441] : No change at all

[0442] O: Slightly damaged

[0443] Δ: Slightly dissolved

[0444] X: Surface whitened, dissolved

[0445] From the results of the above table, it is known that the thermosetting resin composition of the present application is excellent in low-temperature curing performance.

[0446] Synthesis Example 9

[0447] A monomer mixture solution was prepared from 35 parts of n-butyl methacrylate (product of Gohsenol Co., Ltd.: Light Ester NB), 15 parts of methoxy carbonylmethyl methacrylate (product of Gohsenol Co., Ltd.: LIGHT BOM-102), 25 parts of 2-hydroxyethyl methacrylate (product of Gohsenol Co., Ltd.: Light Ester HO-250), 5 parts of styrene, and 20 parts of glycidyl methacrylate (product of Gohsenol Co., Ltd.: Light Ester G), and an initiator solution was prepared by dissolving 5 parts of 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate (Perocta O of NOF Corporation) as an initiator in 20 parts of propylene glycol monomethyl ether (PGME). In a stirrable flask, 80 parts of PGME was added, and the monomer solution and the initiator solution were added dropwise while sealing with nitrogen. The polymerization temperature at this time was set to 100°C. The dropwise addition was performed for 2 hours, and further, aging was performed at 100°C for 4 hours, to obtain a polymer solution G having a weight average molecular weight of 13,000.

[0448] Synthesis Example 10

[0449] Into a four-necked flask were put 180 parts of succinic anhydride and 173 parts of methanol, and the succinic anhydride was dissolved at 60 to 70°C. The disappearance of the succinic anhydride peak was confirmed by NMR, and the methanol was removed under reduced pressure to obtain monomethyl succinate.

[0450] Into the flask were added 190 parts of monomethyl succinate, 205 parts of glycidyl methacrylate, 0.5 parts of triethylbenzylammonium chloride, and a polymerization inhibitor, and the mixture was reacted at 90°C for 10 hours or more to obtain monomer 1.

[0451] A monomer solution was prepared by mixing 35 parts of n-butyl methacrylate (product of Kyoeisha Chemical Co., Ltd.: LIGHT ESTER NB), 115 parts of monomer 1, 25 parts of 2-hydroxyethyl methacrylate (product of Kyoeisha Chemical Co., Ltd.: LIGHT ESTER HO-250), 5 parts of styrene, and 20 parts of glycidyl methacrylate (product of Kyoeisha Chemical Co., Ltd.: LIGHT ESTER G). Next, 5 parts of Perocta O as an initiator was dissolved in 20 parts of propylene glycol monomethyl ether (PGME) to prepare an initiator solution. In a stirrable flask were put 80 parts of PGME, and the monomer solution and the initiator solution were added dropwise while sealing with nitrogen. The polymerization temperature at this time was set to 100°C. The dropwise addition was performed for 2 hours, and further, the temperature was maintained at 100°C for 4 hours to obtain a polymer solution H having a weight average molecular weight of 22,000.

[0452] (Examples 12 to 16)

[0453] A thermosetting resin composition was prepared by mixing the composition obtained in the synthesis example as shown in Table 4 below, and was applied to a PET film using an applicator, and was sintered at each sintering temperature for 30 minutes. The film thickness was 30 to 50 μm (dry). Using the obtained coated film, physical property evaluation was performed.

[0454] [Table 4]

[0455] Example 12 Example 13 Example 14 Example 15 Example 16 Polymer A 180 Polymer C 180 180 Polymer G 200 Polymer H 200 Epolight 100MF 10 10 10 DBU 6 6 6 6 DMAP 6 Sintering 80°C x 30 minutes 80°C x 30 minutes 80°C x 30 minutes 80°C x 30 minutes 80°C x 30 minutes Gel rate ◎ ◎ ◎ ◎ ◎ Xy friction 〇 ◎ 〇 ◎ 〇

[0456] Epolight 100MF: product of Kyoeisha Chemical, trimethylolpropane triglycidyl ether

[0457] DBU: diazabicycloundecene

[0458] DMAP: dimethylaminopyridine

[0459] As is clear from the results of Table 4 above, the thermosetting resin composition of the present application has good low-temperature curing properties even when an alkaline catalyst is used.

[0460] Synthesis Example 11

[0461] A monomer mixture solution was prepared by mixing n-butyl methacrylate (Kohjin Co., Ltd. product: LIGHT ESTER NB) 10 parts, methoxy carbonylmethyl methacrylate (Kohjin Co., Ltd. product: LIGHT BO M-102) 25 parts, 2-hydroxyethyl methacrylate 25 parts, styrene 5 parts, and glycidyl methacrylate (Kohjin Co., Ltd. product: LIGHT ESTER G) 35 parts. A solution of 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate (Nippon Oil & Fats Co., Ltd. Perocta O) 5 parts as an initiator was dissolved in PGME. A 100 parts of PGME was added to a stirrable flask, and the monomer solution and the initiator solution were added dropwise while being sealed with nitrogen. The polymerization temperature at this time was set to 100°C. The dropwise addition was performed for 2 hours, and further, the curing was performed at 100°C for 4 hours to obtain a polymer solution I having a weight average molecular weight of 18000.

[0462] (Example 17)

[0463] A thermosetting resin composition was prepared by adding 1-methylimidazole 9 parts to 200 parts of the polymer solution I. The composition was coated on a PET film using an applicator, and curing was performed at 23°C for 1 week. The film thickness was 30 to 50 μm (dry). Using the obtained coated film, physical property evaluation was performed. For the obtained coated film, the gel fraction was ◎, and the Xy friction was ◎, that is, it was able to be cured at 23°C, and thus it was able to be used as a thermosetting resin composition of the normal dry type.

[0464] Industrial applicability

[0465] The thermosetting resin composition of the present application can be used in a coating composition, an adhesive composition, and other publicly known arbitrary uses of a thermosetting resin composition.

Claims

1. A thermosetting resin composition, characterized by comprising: contains: a resin component (A) containing an ester group (a), an epoxy group (b), and a hydroxyl group (c), the ester group being any one of (a-1) to (a-5) below, and an ester exchange catalyst (B), (a-1) a compound represented by the following general formula (1) [Chemical Formula 1] n1：1～10 in the formula, R4, R5, R6 are the same or different, and are hydrogen, an alkyl group, a carboxyl group, an alkyl ester group, or a structure represented by R7-[COOR8]n1 below; R7 is an aliphatic, alicyclic, or aromatic alkylene group with or without a side chain, the number of atoms in the main chain being 50 or less, and the main chain having or not having 1 or 2 or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and a urethane group; R8 is an alkyl group with 50 or less carbon atoms; in the compound represented by the above general formula (1), the R7-[COOR8]n1 group can be a lactone structure of the following general formula (1-1); [Chemical Formula 2] (a-2) a polymer having the structure of the above (a-1) as a structural unit (a-3) a compound having the structure represented by the following general formula (2); [Chemical Formula 3] n＝0～20 R1 is an alkyl group with 50 or less carbon atoms; R3 is hydrogen or an alkyl group with 10 or less carbon atoms; (a-4) a compound having the structure represented by the following general formula (3) or (4) [Chemical Formula 4] [Chemical Formula 5] in either of the above general formula (3) and general formula (4), R1 is an alkyl group with 50 or less carbon atoms; R2 is an alkylene group with 50 or less carbon atoms, which may or may not contain an oxygen atom and a nitrogen atom as a part thereof; (a-5) the following general formula (5) and / or general formula (6) [Chemical Formula 6] R1 represents a primary alkyl group or a secondary alkyl group; X represents a hydrocarbon group with 5 or less carbon atoms or an -OR1 group.

2. The thermosetting resin composition according to claim 1, wherein, The resin component (A) further contains an unsaturated functional group.

3. The thermosetting resin composition according to claim 1 or 2, wherein, The resin component (A) further has a carboxyl group.

4. The thermosetting resin composition according to claim 1 or 2, wherein, The resin component (A) is an aqueous composition.

5. The thermosetting resin composition according to claim 4, wherein, The resin component (A) is water-based by neutralizing a carboxyl group.

6. A cured film characterized by, which is obtained by curing the thermosetting resin composition according to claim 1 or 2.

Images