Surface modifiers and thermosetting resin compositions

Abstract

To provide a surface conditioner which can suitably exhibit an effect by reacted with a resin component in various thermosetting resin compositions, and a coating composition blended with the same.SOLUTION: A surface conditioner contains a structural unit (A) derived from at least one monomer selected from the group consisting of (A-1) (meth)acrylate having an alkyl group having 1 to 24 carbon atoms, and (A-2) alkyl vinyl ester having an alkyl group having 1 to 24 carbon atoms, and a structural unit (B) derived from a monomer represented by the following general formula (4) as essential components, and has a solubility parameter of 7.6-12.0, and a weight average molecular weight of 3,000-500,000.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a surface modifier and a thermosetting resin composition. [Background technology]

[0002] In recent years, the applicant has been studying thermosetting resin compositions that use transesterification as a curing reaction (Patent Documents 1-3). In these studies, the applicant has conducted many investigations into compounds that readily undergo transesterification.

[0003] On the other hand, Patent Document 4 describes a paint additive that is a polymer obtained using monomers having functional groups that react with various paint compositions. Such a paint additive reacts with the base resin of the paint composition and does not reduce properties such as water resistance of the cured film of the paint composition. The use of transesterification reactions in such paint additives is not described.

[0004] Patent Document 5 describes the incorporation of known general additives into a thermosetting resin composition that uses an ester curing reaction as the curing reaction. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Patent No. 6398026 [Patent Document 2] International Publication No. 2019 / 069783 [Patent Document 3] International Publication No. 2019 / 139069 [Patent Document 4] Japanese Patent Publication No. 2007-320993 [Patent Document 5] Japanese Patent Publication No. 2020-132710 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] In view of the above, the present invention aims to provide a surface modifier that can suitably exhibit its effects by reacting with resin components in various thermosetting resin compositions, and a paint composition containing the same. [Means for solving the problem]

[0007] The present invention The following general formula (1) [ka] (In the formula, R1 represents an alkyl group having 1 to 24 carbon atoms.) (R2 represents a hydrogen or methyl group.) A constituent unit (A) derived from at least one monomer selected from the group consisting of (meth)acrylic acid ester (A-1) represented by and alkyl vinyl ether (A-2) having 1 to 24 carbon atoms in the alkyl group, and the following general formula (4) [ka] n1:1~10 (In the formula, R4, R5, and R6 are the same or different hydrogen, alkyl group, carboxyl group, alkyl ester group, or structure represented by R7-[COOR8]n1 below.) R7 has 50 or fewer atoms in its main chain, and contains ester groups, ether groups, amide groups, An aliphatic, alicyclic, or aromatic alkylene group having one or more functional groups selected from the group consisting of urethanes, and which may have a side chain. R8 is an alkyl group with 50 or fewer carbon atoms. The compound represented by the above general formula (4) may also have a lactone structure in which the R7-[COOR8]n1 group is represented by the following general formula (4-1). [ka] (Rx is a hydrocarbon group having 2 to 10 carbon atoms, which may have a branched chain.) The constituent unit (B) derived from the monomer represented by is an essential component, The solubility parameter is 7.6 to 12.0. This surface modifier is characterized by having a weight-average molecular weight of 3,000 to 500,000.

[0008] The present invention relates to a resin or resin composition (X) having a hydroxyl group. The above-mentioned surface modifier and Transesterification catalyst (Z) It is also a thermosetting resin composition characterized by containing [a specific substance].

[0009] In the above thermosetting resin composition, it is preferable that the solubility parameter of the surface modifier is smaller for the resin or resin composition (X) and the difference between them is 3.0 or less. [Effects of the Invention]

[0010] The surface modifier of the present invention, when used in a thermosetting resin composition, reacts with the resin components of the thermosetting resin composition to produce a good effect, and this effect can be maintained over a long period of time. [Modes for carrying out the invention]

[0011] The surface modifier of the present invention has ester groups that undergo a transesterification reaction. By using this as a surface modifier, the surface condition when a coating film is formed using a thermosetting resin composition can be improved. Furthermore, these ester groups react with hydroxyl groups in the paint, allowing the additive to exhibit a desirable effect.

[0012] The surface modifier of the present invention is used as a surface modifier. Therefore, when a thermosetting resin composition is heated and cured, it is preferable that the surface modifier separates from the base resin and is unevenly distributed on the surface. In order to obtain a resin with such properties, the solubility parameter is 7.6 to 12.0. By using such solubility parameters, the surface modifier can exhibit suitable functionality.

[0013] The above solubility parameter range is more preferably 8.0 to 12.0 for leveling agents and more preferably 7.6 to 8.0 for defoaming agents. In this invention, the solubility parameter is calculated using the known method for calculating the SP value by the n-hexane tolerance method. Two resin solids dissolved in tetrahydrofuran are prepared, and deionized water is added dropwise to one of the resin solutions, while n-hexane is added dropwise to the other. The solubility parameter is then calculated from the volume of deionized water and n-hexane added at which the resin solution becomes cloudy.

[0014] The constituent units (A) and (B) are described in detail below. (Constituent unit (A)) The constituent unit (A) is given by the following general formula (1)

[0015] [ka] (In the formula, R1 represents an alkyl group having 1 to 24 carbon atoms.) (R2 represents a hydrogen or methyl group.) The constituent unit is derived from at least one monomer selected from the group consisting of (meth)acrylic acid esters (A-1) and alkyl vinyl ethers (A-2) represented by [formula].

[0016] In this invention, in order to achieve this objective, at least one monomer selected from the group consisting of (A-1) and (A-2) above is essential.

[0017] The monomer represented by (A-1) above is a (meth)acrylic acid ester represented by the following general formula (1). Examples of such monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate. Examples include acrylates, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, tricyclodecanyl (meth)acrylate, etc.

[0018] The alkyl vinyl ether (A-2) described above is not particularly limited and is an ether compound of a vinyl group and an alkyl group, wherein the alkyl group is an aliphatic, alicyclic, or aromatic short hydrogen having 1 to 24 carbon atoms. Examples of such monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, and tetradioxide. Various alkyl vinyl ethers or substituted alkyl vinyl ethers, such as silvinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, chloromethyl vinyl ether, chloroethyl vinyl ether, benzyl vinyl ether, or phenylethyl vinyl ether; Examples include various cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether, or methylcyclohexyl vinyl ether.

[0019] (Meth)acrylic acid ester (A-1) and alkyl vinyl ether (A-2) are components necessary for the surface modifier described above to function, so it is preferable to select a structure appropriate to the purpose. In particular, it is preferable to adjust the components and composition used so that they satisfy the solubility parameters described above.

[0020] As surface modifiers, leveling agents used to improve coating defects on surfaces and defoaming agents used to reduce the inclusion of foam during the manufacturing and painting processes of paints, particularly preventing the inclusion of very small bubbles, are commonly known. When used as such leveling agents, particularly preferred (meth)acrylic acid esters (A-1) include ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. A combination of several of these may also be used.

[0021] When the surface modifier of the present invention is used as an antifoaming agent, the monomer represented by (A-1) above is preferably such that R1 has 4 to 24 carbon atoms, such as lauryl (meth)acrylate or stearyl (meth)acrylate. The lower limit of the carbon number is more preferably 12. Being such a long-chain aliphatic hydrocarbon allows for good antifoaming performance.

[0022] (Constituent unit (B)) In the surface modifier of the present invention, the constituent unit (B) is derived from a monomer having an alkyl ester group that facilitates transesterification reactions. The constituent unit (B) is a compound having the structure represented by the following general formula (4). [ka] n1:1~10 (In the formula, R4, R5, and R6 are the same or different hydrogen, alkyl group, carboxyl group, alkyl ester group, or structure represented by R7-[COOR8]n1 below.) R7 is an aliphatic, alicyclic, or aromatic alkylene group having 50 or fewer atoms in its main chain, which may have one or more functional groups selected from the group consisting of ester groups, ether groups, amide groups, and urethanes in its main chain, and which may have a side chain. R8 is an alkyl group with 50 or fewer carbon atoms. The compound represented by the above general formula (4) may also have a lactone structure in which the R7-[COOR8]n1 group is represented by the following general formula (4-1).

[0023] [ka] (Rx is a hydrocarbon group having 2 to 10 carbon atoms, which may have a branched chain.)

[0024] Polymers obtained using the monomer represented by the above general formula (4) can exhibit particularly excellent transesterification reactivity. For this reason, it is particularly preferable to obtain a resin composition in which the curing start temperature is 130°C or lower and the gel fraction when cured under conditions of baking at 150°C for 30 minutes is 80% or more.

[0025] The monomer represented by the above general formula (4) is more preferably one in which R8 is a primary or secondary alkyl ester. The primary or secondary alkyl ester group derived from such a monomer readily reacts with hydroxyl groups, and for this reason the objectives of the present invention can be fully achieved.

[0026] Such compounds can be polymerized by polymerization reactions involving unsaturated bonds. When the polymer obtained in this way is used in a thermosetting resin composition cured by transesterification, the main chain formed based on the polymerization of unsaturated bonds and the alkyl ester groups are separated by linking groups. As a result, the alkyl ester groups can move relatively freely. This allows the alkyl ester groups and hydroxyl groups to approach each other more easily, and the inventors have found that this improves the reactivity of the transesterification reaction. This improved reactivity of the transesterification reaction enables shorter curing times and lower curing temperatures, thereby increasing the usefulness of thermosetting resin compositions obtained by transesterification.

[0027] The alkyl ester group is not particularly limited, and known ester groups such as methyl ester group, ethyl ester group, benzyl ester group, n-propyl ester group, isopropyl ester group, n-butyl ester group, isobutyl ester group, and sec-butyl ester group can be used. It is preferable that the alkyl group has 50 or fewer carbon atoms. Since the alkyl group is preferably generated as an alcohol during the transesterification reaction and volatilizes, it is more preferable that the alkyl group has 20 or fewer carbon atoms, and even more preferable that it has 10 or fewer carbon atoms. Furthermore, it is preferable that the boiling point of the alcohol volatilized during the curing reaction is 300°C or lower, and even more preferable that it is 200°C or lower.

[0028] The alkyl group in the alkyl ester group (i.e., R8 in the general formula (4) above) is an alkyl group having 50 or fewer carbon atoms, more preferably in the range of 1 to 20 carbon atoms, even more preferably in the range of 1 to 10 carbon atoms, and even more preferably in the range of 1 to 6 carbon atoms. Most preferably in the range of 1 to 4 carbon atoms. This range is preferable because it allows the curing reaction to proceed smoothly.

[0029] Furthermore, the present invention also includes cases where the alkyl ester group is a lactone group. Such lactone ester groups can also undergo the transesterification reaction of the present invention and can be used in the curing reaction. Such compounds have the chemical structure of (4-1) above.

[0030] More specifically, compounds represented by the above general formula (4) include those represented by the following general formula (5).

[0031] [ka] n2:1~10 (In the formula, R9 is H or a methyl group.) R 10 This is an alkylene group having 48 or fewer atoms in its main chain, which may contain an ester group, an ether group, and / or an amide group in its main chain, and which may have a side chain. R 11 (This refers to alkyl groups with 50 or fewer carbon atoms.) Examples of compounds represented by [formula] are shown. Such compounds are derivatives of (meth)acrylic acid and can be obtained by known synthesis methods using (meth)acrylic acid or its derivatives as raw materials.

[0032] The above R 10 The number of atoms in the main chain is more preferably 40 or less, even more preferably 30 or less, and even more preferably 20 or less. 10 The atoms that may be included in the main chain are not particularly limited, and may include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, etc., in addition to carbon atoms. More specifically, R 10 The main chain may contain, in addition to alkyl groups, ether groups, ester groups, amino groups, amide groups, thioether groups, sulfonic acid ester groups, thioester groups, siloxane groups, and the like.

[0033] More specifically, examples of structures represented by the above general formula (5) include compounds represented by the following general formula (12).

[0034] [Chemical formula] (In the formula, R 20 is an alkyl group having 1 to 50 carbon atoms. R 21 is an alkylene group having 44 or fewer atoms in the main chain, which may have an ester group, an ether group and / or an amide group in the main chain, and may have a side chain. R 22 is H or a methyl group. R 23 is an alkyl group having 50 or fewer carbon atoms. R 24 is H or a methyl group. n7 is 0 or 1. n8 is 1 or 2.)

[0035] The compound represented by the above general formula (12) is a compound synthesized by the reaction of a compound that generates an active anion such as a malonic ester or acetoacetic ester having an unsaturated bond in the molecule with an unsaturated compound having an alkyl ester group.

[0036] That is, malonic ester and acetoacetic ester have a methylene group sandwiched between carboxy carbons, and this methylene group is easily anionized and is widely known as a group that easily causes an anion reaction. By reacting a compound having an unsaturated bond in the alkyl group of such a malonic ester or acetoacetic ester (for example, an ester compound of malonic acid or acetoacetic acid and an unsaturated monomer having a hydroxyl group, which will be described in detail below as a "hydroxyl group-containing monomer") with an alkyl ester compound having an unsaturated group, a compound having both an unsaturated group and an alkyl ester group can be synthesized.

[0037] The production method of such a compound can be carried out according to the method described in International Publication No. 2019 / 139069 and the like.

[0038] The compound represented by the above general formula (4) may also be a compound having a functional group and an unsaturated group represented by the following general formula (31).

[0039] [ka]

[0040] n=0~20 R1 is an alkyl group with 50 or fewer carbon atoms. R3 is hydrogen or an alkyl group with 10 or fewer carbon atoms.

[0041] In other words, in a compound represented by general formula (4), the COOR8 group may have a structure as represented by the above general formula (31).

[0042] The ester group represented by the above general formula (31) exhibits high reactivity in transesterification reactions, although the reason for this is unknown. Therefore, by using an ester compound having this functional group as part or all of the resin component, a thermosetting resin composition with superior curing performance compared to conventional compositions can be obtained. Therefore, it can be suitably used as a resin to obtain a thermosetting resin composition that has a curing start temperature of 130°C or lower and satisfies a gel fraction of 80% or more when cured under the conditions of baking at 150°C for 30 minutes.

[0043] More specifically, such compounds can be exemplified by the compound represented by the following general formula (36). [ka] (In the formula, R1 is an alkyl group having 50 or fewer carbon atoms.) R2 is either a hydrogen atom or a methyl group. R3 is hydrogen or an alkyl group with 10 or fewer carbon atoms. n is between 0 and 20.

[0044] (Regarding the structure of general formula (31)) The structure of the above general formula (31) is based on an α-substituted carboxylic acid ester skeleton. In general formula (31), n ​​is between 0 and 20. The lower limit of n is more preferably 1. The upper limit of n is more preferably 5. Furthermore, the mixture may consist of multiple components with different values ​​of n in the general formula (31) described above. In this case, the mean value of n, nav, is preferably between 0 and 5. The lower limit of nav is more preferably 1. The upper limit of nav is more preferably 3. nav can be measured by NMR analysis. Furthermore, the value of n can also be measured by NMR analysis.

[0045] n may be 0, but a value greater than 0 indicates a more reactive thermosetting resin. It is preferable in that it allows for the acquisition of a composition. In other words, when n is 1 or greater, curing can be achieved at a lower temperature, thereby allowing the effects of the present invention to be exhibited more favorably.

[0046] In the above general formula (31), R1 can be any alkyl group having 50 or fewer carbon atoms, and may be primary, secondary, or tertiary.

[0047] The alkyl group in the alkyl ester group (i.e., R1 in the general formula above) is an alkyl group with 50 or fewer carbon atoms, more preferably in the range of 1 to 20 carbon atoms, even more preferably in the range of 1 to 10 carbon atoms, and even more preferably in the range of 1 to 6 carbon atoms. Most preferably in the range of 1 to 4 carbon atoms. This range is preferable because it allows the curing reaction to proceed smoothly.

[0048] Specifically, known ester groups such as methyl ester group, ethyl ester group, benzyl ester group, n-propyl ester group, isopropyl ester group, n-butyl ester group, isobutyl ester group, sec-butyl ester group, and t-butylalkyl group can be used as the alkyl ester group.

[0049] Compounds having the above-mentioned functional group (31) can be produced by known methods. Specifically, they can be produced by the method described in International Publication 2021 / 095202.

[0050] The compound represented by the above general formula (4) may also be a compound having a functional group represented by the following general formula (41) and / or a functional group represented by the following general formula (42), as well as an unsaturated group.

[0051] [ka]

[0052] [ka] (In both of the above general formulas (41) and (42), R1 is an alkyl group having 50 or fewer carbon atoms.) R2 is an alkylene group with 50 or fewer carbon atoms, which may contain oxygen and nitrogen atoms in part.

[0053] In other words, in a compound represented by general formula (4), the COOR8 group may have a structure as represented by general formula (41) and / or as represented by general formula (42). Therefore, it can be suitably used as a resin to obtain a thermosetting resin composition that has a curing start temperature of 130°C or lower and satisfies a gel fraction of 80% or more when cured under the conditions of baking at 150°C for 30 minutes.

[0054] The alkyl group in the alkyl ester group (i.e., R1 in the general formula above) is an alkyl group with 50 or fewer carbon atoms, more preferably in the range of 1 to 20 carbon atoms, even more preferably in the range of 1 to 10 carbon atoms, and even more preferably in the range of 1 to 6 carbon atoms. Most preferably in the range of 1 to 4 carbon atoms. This range is preferable because it allows the curing reaction to proceed smoothly.

[0055] Specifically, known alkyl groups can be used, such as methyl ester group, ethyl ester group, benzyl ester group, n-propyl ester group, isopropyl ester group, n-butyl ester group, isobutyl ester group, sec-butyl ester group, and t-butyl alkyl group, which have known ester groups.

[0056] In the above general formula (41), the R2 group is an alkylene group having 50 or fewer carbon atoms, which may contain oxygen and nitrogen atoms in part. Specifically, it may contain a methylene group, an ethylene group, an n-propylene group, an i-propylene group, an n-butylene group, or a cyclic structure such as a benzene ring or a cyclohexyl ring (carbon chain 1 to 50). Among these, an ethylene group is particularly preferred because it is inexpensive to produce and has excellent reactivity.

[0057] Examples of compounds having the structure represented by the above general formula (41) include the compound represented by the following general formula (43).

[0058] [ka] (In the formula, R1 is an alkyl group having 50 or fewer carbon atoms.) R2 is an alkylene group with 50 or fewer carbon atoms, which may contain oxygen and nitrogen atoms in part. R3 is either a hydrogen atom or a methyl group.

[0059] Among the ester compounds represented by the above general formula (43), the ester compound represented by the following general formula (45) is more preferred.

[0060] [ka]

[0061] The method for producing an ester compound having a functional group represented by the above general formula (41) is not particularly limited, but it can be produced by the method described in International Publication 2021 / 132251.

[0062] The following are examples of specific chemical structures of compounds represented by general formula (4) that can be synthesized by the methods illustrated above. Note that the present invention is not limited to the compounds illustrated below.

[0063] [ka] (In the above general formula, R represents an alkyl group with 50 or fewer carbon atoms.)

[0064] In the compound represented by the above general formula, R in the general formula is an alkyl group with 50 or fewer carbon atoms, more preferably in the range of 1 to 20 carbon atoms, even more preferably in the range of 1 to 10 carbon atoms, and even more preferably in the range of 1 to 6 carbon atoms. Most preferably in the range of 1 to 4 carbon atoms. This range is preferable because it allows the curing reaction to proceed smoothly.

[0065] The above-mentioned constituent unit (B) is preferably included in a proportion of 1 to 30% by weight relative to the surface modifier. If used in a proportion exceeding 30% by weight, it reacts with the resin composition having hydroxyl groups before it can orient itself on the surface, and is therefore undesirable in that it does not function as a surface modifier. If the content is less than 1% by weight, it is undesirable in that the effects of the present invention described above cannot be fully obtained.

[0066] The above blending ratio range is more preferably 1 to 10% by weight, and even more preferably 1 to 5% by weight.

[0067] (1-3) Other monomers The surface modifier of the present invention may consist only of the above-described constituent units (A) and (B), or it may also contain other monomers in combination, as long as the effects of the present invention are not impaired. When other monomers are used, it is preferable that their amount is 30% by weight or less of the total amount of the surface modifier.

[0068] Other monomer-based constituent units that can be used in the surface modifier of the present invention include the following: Various α-olefins such as ethylene, propylene, or butene-1; Various halogenated olefins, excluding fluoroolefins such as vinyl chloride or vinylidene chloride; Various aromatic vinyl compounds such as styrene, α-methylstyrene, or vinyltoluene; various amino group-containing amide 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 group-containing monomers such as tert-butylaminoethyl(meth)acrylate, tert-butylaminopropyl(meth)acrylate, aziridinylethyl(meth)acrylate, pyrrolidinylethyl(meth)acrylate or piperidinylethyl(meth)acrylate; N,N-dimethylacrylamide, N, Dimethyl(meth)acrylamide monomers such as N-diethylacrylamide and diethyl(meth)acrylamide monomers; unsaturated group-containing morpholinamide monomers such as acryloylmorpholine; vinyl-substituted 5- to 7-membered ring lactam monomers such as N-vinyl-2-pyrrolidone and N-vinyl-epsilon-caprolactam; various carboxyl group-containing monomers such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, or fumaric acid; glycidyl(meth)acrylate, β-methylglycidyl Various epoxy group-containing monomers such as sidyl (meth)acrylate or (meth)allyl glycidyl ether; mono- or diesters of various α,β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid with monohydric alcohols having 1 to 18 carbon atoms; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripoxysilane, vinylmethyldiethoxysilane, vinyltris(β-methoxyethoxy)silane, allyl Monomers containing various hydrolyzable silyl groups, such as trimethoxysilane, trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylpropyl vinyl ether, methyldiethoxysilylpropyl vinyl ether, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, or γ-(meth)acryloyloxypropylmethyldimethoxysilane;

[0069] [ka] (In formula (I), R 1 is a hydrogen atom, or a methyl group, R 2 This is an alkylene group having 1 to 10 carbon atoms. R 3 (where m represents an alkyl group with 1 to 12 carbon atoms, and m represents a positive number between 2 and 150 carbon atoms.)

[0070] [ka] (In formula (II), R 4 is a hydrogen atom, or a methyl group, R 5 (This indicates an alkylene group with 1 to 10 carbon atoms.)

[0071] Siloxy group-containing (meth)acrylate monomers represented by the above chemical formula (I) or (II), such as Cyraplane FM-0711, Cyraplane FM-0721, Cyraplane FM-0725, Cyraplane TM-0701, Cyraplane TM-0701T (all product names of Chisso Corporation; Cyraplane is a registered trademark of Chisso Corporation), KF-2012, X-22-2426, X-22-2475 (all product names of Shin-Etsu Chemical Co., Ltd.);

[0072] [ka] (In formula (III), R 6 , R 9 R is the same or different hydrogen atom, or a methyl group, 7 , R 8 (where n is a positive number between 2 and 150, and represents identical or different alkylene groups with 1 to 10 carbon atoms.)

[0073] Siloxy group-containing di(meth)acrylate monomers such as Cyraplane FM-7711, Cyraplane FM-7721, Cyraplane FM-7725 (all product names of Chisso Corporation), X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164C, and X-22-164E (all product names of Shin-Etsu Chemical Co., Ltd.), represented by the above chemical formula (III);

[0074] Various fluorine-containing α-olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene, or hexafluoropropylene; or various fluorine atom-containing monomers such as various perfluoroalkyl perfluorovinyl ethers or (per)fluoroalkyl vinyl ethers (provided that the number of carbon atoms in the alkyl group is in the range of 1 to 18), such as trifluoromethyltrifluorovinyl ether, pentafluoroethyltrifluorovinyl ether, or heptafluoropropyltrifluorovinyl ether;

[0075] More specifically, the following can be cited as examples of the above-mentioned fluorine atom-containing monomers. Perfluoromethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoropropyl (meth)acrylate, perfluorobutyl (meth)acrylate, perfluoropentyl (meth)acrylate, perfluorohexyl (meth)acrylate, perfluoroheptyl (meth)acrylate, perfluorooctyl (meth)acrylate, perfluorononyl (meth)acrylate, perfluorodecyl (meth)acrylate, perfluoroundecyl (meth)acrylate, perfluorododecyl (meth)acrylate, perfluoro - Fluoriso-propyl (meth)acrylate, perfluoroiso-butyl (meth)acrylate, perfluorotert-butyl (meth)acrylate, perfluorosec-butyl (meth)acrylate, perfluoroiso-pentyl (meth)acrylate, perfluoroiso-hexyl (meth)acrylate, perfluoroiso-heptyl (meth)acrylate, perfluoroiso-octyl (meth)acrylate, perfluoroiso-nonyl (meth)acrylate, perfluoroiso-decyl (meth)acrylate, perfluoro Oro-iso-undecyl (meth)acrylate, perfluoroiso-dodecyl (meth)acrylate, perfluorocyclopentyl (meth)acrylate, perfluorocyclohexyl (meth)acrylate, perfluorocycloheptyl (meth)acrylate, perfluorocyclooctyl (meth)acrylate, perfluorocyclononyl (meth)acrylate, perfluorocyclodecyl (meth)acrylate, perfluorocycloundecyl (meth)acrylate, perfluorocyclododecyl (meth)acrylate, perfluoromethylmeth Perfluoro(meth)acrylate, perfluoroethylmethyl(meth)acrylate, perfluoropropylmethyl(meth)acrylate, perfluorobutylmethyl(meth)acrylate, perfluoropentylmethyl(meth)acrylate, perfluorohexylmethyl(meth)acrylate, perfluoroheptylmethyl(meth)acrylate, perfluorooctylmethyl(meth)acrylate, perfluorononylmethyl(meth)acrylate, perfluorodecylmethyl(meth)acrylate, perfluoroundecylmethyl(meth)acrylate,Perfluorododecylmethyl (meth)acrylate, perfluoroiso-propylmethyl (meth)acrylate, perfluoroiso-butylmethyl (meth)acrylate, perfluorotert-butylmethyl (meth)acrylate, perfluorosec-butylmethyl (meth)acrylate, perfluoroiso-pentylmethyl (meth)acrylate, perfluoroiso-hexylmethyl (meth)acrylate, perfluoroiso-heptylmethyl (meth)acrylate, perfluoroiso-octylmethyl (meth)acrylate, perfluorododecylmethyl (meth)acrylate Fluoriso-nonylmethyl (meth)acrylate, perfluoroiso-decylmethyl (meth)acrylate, perfluoroiso-undecylmethyl (meth)acrylate, perfluoroiso-dodecylmethyl (meth)acrylate, perfluorocyclopentylmethyl (meth)acrylate, perfluorocyclohexylmethyl (meth)acrylate, perfluorocycloheptylmethyl (meth)acrylate, perfluorocyclooctylmethyl (meth)acrylate, perfluorocyclononylmethyl (meth)acrylate, perfluoro Cyclodecylmethyl (meth)acrylate, perfluorocycloundecylmethyl (meth)acrylate, perfluorocyclododecylmethyl (meth)acrylate, perfluoromethyl ethyl (meth)acrylate, perfluoroethyl ethyl (meth)acrylate, perfluoropropyl ethyl (meth)acrylate, perfluorobutyl ethyl (meth)acrylate, perfluoropentyl ethyl (meth)acrylate, perfluorohexyl ethyl (meth)acrylate, perfluoroheptyl ethyl (meth)acrylate, perfluoro oxy Perfluoroethyl (meth)acrylate, perfluorononyl ethyl (meth)acrylate, perfluorodecyl ethyl (meth)acrylate, perfluoroundecyl ethyl (meth)acrylate, perfluorododecyl ethyl (meth)acrylate, perfluoroiso-propyl ethyl (meth)acrylate, perfluoroiso-butyl ethyl (meth)acrylate, perfluorotert-butyl ethyl (meth)acrylate, perfluorosec-butyl (meth)ethyl acrylate, perfluoroiso-pentyl ethyl (meth)acrylate,Perfluoroiso-hexylethyl (meth)acrylate, perfluoroiso-heptylethyl (meth)acrylate, perfluoroiso-octylethyl (meth)acrylate, perfluoroiso-nonylethyl (meth)acrylate, perfluoroiso-decylethyl (meth)acrylate, perfluoroiso-undecylethyl (meth)acrylate, perfluoroiso-dodecylethyl (meth)acrylate, perfluorocyclopentylethyl (meth)acrylate, perfluorocyclohexylethyl (meth)acrylate Perfluorocycloheptylethyl (meth)acrylate, perfluorocyclooctylethyl (meth)acrylate, perfluorocyclononylethyl (meth)acrylate, perfluorocyclodecylethyl (meth)acrylate, perfluorocycloundecylethyl (meth)acrylate, perfluorocyclododecylethyl (meth)acrylate, perfluoromethylpropyl (meth)acrylate, perfluoroethylpropyl (meth)acrylate, perfluoropropylpropyl (meth)acrylate, perfluorobutylpropyl Perfluoro(meth)acrylate, perfluoropentylpropyl(meth)acrylate, perfluorohexylpropyl(meth)acrylate, perfluoroheptylpropyl(meth)acrylate, perfluorooctylpropyl(meth)acrylate, perfluorononylpropyl(meth)acrylate, perfluorodecylpropyl(meth)acrylate, perfluoroundecylpropyl(meth)acrylate, perfluorododecylpropyl(meth)acrylate, perfluoroiso-propyl(meth)acrylate, perfluoroiso- Butylpropyl (meth)acrylate, perfluorotert-butylpropyl (meth)acrylate, perfluorosec-butyl(meth)propyl acrylate, perfluoroiso-pentylpropyl (meth)acrylate, perfluoroiso-hexylpropyl (meth)acrylate, perfluoroiso-heptylpropyl (meth)acrylate, perfluoroiso-octylpropyl (meth)acrylate, perfluoroiso-nonylpropyl (meth)acrylate, perfluoroiso-decylpropyl (meth)acrylate,Perfluoroiso-undecylpropyl (meth)acrylate, perfluoroiso-dodecylpropyl (meth)acrylate, perfluorocyclopentylpropyl (meth)acrylate, perfluorocyclohexylpropyl (meth)acrylate, perfluorocycloheptylpropyl (meth)acrylate, perfluorocyclooctylpropyl (meth)acrylate, perfluorocyclononylpropyl (meth)acrylate, perfluorocyclodecylpropyl (meth)acrylate, perfluorocycloundecylpropyl (meth)acrylate, perfluorocyclododecylpropyl (meth)acrylate, perfluoromethylbutyl (meth)acrylate, perfluoroethylbutyl (meth)acrylate, perfluoropropylbutyl (meth)acrylate, perfluorobutylbutyl (meth)acrylate, perfluoropentylbutyl (meth)acrylate, perfluorohexylbutyl (meth)acrylate, perfluoroheptylbutyl (meth)acrylate, perfluorooctylbutyl (meth)acrylate, perfluorononylbutyl (meth)acrylate Perfluorodecylbutyl (meth)acrylate, perfluoroundecylbutyl (meth)acrylate, perfluorododecylbutyl (meth)acrylate, perfluoroiso-propylbutyl (meth)acrylate, perfluoroiso-butylbutyl (meth)acrylate, perfluorotert-butylbutyl (meth)acrylate, perfluorosec-butyl (meth)acrylate, perfluoroiso-pentylbutyl (meth)acrylate, perfluoroiso-hexylbutyl (meth)acrylate, perfluoro Perfluoroiso-heptylbutyl (meth)acrylate, perfluoroiso-octylbutyl (meth)acrylate, perfluoroiso-nonylbutyl (meth)acrylate, perfluoroiso-decylbutyl (meth)acrylate, perfluoroiso-undecylbutyl (meth)acrylate, perfluoroiso-dodecylbutyl (meth)acrylate, perfluorocyclopentylbutyl (meth)acrylate, perfluorocyclohexylbutyl (meth)acrylate, perfluorocycloheptylbutyl (meth)acrylate,Perfluorocyclooctylbutyl (meth)acrylate, perfluorocyclononylbutyl (meth)acrylate, perfluorocyclodecylbutyl (meth)acrylate, perfluorocycloundecylbutyl (meth)acrylate, perfluorocyclododecylbutyl (meth)acrylate, perfluoromethylpentyl (meth)acrylate, perfluoroethylpentyl (meth)acrylate, perfluoropropylpentyl (meth)acrylate, perfluorobutylpentyl (meth)acrylate, perfluoropentylpentyl (meth)acrylate Acrylate, perfluorohexylpentyl (meth)acrylate, perfluoroheptylpentyl (meth)acrylate, perfluorooctylpentyl (meth)acrylate, perfluorononylpentyl (meth)acrylate, perfluorodecylpentyl (meth)acrylate, perfluoroundecylpentyl (meth)acrylate, perfluorododecylpentyl (meth)acrylate, perfluoroiso-propylpentyl (meth)acrylate, perfluoroiso-butylpentyl (meth)acrylate, perfluorotert- Perfluoroiso-Pentylpentyl(meth)acrylate, Perfluorosec-Butyl(meth)pentylacrylate, Perfluoroiso-Pentylpentyl(meth)acrylate, Perfluoroiso-Heptylpentyl(meth)acrylate, Perfluoroiso-Octylpentyl(meth)acrylate, Perfluoroiso-Nonylpentyl(meth)acrylate, Perfluoroiso-Decylpentyl(meth)acrylate, Perfluoroiso-Undecylpentyl(meth)acrylate, Per Fluoriso-dodecylpentyl (meth)acrylate, perfluorocyclopentylpentyl (meth)acrylate, perfluorocyclohexylpentyl (meth)acrylate, perfluorocycloheptylpentyl (meth)acrylate, perfluorocyclooctylpentyl (meth)acrylate, perfluorocyclononylpentyl (meth)acrylate, perfluorocyclodecylpentyl (meth)acrylate, perfluorocycloundecylpentyl (meth)acrylate, perfluorocyclododecylpentyl (meth)acrylate,Perfluoromethylhexyl (meth)acrylate, perfluoroethylhexyl (meth)acrylate, perfluoropropylhexyl (meth)acrylate, perfluorobutylhexyl (meth)acrylate, perfluoropentylhexyl (meth)acrylate, perfluorohexylhexyl (meth)acrylate, perfluoroheptylhexyl (meth), Acrylate, perfluorooctylhexyl (meth)acrylate, perfluorononylhexyl (meth)acrylate, perfluorodecylhexyl (meth)acrylate, perfluoroundecylhexyl (meth)acrylate, perfluorododecylhexyl (meth)acrylate, perfluoroiso-propylhexyl (meth)acrylate, perfluoroiso-butylhexyl (meth)acrylate, perfluorotert-butylhexyl (meth)acrylate, perfluorosec-butyl (meth)hexyl acrylate, perfluoro Perfluoroiso-pentylhexyl (meth)acrylate, perfluoroiso-hexylhexyl (meth)acrylate, perfluoroiso-heptylhexyl (meth)acrylate, perfluoroiso-octylhexyl (meth)acrylate, perfluoroiso-nonylhexyl (meth)acrylate, perfluoroiso-decylhexyl (meth)acrylate, perfluoroiso-undecylhexyl (meth)acrylate, perfluoroiso-dodecylhexyl (meth)acrylate, perfluorocyclopentylhexyl (meth)acrylate Acrylate, perfluorocyclohexylhexyl (meth)acrylate, perfluorocycloheptylhexyl (meth)acrylate, perfluorocyclooctylhexyl (meth)acrylate, perfluorocyclononylhexyl (meth)acrylate, perfluorocyclodecylhexyl (meth)acrylate, perfluorocycloundecylhexyl (meth)acrylate, perfluorocyclododecylhexyl (meth)acrylate, perfluoromethylheptyl (meth)acrylate, perfluoroethylheptyl (meth)acrylate Perfluoropropylheptyl (meth)acrylate, perfluorobutylheptyl (meth)acrylate, perfluoropentylheptyl (meth)acrylate, perfluorohexylheptyl (meth)acrylate, perfluoroheptylheptyl (meth)acrylate, perfluorooctylheptyl (meth)acrylate, perfluorononylheptyl (meth)acrylate, perfluorodecylheptyl (meth)acrylate, perfluoroundecylheptyl (meth)acrylate, perfluorododecylheptyl (meth)acrylate,Perfluoroiso-propylheptyl (meth)acrylate, perfluoroiso-butylheptyl (meth)acrylate, perfluorotert-butylheptyl (meth)acrylate, perfluorosec-butyl (meth)heptyl acrylate, perfluoroiso-pentylheptyl (meth)acrylate, perfluoroiso-hexylheptyl (meth)acrylate, perfluoroiso-heptylheptyl (meth)acrylate, perfluoroiso-octylheptyl (meth)acrylate, perfluoroiso-nonylheptyl Butyl (meth)acrylate, perfluoroiso-decylheptyl (meth)acrylate, perfluoroiso-undecylheptyl (meth)acrylate, perfluoroiso-dodecylheptyl (meth)acrylate, perfluorocyclopentylheptyl (meth)acrylate, perfluorocyclohexylheptyl (meth)acrylate, perfluorocycloheptylheptyl (meth)acrylate, perfluorocyclooctylheptyl (meth)acrylate, perfluorocyclononylheptyl (meth)acrylate, perfluoro Rocyclodecylheptyl (meth)acrylate, perfluorocycloundecylheptyl (meth)acrylate, perfluorocyclododecylheptyl (meth)acrylate, perfluoromethyloctyl (meth)acrylate, perfluoroethyloctyl (meth)acrylate, perfluoropropyloctyl (meth)acrylate, perfluorobutyloctyl (meth)acrylate, perfluoropentyloctyl (meth)acrylate, perfluorohexyloctyl (meth)acrylate, perfluoroheptyloctyl (meth)acrylate Acrylate, perfluorooctyloctyl(meth)acrylate, perfluorononyloctyl(meth)acrylate, perfluorodecyloctyl(meth)acrylate, perfluoroundecyloctyl(meth)acrylate, perfluorododecyloctyl(meth)acrylate, perfluoroiso-propyloctyl(meth)acrylate, perfluoroiso-butyloctyl(meth)acrylate, perfluorotert-butyloctyl(meth)acrylate, perfluorosec-butyl(meth)octylacrylate,Perfluoroiso-pentyloctyl (meth)acrylate, perfluoroiso-hexyloctyl (meth)acrylate, perfluoroiso-heptyloctyl (meth)acrylate, perfluoroiso-octyloctyl (meth)acrylate, perfluoroiso-nonyloctyl (meth)acrylate, perfluoroiso-decyloctyl (meth)acrylate, perfluoroiso-undecyloctyl (meth)acrylate, perfluoroiso-dodecyloctyl (meth)acrylate, perfluorocyclopentyloctyl Perfluorocyclohexyl octyl (meth)acrylate, perfluorocyclohexyl octyl (meth)acrylate, perfluorocycloheptyl octyl (meth)acrylate, perfluorocyclooctyl octyl (meth)acrylate, perfluorocyclononyl octyl (meth)acrylate, perfluorocyclodecyl octyl (meth)acrylate, perfluorocycloundecyl octyl (meth)acrylate, perfluorocyclododecyl octyl (meth)acrylate, perfluoromethyl nonyl (meth)acrylate, perfluoroethyl nonyl (meth) Acrylate, perfluoropropyl nonyl (meth)acrylate, perfluorobutyl nonyl (meth)acrylate, perfluoropentyl nonyl (meth)acrylate, perfluorohexyl nonyl (meth)acrylate, perfluoroheptyl nonyl (meth)acrylate, perfluorooctyl nonyl (meth)acrylate, perfluorononyl nonyl (meth)acrylate, perfluorodecyl nonyl (meth)acrylate, perfluoroundecyl nonyl (meth)acrylate, perfluorododecyl nonyl (meth)acrylate, perfluoro Fluoriso-propylnonyl (meth)acrylate, perfluoroiso-butylnonyl (meth)acrylate, perfluorotert-butylnonyl (meth)acrylate, perfluorosec-butylnonyl (meth)acrylate, perfluoroiso-pentylnonyl (meth)acrylate, perfluoroiso-hexylnonyl (meth)acrylate, perfluoroiso-heptylnonyl (meth)acrylate, perfluoroiso-octylnonyl (meth)acrylate, perfluoroiso-nonylnonyl (meth)acrylate,Perfluoroiso-decylnonyl (meth)acrylate, perfluoroiso-undecylnonyl (meth)acrylate, perfluoroiso-dodecylnonyl (meth)acrylate, perfluorocyclopentylnonyl (meth)acrylate, perfluorocyclohexylnonyl (meth)acrylate, perfluorocycloheptylnonyl (meth)acrylate, perfluorocyclooctylnonyl (meth)acrylate, perfluorocyclononylnonyl (meth)acrylate, perfluorocyclodecylnonyl (meth)acrylate, perfluoro Rocycloundecylnonyl (meth)acrylate, perfluorocyclododecylnonyl (meth)acrylate, perfluoromethyldecyl (meth)acrylate, perfluoroethyldecyl (meth)acrylate, perfluoropropyldecyl (meth)acrylate, perfluorobutyldecyl (meth)acrylate, perfluoropentyldecyl (meth)acrylate, perfluorohexyldecyl (meth)acrylate, perfluoroheptyldecyl (meth)acrylate, perfluorooctyldecyl (meth)acrylate, perfluorononyl Syl(meth)acrylate, perfluorodecyldecyl(meth)acrylate, perfluoroundecyldecyl(meth)acrylate, perfluorododecyldecyl(meth)acrylate, perfluoroiso-propyldecyl(meth)acrylate, perfluoroiso-butyldecyl(meth)acrylate, perfluorotert-butyldecyl(meth)acrylate, perfluorosec-butyl(meth)decylacrylate, perfluoroiso-pentyldecyl(meth)acrylate, perfluoroiso-hexyldecyl(meth)acrylate Perfluoroiso-heptyldecyl (meth)acrylate, perfluoroiso-octyldecyl (meth)acrylate, perfluoroiso-nonyldecyl (meth)acrylate, perfluoroiso-decyldecyl (meth)acrylate, perfluoroiso-undecyldecyl (meth)acrylate, perfluoroiso-dodecyldecyl (meth)acrylate, perfluorocyclopentyldecyl (meth)acrylate, perfluorocyclohexyldecyl (meth)acrylate, perfluorocycloheptyldecyl (meth)acrylate,Perfluorocyclooctyldecyl (meth)acrylate, perfluorocyclononyldecyl (meth)acrylate, perfluorocyclodecyldecyl (meth)acrylate, perfluorocycloundecyldecyl (meth)acrylate, perfluorocyclododecyldecyl (meth)acrylate, perfluoromethylundecyl (meth)acrylate, perfluoroethylundecyl (meth)acrylate, perfluoropropylundecyl (meth)acrylate, perfluorobutylundecyl (meth)acrylate, perfluoropentylundecyl (meth)acrylate, perfluorohexyl undecyl (meth)acrylate, perfluoroheptyl undecyl (meth)acrylate, perfluorooctyl undecyl (meth)acrylate, perfluorononyl undecyl (meth)acrylate, perfluorodecyl undecyl (meth)acrylate, perfluoroundecyl undecyl (meth)acrylate, perfluorododecyl undecyl (meth)acrylate, perfluoroiso-propyl undecyl (meth)acrylate, perfluoroiso-butyl undecyl (meth)acrylate Perfluorotert-butyl undecyl (meth)acrylate, perfluorosec-butyl (meth) undecyl acrylate, perfluoroiso-pentyl undecyl (meth)acrylate, perfluoroiso-hexyl undecyl (meth)acrylate, perfluoroiso-heptyl undecyl (meth)acrylate, perfluoroiso-octyl undecyl (meth)acrylate, perfluoroiso-nonyl undecyl (meth)acrylate, perfluoroiso-decyl undecyl (meth)acrylate, perfluoroiso-un Decylundecyl(meth)acrylate, perfluoroiso-dodecylundecyl(meth)acrylate, perfluorocyclopentylundecyl(meth)acrylate, perfluorocyclohexylundecyl(meth)acrylate, perfluorocycloheptylundecyl(meth)acrylate, perfluorocyclooctylundecyl(meth)acrylate, perfluorocyclononylundecyl(meth)acrylate, perfluorocyclodecylundecyl(meth)acrylate, perfluorocycloundecylundecyl(meth)acrylate,Per, Fluorocyclododecylundecyl(meth)acrylate, perfluoromethyldodecyl(meth)acrylate, perfluoroethyldodecyl(meth)acrylate, perfluoropropyldodecyl(meth)acrylate, perfluorobutyldodecyl(meth)acrylate, perfluoropentyldodecyl(meth)acrylate, perfluorohexyldodecyl(meth)acrylate, perfluoroheptyldodecyl(meth)acrylate, perfluorooctyldodecyl(meth)acrylate Perfluorononyl dodecyl (meth)acrylate, perfluorodecyl dodecyl (meth)acrylate, perfluoroundecyl dodecyl (meth)acrylate, perfluorododecyl dodecyl (meth)acrylate, perfluoroiso-propyl dodecyl (meth)acrylate, perfluoroiso-butyl dodecyl (meth)acrylate, perfluorotert-butyl dodecyl (meth)acrylate, perfluorosec-butyl (meth) dodecyl acrylate, perfluoroiso- Pentyldodecyl (meth)acrylate, perfluoroiso-hexyldodecyl (meth)acrylate, perfluoroiso-heptyldodecyl (meth)acrylate, perfluoroiso-octyldodecyl (meth)acrylate, perfluoroiso-nonyldodecyl (meth)acrylate, perfluoroiso-decyldodecyl (meth)acrylate, perfluoroiso-undecyldodecyl (meth)acrylate, perfluoroiso-dodecyldodecyl (meth)acrylate, perfluoroiso-dodecyldodecyl (meth)acrylate, perfluoroiso- Fluorocyclopentyldodecyl (meth)acrylate, perfluorocyclohexyldodecyl (meth)acrylate, perfluorocycloheptyldodecyl (meth)acrylate, perfluorocyclooctyldodecyl (meth)acrylate, perfluorocyclononyldodecyl (meth)acrylate, perfluorocyclodecyldodecyl (meth)acrylate, perfluorocycloundecyldodecyl (meth)acrylate, perfluorocyclododecyldodecyl (meth)acrylate, etc.

[0076] CH2=C(R 3 )-CO-O-TRI2-CF2-O-(CF2-CF2-O)n -(CF2-CF2-CF2-O) m -(CFCF3-CF2-O) p -R F2 (IV) (In formula (IV), R 3 n is a hydrogen atom or methyl group, n, m, p are numbers from 0 to 8, R F2 (This represents a perfluoroalkyl group with 1 to 6 carbon atoms.) CH2=C(R 4 )-CO-O-(CH2)2-NH-CO-O-CH2-CF2-O-(CF2-CF2-O) q -(CF2-CF2-CF2-O) r -(CFCF3-CF2-O) s -R F3 (V) (In formula (V), R 4 is a hydrogen atom or methyl group, q, r, s are numbers from 0 to 8, R F3 ) represents a perfluoroalkyl group having 1 to 6 carbon atoms. )(IV), (V) represents a fluorine-containing (meth)acrylate monomer, a perfluoropolyether group-containing monomer;

[0077] Vinyl-2,2-dimethylpropanoate, vinyl-2,2-dimethylbutanoate, vinyl-2,2-dimethylpentanoate, vinyl-2,2-dimethylhexanoate, vinyl-2-ethyl-2-methylbutanoate, vinyl-2-ethyl-2-methylpentanoate, vinyl-3-chloro-2,2-dimethylpropanoate, and others, as well as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate or vinyl laurate, C9 branched aliphatic vinyl carboxylate, C 10 branched aliphatic vinyl carboxylate, C 11 branched aliphatic calcium Examples include various aliphatic vinyl carboxylates such as vinyl benzoate or vinyl stearate; or vinyl esters of cyclic carboxylic acids such as vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate, or p-tert-butylbenzoate.

[0078] Furthermore, the hydroxyl group-containing monomers exemplified below can also be used as other monomers. However, it is more preferable not to use hydroxyl group-containing monomers because they self-crosslink and inhibit surface orientation. If they are used, it is preferable to use them in amounts of 5% by weight or less.

[0079] The hydroxyl group-containing monomers include 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, or 6-hydroxyhexyl vinyl ether; or the addition reaction products of these 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; 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 the main component of the addition reaction between these various (meth)acrylates and ε-caprolactone.

[0080] The surface modifier of the present invention has a weight-average molecular weight of 3,000 to 500,000. Outside this range, the basic properties of the surface modifier, such as smoothness and defoaming properties, cannot be sufficiently maintained. The weight-average molecular weight of the surface modifier of the present invention is the value measured by the method described in the examples.

[0081] In the present invention, a desired surface modifier can be obtained by combining and polymerizing the various monomers (A) to (C) described above as needed.

[0082] Furthermore, it is preferable that the surface modifier of the present invention does not have hydroxyl groups. If it has hydroxyl groups, it becomes difficult to adjust the solubility parameter within an appropriate range, and is therefore undesirable as it cannot be suitably used for the purposes of the present invention.

[0083] The above-mentioned surface modifier is not limited in its manufacturing method and can be produced by polymerization using known methods. More specifically, polymerization methods include solution polymerization in organic solvents, emulsion polymerization in water, miniemulsion polymerization in water, aqueous solution polymerization, suspension polymerization, and UV curing.

[0084] The surface modifier of the present invention is preferably unevenly distributed in the upper layer of the coating-forming resin during coating film formation. From this viewpoint, a solubility parameter of 7.6 to 12.0 is preferred. More specifically, the surface modifier includes additives also known as leveling agents and defoaming agents.

[0085] The weight-average molecular weight range of the above surface modifier is more preferably 3,000 to 100,000 for leveling agents, and even more preferably 3,000 to 60,000. For defoaming agents, it is more preferably 10,000 to 500,000, and even more preferably 10,000 to 400,000. The lower limit of the weight-average molecular weight of component (X) is more preferably 3,000, and even more preferably 5,000.

[0086] A thermosetting resin composition to which the surface modifier of the present invention has been added preferably contains a resin or resin composition (X) having hydroxyl groups. The presence of hydroxyl groups allows for a transesterification reaction based on the hydroxyl groups and the alkyl ester groups of the constituent unit (B), thereby enabling the effects of the present invention to be suitably expressed. The surface modifier of the present invention is suitably used as an additive to a resin or resin composition (X) having hydroxyl groups, which serves as the main component of the thermosetting resin composition. Such a thermosetting resin composition is also one of the present inventions.

[0087] When the surface modifier of the present invention is used as an additive to a thermosetting resin composition, the amount blended is preferably 0.1 to 2.0% by weight relative to the total amount of solid resin components of the thermosetting resin composition. The lower limit is more preferably 0.1% by weight, and even more preferably 0.2% by weight. The upper limit is more preferably 2.0% by weight, and even more preferably 1.0% by weight.

[0088] The compound containing a hydroxyl group that can be used as the above-mentioned resin or resin composition (X) is not particularly limited, and various polyols commonly used for this purpose can be listed. Examples of such polyols include acrylic polyols, polyester polyols, polyurethane polyols, and polycarbonate polyols. Any known polyol can be used.

[0089] The above-mentioned resin or resin composition (X) preferably has a curing agent or curable functional group that reacts with hydroxyl groups in such polyols. That is, a curing agent may be added to the polyol, or the polyol resin may have a functional group that reacts with hydroxyl groups.

[0090] The thermosetting resin compositions having hydroxyl groups described above are not particularly limited, but examples include compositions incorporating isocyanate compounds, melamine resins, silane compounds, etc., as curing agents. Furthermore, they may also be thermosetting resin compositions based on transesterification reactions between hydroxyl groups and alkyl ester groups, as disclosed in International Publications 2019 / 054136, 2019 / 069398, 2019 / 139069, 2021 / 095202, 2021 / 132251, etc.

[0091] The resin or resin composition (X) of the present invention may be a single resin or a mixture of multiple resins. In either case, hydroxyl groups are present in the resin or resin composition.

[0092] More specifically, the resin or resin composition (X) may be a mixture of a hydroxyl group-containing resin and a curing agent, or it may have both a functional group that reacts with a hydroxyl group and a hydroxyl group in the same resin.

[0093] Examples of curing agents that can be used in combination with such polyols include the following:

[0094] Polyisocyanate compounds Polyisocyanate compounds are compounds having at least two isocyanate groups in one molecule, and examples include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of said polyisocyanates.

[0095] Examples of the above aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, diisocyanate dimer, and methyl 2,6-diisocyanatohexanoate (common name: lysine). Examples include aliphatic diisocyanates such as diisocyanates; and aliphatic triisocyanates such as 2-isocyanatoethyl 2,6-diisocyanatohexanoate, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane.

[0096] Examples of the above alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name: isophorone diisocyanate), 4-methyl-1,3-cyclohexylene diisocyanate (common name: hydrogenated TDI), and 2-methyl-1,3-cyclohexylene diisocyanate. Alicyclic diisocyanates such as nate, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane (common name: hydrogenated xylylene diisocyanate) or mixtures thereof, methylenebis(4,1-cyclohexanediyl) diisocyanate (common name: hydrogenated MDI), norbornane diisocyanate; 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2-(3-isocyanatopropyl)- 2,5-di(isocyanatomethyl)-bicyclo(2.2.1)heptane, 2-(3-isocyanatopropyl)-2,6-di(isocyanatomethyl)-bicyclo(2.2.1)heptane, 3-(3-isocyanatopropyl)-2,5-di(isocyanatomethyl)-bicyclo(2.2.1)heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane, 6-(2-iso Examples include alicyclic triisocyanates such as cyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane, and 6-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane.

[0097] Examples of the above-mentioned aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates such as methylenebis(4,1-phenylene) diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω,ω'-diisocyanato-1,4-diethylbenzene, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (common name: tetramethylxylylene diisocyanate) or mixtures thereof; and aromatic aliphatic triisocyanates such as 1,3,5-triisocyanatomethylbenzene.

[0098] Examples of the above-mentioned aromatic polyisocyanates include aromatic diisocyanates such as m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenylenediisocyanate, 1,5-naphthalenediisocyanate, 2,4-tolyleneenediisocyanate (common name: 2,4-TDI) or 2,6-tolyleneenediisocyanate (common name: 2,6-TDI) or mixtures thereof, 4,4'-toluidinediisocyanate, and 4,4'-diphenyletherdiisocyanate; aromatic triisocyanates such as triphenylmethane-4,4',4''-triisocyanate, 1,3,5-triisocyanatobenzene, and 2,4,6-triisocyanatotoluene; and aromatic tetraisocyanates such as 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate.

[0099] Furthermore, examples of derivatives of the above-mentioned polyisocyanates include dimers, trimers, biuretes, allophanates, uretodiones, uretoimines, isocyanurates, oxadiazinetriones, polymethylene polyphenyl polyisocyanates (crude MDI, polymeric MDI), crude TDI, and the like.

[0100] From the viewpoint of adhesion to the substrate and resistance to cold and heat loads, the above-mentioned aliphatic diisocyanates, alicyclic diisocyanates, and their derivatives can be suitably used as polyisocyanate compounds.

[0101] Furthermore, as the polyisocyanate compound, a prepolymer obtained by reacting the polyisocyanate and its derivatives with a compound that can react with the polyisocyanate under conditions of excess isocyanate groups may be used. Examples of compounds that can react with the polyisocyanate include compounds having active hydrogen groups such as hydroxyl groups and amino groups, and specifically, for example, polyhydric alcohols, low molecular weight polyester resins, amines, water, etc. can be used.

[0102] Furthermore, as the polyisocyanate compound, a polymer of an isocyanate group-containing polymerizable unsaturated monomer, or a copolymer of the isocyanate group-containing polymerizable unsaturated monomer and a polymerizable unsaturated monomer other than the isocyanate group-containing polymerizable unsaturated monomer may be used.

[0103] Furthermore, the polyisocyanate compound may be a polyisocyanate compound in which the isocyanate group is blocked with a blocking agent, a so-called blocked polyisocyanate compound.

[0104] Examples of the above-mentioned blocking agents include phenols such as phenol, cresol, xylenol, nitrophenol, ethylphenol, hydroxydiphenyl, butylphenol, isopropylphenol, nonylphenol, octylphenol, and methyl hydroxybenzoate; lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; aliphatic alcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol, and lauryl alcohol; and ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol. Ethers such as monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and methoxymethanol; alcohols such as benzyl alcohol, glycolic acid, methyl glycolate, ethyl glycolate, butyl glycolate, lactic acid, methyl lactate, ethyl lactate, butyl lactate, methylolurea, methylolmelamine, diacetone alcohol, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate; oximes such as formamide oxime, acetamide oxime, acetooxime, methyl ethyl ketoxime, diacetylmonoxime, benzophenone oxime, and cyclohexane oxime; active methylene compounds such as dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, and acetylacetone; and butyl mercaptan, t-butyl mercaptan, hexyl mercaptan, and t-dodecyl mercaptan. Examples include mercaptan compounds such as captan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol, and ethylthiophenol; acid amide compounds such as acetanilide, acetanisidide, acetoluid, acrylamide, methacrylamide, acetic acid amide, stearic acid amide, and benzamide; imide compounds such as succinimide, phthalimide, and maleimide; amine compounds such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine, and butylphenylamine; imidazole compounds such as imidazole and 2-ethylimidazole; urea compounds such as urea, thiourea, ethyleneurea, ethylenethiourea, and diphenylurea; carbamic acid ester compounds such as phenyl N-phenylcarbamate; imine compounds such as ethyleneimine and propyleneimine; sulfite compounds such as sodium bisulfite and potassium bisulfite; and azole compounds.Examples of the above-mentioned azole compounds include pyrazoles or pyrazole derivatives such as pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, and 3-methyl-5-phenylpyrazole; imidazoles or imidazole derivatives such as imidazole, benzimidazole, 2-methylimidazole, 2-ethylimidazole, and 2-phenylimidazole; and imidazoline derivatives such as 2-methylimidazoline and 2-phenylimidazoline.

[0105] Among these, preferred blocking agents include oxime-based blocking agents, active methylene-based blocking agents, pyrazoles, or pyrazole derivatives.

[0106] When performing the blocking reaction (reacting with the blocking agent), a solvent may be added as needed. Suitable solvents for the blocking reaction are those that are not reactive with isocyanate groups. Examples include acetone, ketones such as methyl ethyl ketone, esters such as ethyl acetate, and solvents such as N-methyl-2-pyrrolidone (NMP).

[0107] Melamine resin The melamine resin that can be used in the present invention is not particularly limited, and any commonly used curing agent can be used. Preferably, alkyl etherified melamine resins are those in which the methylol group of a methylolated melamine resin is partially or completely etherified with methyl alcohol, such as methyl etherified melamine resins, butyl etherified melamine resins, and methyl-butyl mixed etherified melamine resins, which are partially or completely etherified with methyl alcohol and butyl alcohol. Such alkyl etherified melamine resins can be cured. It is particularly desirable due to its superior performance.

[0108] epoxy compounds The epoxy compounds that can be used in the present invention are not particularly limited, and any known epoxy compounds such as epoxy group-containing acrylic resins, bisphenol-type epoxy resins, and alicyclic epoxy compounds can be cited.

[0109] The epoxy group-containing acrylic resin described above is preferably an epoxy group-containing acrylic resin having an epoxy group equivalent of 50 to 700. Furthermore, it is preferable that it has an average of 2 or more epoxy groups per molecule, preferably 2 to 10, and more preferably 3 to 8.

[0110] The number-average molecular weight of the epoxy group-containing acrylic resin is preferably 200 to 10,000. More preferably 500 to 8,000, and more preferably 800 to 5,000. A higher number-average molecular weight is preferable when considering sufficient curability of the coating film, and a lower number-average molecular weight is preferable when considering a higher solid content in the resulting paint. The epoxy group equivalent is 50 to 700, preferably 80 to 600, and more preferably 100 to 500. A lower epoxy group equivalent is preferable when considering sufficient curability of the coating film, and a higher number-average epoxy group equivalent is preferable when considering the brittleness of the coating film.

[0111] The epoxy group-containing acrylic resin (B) described above is preferably an acrylic polyepoxide obtained by copolymerizing 10 to 60% by mass, preferably 15 to 50% by mass, of an epoxy group-containing ethylenically unsaturated monomer with 40 to 90% by mass, preferably 50 to 85% by mass, of an ethylenically unsaturated monomer that does not contain epoxy groups. The amount of epoxy group-containing ethylenically unsaturated monomer is preferably higher when considering sufficient curability of the coating film, and preferably lower when considering weather resistance of the coating film.

[0112] Examples of epoxy group-containing ethylenically unsaturated monomers include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, and 3,4-epoxycyclohexanyl (meth)acrylate. To prepare a paint that exhibits balanced curability and storage stability, it is preferable to use glycidyl (meth)acrylate. Examples of ethylenically unsaturated monomers that do not contain epoxy groups include various unsaturated group-containing monomers, which are described in detail below.

[0113] Furthermore, when a hydroxyl group-containing monomer is used in combination with the epoxy group-containing ethylenically unsaturated monomer described above, the hydroxyl group can participate in the transesterification reaction detailed below. Therefore, this is preferable in that a higher crosslink density can be more readily obtained. Moreover, since epoxy groups can also react with hydroxyl groups, this is also preferable in terms of obtaining a good crosslink density.

[0114] If the above-mentioned acid group-containing acrylic resin also contains hydroxyl groups, the hydroxyl group-containing monomers that can be used here include the hydroxyl group-containing monomers exemplified in "Resin Component (B)" described in detail below.

[0115] If the epoxy group-containing acrylic resin has hydroxyl groups, the hydroxyl value of the epoxy group-containing acrylic resin is 5 to 300 mgKOH / g, preferably 10 to 200 mgKOH / g, and more preferably 15 to 150 mgKOH / g. If the hydroxyl value exceeds 300, the paint solid content decreases or the water resistance of the cured coating film is insufficient, and if it is less than 5, the adhesion is poor.

[0116] Particularly preferred epoxy group-containing acrylic resins can be obtained by copolymerizing (ii) 5 to 70% by mass of a hydroxyl group-containing ethylenically unsaturated monomer, (ii) 10 to 60% by mass of an epoxy group-containing ethylenically unsaturated monomer, and (iii) 0 to 85% by mass of an ethylenically unsaturated monomer that does not have either a hydroxyl group or an epoxy group, if necessary. In this case, the epoxy group-containing acrylic resin has an average of preferably 2 to 12 epoxy groups, more preferably 3 to 10 epoxy groups, and an average of preferably 0.5 to 10 hydroxyl groups, more preferably 1 to 8 hydroxyl groups per molecule. Furthermore, the hydroxyl group-containing monomers that can be used here are those exemplified in "Resin Component (B)" described in detail below.

[0117] Furthermore, as resins containing epoxy groups, in addition to the epoxy group-containing acrylic resins mentioned above, examples include polyglycol ether type epoxy compounds such as novolac type polyepoxy, epichlorohydrin-bisphenol type polyepoxy, butanediol diglycidyl ether, 1,6-hexanethiol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and glycerin triglycidyl ether; polycarboxylic acid ester type epoxy compounds such as phthalate diglycidyl ester; isocyanurate type epoxy compounds such as triglycidyl isocyanurate; epoxidized fatty acid esters such as epoxidized soybean oil; and epoxy group-containing radical polymerizable unsaturated monomers (e.g., glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, etc.).

[0118] When using an epoxy compound as the curing agent, it is preferable to use a compound having a carboxylic acid group in combination to form an acid epoxy curing resin composition. Examples of carboxylic acid-containing compounds that can be used here include acid-containing acrylic resins containing carboxyl groups and carboxylic acid ester groups with an acid value of 50 to 300 mg KOH / g (solids). Furthermore, the epoxy-containing compound mentioned above may also contain a carboxyl group. In addition, it may also contain a hydroxyl group.

[0119] Acrylic resins containing acid groups are not particularly limited as long as they have acid groups, and examples include acrylic resins having constituent units derived from (meth)acrylic acid and itaconic acid.

[0120] Furthermore, the above-mentioned acid group-containing acrylic resin may be obtained by reacting an acrylic resin having an acid anhydride group with a monoalcohol. Acrylic resins having acid anhydride groups can be obtained, for example, by copolymerizing an acid anhydride group-containing ethylenically unsaturated monomer, preferably 15 to 40% by mass, more preferably 15 to 35% by mass, with an ethylenically unsaturated monomer without acid anhydride groups, preferably 60 to 85% by mass, more preferably 65 to 85% by mass. If the amount of acid anhydride group-containing ethylenically unsaturated monomer is less than 15% by mass, the curability will be insufficient, and if it exceeds 40% by mass, the resulting coating film tends to become too hard and brittle, resulting in insufficient weather resistance. Examples of acid anhydride group-containing ethylenically unsaturated monomers include itaconic anhydride, maleic anhydride, and citraconic anhydride.

[0121] Ethylene-unsaturated monomers that do not have an acid anhydride group are not particularly limited as long as they do not adversely affect the acid anhydride group, and monomers having 3 to 15 carbon atoms, particularly 3 to 12 carbon atoms, that have one ethylenically unsaturated bond are preferred. Specific examples include styrene, α-methylstyrene, pt-butylstyrene, and (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, and isobolonyl (meth)acrylate, as well as Shell's VeoVa-9 and VeoVa-10. Monomers having a carboxyl group, such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid, are also acceptable. In particular, using a long-chain carboxylic acid monomer having a spacer portion of about 5 to 20 carbon atoms between the ethylenically unsaturated group and the carboxyl group, such as ε-caprolactone 2-molar modified acrylic acid [manufactured by Toagosei Chemical Industry Co., Ltd., Aronics M-5300, molecular weight 300], improves the scratch resistance of the coating film and is especially preferable.

[0122] This acid anhydride group-containing acrylic resin can be obtained, for example, by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer, which is obtained by half-esterifying a hydroxyl group-containing monomer and an acid anhydride group-containing compound in a molar ratio of hydroxyl groups to acid anhydride groups of 1 / 0.5 to 1 / 1.0, preferably 1 / 0.8 to 1 / 1.0, with an ethylenically unsaturated monomer that does not contain acid anhydride groups. If the molar ratio of hydroxyl groups to acid anhydride groups exceeds 1 / 0.5, the polymer viscosity increases, resulting in poor workability. If it is less than 1 / 1.0, an excess of the acid anhydride group-containing compound remains, reducing the water resistance of the coating film.

[0123] Specific examples of acid anhydride group-containing compounds used here include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trimellitic anhydride, succinic anhydride, etc., and these can also be used in combination. The half-esterification reaction between a hydroxyl group-containing ethylenically unsaturated monomer and an acid anhydride group-containing compound is carried out according to the usual method at a temperature from room temperature to 150°C. Copolymerization of an acid anhydride-containing ethylenically unsaturated monomer with an acid anhydride-free ethylenically unsaturated monomer, and copolymerization of the above monomer with an acid anhydride-free ethylenically unsaturated monomer, can be carried out by known methods such as solution polymerization, including radical polymerization. For example, it can be carried out under atmospheric pressure or under pressure at a polymerization temperature of 100-200°C for 3-8 hours. Azo-based or peroxide-based initiators are preferably used as initiators. Other additives such as chain transfer agents can also be used.

[0124] The number-average molecular weight of the resulting polymer is preferably 500 to 8000, more preferably 800 to 6000, and particularly preferably 1500 to 4000. If the number-average molecular weight exceeds 8000, the compatibility between the resins decreases, and the appearance deteriorates. If the number-average molecular weight falls below 500, the curability of the resin composition becomes insufficient. The resulting polymer has an average of at least 2, preferably 2 to 15, acid anhydride groups per molecule. If the number of acid anhydride groups contained in one molecule is less than 2, the curability of the resin composition becomes insufficient. If it exceeds 15, it becomes too hard and brittle, and the weather resistance is insufficient. The above number-average molecular weight can be obtained as a converted value using styrene polymer standards with gel permeation chromatography (GPC).

[0125] Next, the acrylic resin having acid anhydride groups obtained is reacted with a monoalcohol in an amount such that the molar ratio of acid anhydride groups to hydroxyl groups is 1 / 10 to 1 / 1, preferably 1 / 5 to 1 / 1, and more preferably 1 / 2 to 1 / 1, to prepare an acid group-containing acrylic resin having carboxyl groups and carboxylic acid ester groups. If this molar ratio is less than 1 / 10, there is too much excess alcohol, which causes bubbling during curing, and if it is greater than 1 / 1, unreacted anhydride groups remain, resulting in poor storage stability.

[0126] The above monoalcohol preferably has 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. When an acrylic resin containing acid groups is heated, these alcohol components readily detach and volatilize, making it easy to regenerate the acid anhydride groups. Preferred monoalcohols include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, n-hexyl alcohol, lauryl alcohol, methyl cellosolve, ethyl cellosolve, methoxypropanol, ethoxypropanol, fryfuryl alcohol, dimethylaminoethanol, diethylaminoethanol, acetol, allyl alcohol, and propargyl alcohol, and these can be used in combination. Particularly preferred are acetol, fryfuryl alcohol, allyl alcohol, propargyl alcohol, ethanol, and methanol.

[0127] The acid value of the resulting acid group-containing acrylic resin is 50 to 300 mgKOH / g, preferably 50 to 250 mgKOH / g. If the acid value is below 50 mgKOH / g, the curing ability of the coating film will be insufficient, and if it is above 300 mgKOH / g, the storage stability of the intermediate coating will be poor, which is undesirable.

[0128] The acid group-containing acrylic resin component is blended into the thermosetting resin composition in a proportion of 10 to 70% by mass, preferably 15 to 50% by mass, and more preferably 20 to 45% by mass, based on the total mass of the solids content of the thermosetting resin composition. A higher blending amount is preferable when considering the acid resistance of the coating film, and a lower blending amount is preferable when considering the brittleness of the cured product.

[0129] Alkoxysilane compounds The alkoxysilane compounds that can be used in the present invention are not particularly limited, and examples include compounds having a Si-OR group that can be crosslinked by reacting with a hydroxyl group. More specifically,

[0130] [ka] Si(R a ) n (OR b ) 4-n (R a This represents an alkyl group having 1 to 50 carbon atoms, which may have substituents. R b This represents an alkyl group with 1 to 4 carbon atoms. n represents an integer between 0 and 2. Examples include their low-molecular-weight condensates.

[0131] The above-mentioned alkoxysilane compound may be a silicon compound having a functional group such as a vinyl group, epoxy group, amino group, (meth)acryloyl group, carboxyl group, or mercapto group in addition to the alkoxy group. These compounds are also called alkoxysilanes, and such compounds can also be suitably used as the alkoxysilane compound of the present invention. Specific examples of such alkoxysilane compounds include, for example, amino group-containing alkoxysilane compounds such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane; mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropylmethyldiethoxysilane; γ Examples include epoxy group-containing alkoxysilane compounds such as -glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; carboxy-containing alkoxysilane compounds such as β-carboxylethylphenylbis(2-methoxyethoxy)silane and N-β-(N-carboxylmethylaminoethyl)-γ-aminopropyltrimethoxysilane; vinyl group-containing alkoxysilane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriacetoxysilane; and (meth)acryloyl group-containing alkoxysilane compounds such as 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane. These may be used individually or in combination of two or more.

[0132] Examples of alkoxysilane compounds that do not have the functional groups mentioned above include dialkoxysilanes, trialkoxysilanes, and tetraalkoxysilanes.

[0133] Examples of the above-mentioned dialkoxysilanes include dimethoxydimethylsilane, dimethoxydiethylsilane, dimethoxydiphenylsilane, diethoxydimethylsilane, diethoxydiethylsilane, diethoxydiphenylsilane, dipropoxydimethylsilane, dipropoxydiethylsilane, dipropoxydipropylsilane, dipropoxydiphenylsilane, dibutoxydimethylsilane, dibutoxydiethylsilane, dibutoxydibutylsilane, and dibutoxydiphenylsilane.

[0134] Examples of the trialkoxysilanes mentioned above include trimethoxymethylsilane, trimethoxyethylsilane, trimethoxypropylsilane, trimethoxybutylsilane, trimethoxyphenylsilane, triethoxymethylsilane, triethoxyethylsilane, triethoxybutylsilane, triethoxyphenylsilane, tripropoxymethylsilane, tripropoxypropylsilane, tripropoxyphenylsilane, and tripbutoxyphenylsilane.

[0135] Examples of the tetraalkoxysilanes mentioned above include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and dimethoxydiethoxysilane.

[0136] Of the above alkoxysilanes, trialkoxysilane and tetraalkoxysilane are preferred in terms of crosslinking properties and other factors.

[0137] The alkoxy groups of these alkoxysilanes are not particularly limited, and examples include alkoxy groups having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably 1 to 2 carbon atoms.

[0138] The low-molecular-weight compound, which includes at least one of the di-, tri-, and tetra-alkoxysilanes, may be a low-molecular-weight compound of a single mono-, di-, tri-, or tetra-alkoxysilane, or a low-molecular-weight compound of two or more alkoxysilanes. The degree of polymerization of the low-molecular-weight compound is preferably 10 or less, particularly around 2 to 6. Furthermore, in such a low-molecular-weight compound, a mono-alkoxysilane may be used in part.

[0139] Furthermore, many compounds possessing both alkoxysilyl groups and polymerizable unsaturated groups are known. Therefore, polymers comprising some or all of these compounds can also be used in the present invention.

[0140] Silane compounds (d-1) such as γ-(meth)acryloxypropyltrimethoxysilane, γ(meth)acryloxypropyltriethoxysilane, γ(meth)acryloxypropyltrisilanol, γ-(meth)acryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-styrylethyltrimethoxysilane, and allyltriethoxysilane; homopolymers of the reaction product (d-2) of the silane compound (d-1) with a trialkoxy or trihydroxysilane compound (e.g., methyltrimethoxysilane, phenyltrimethoxysilane, methyltrisilanol) (e.g., polysiloxane-based macromonomers described in Japanese Patent Publication No. 2-160879) or copolymers with other polymerizable unsaturated monomers (b) can be suitably used.

[0141] When the curing agent is a polyisocyanate compound and / or melamine resin, the amount of curing agent relative to the total amount of resin component (B) and curing agent (i.e., (amount of curing agent) / (amount of curing agent + amount of resin component) is preferably 0.01 to 50% by weight. This range of amounts is preferable because it allows for the simultaneous occurrence of curing reactions by transesterification and curing reactions by other curing agents. The lower limit is more preferably 0.01% by weight, and even more preferably 1% by weight. The upper limit is more preferably 30% by weight, and even more preferably 20% by weight.

[0142] When the curing agent is an alkoxysilane compound, it is preferable that (amount of curing agent) / (amount of curing agent + amount of resin component) is 0.001 to 10% by weight. This range of blending amounts is preferable because it allows the curing reaction by transesterification and the curing reaction by other curing agents to occur simultaneously.

[0143] In this invention, even when the blending ratio of the curing agent is relatively low, with (amount of curing agent) / (amount of curing agent + amount of resin component) being 1 to 20% by weight, sufficient curing performance is achieved. This is presumed to be because curing by the resin component (B) proceeds preferentially, and the curing reaction by the curing agent proceeds auxiliaryly, thereby accelerating the curing reaction.

[0144] The curing agent described above may be a combination of two or more of the polyisocyanate compounds, melamine resins, epoxy compounds, and alkoxysilane compounds mentioned above.

[0145] In the thermosetting resin composition of the present invention, when using the above-mentioned polyisocyanate compound, melamine resin, epoxy compound, and alkoxysilane compound as a curing agent, it is preferable that the polyol does not contain the above-mentioned structural unit (B) in its molecule. This is because curing proceeds sufficiently with these curing agents, and there is no advantage in having structural unit (B) present in the resin or resin composition (X).

[0146] Furthermore, the thermosetting resin composition containing the polymer of the present invention may be a thermosetting resin composition that uses transesterification as the curing reaction, as described in prior art publications such as International Publication 2021 / 132251, International Publication 2021 / 172307, International Publication 2021 / 095202, International Publication 2020 / 204089, International Publication 2019 / 139069, International Publication 2019 / 069783, and International Publication 2019 / 054136.

[0147] In this case, the resin or resin composition (X) has hydroxyl groups and alkyl ester groups. If the transesterification reaction is to be facilitated to the extent that it can be used as a thermosetting resin composition, it is preferable to introduce alkyl ester groups into the resin or resin composition (X) using components as described in the above-mentioned literature. These points will be explained in detail below.

[0148] (1) A polymer having some constituent units derived from the monomer represented by the general formula (4) described above. As described above, ester groups based on such structural units readily undergo transesterification reactions. Therefore, it is preferable to include such polymers as part of the resin or resin composition (X).

[0149] Furthermore, it is preferable that such polymers also have hydroxyl groups. That is, it is preferable that the same resin contains both hydroxyl groups and constituent units derived from the monomer represented by the general formula (4) described above.

[0150] (2) Compounds having two or more structures represented by the following general formula in their molecule

[0151] (3) Ester compounds In the present invention, an ester compound having an alkyl ester group can also be used as the resin component (A). Examples of such ester compounds include those listed below.

[0152] (3-1) (Compounds obtained by addition reaction between a compound having an active methylene group and a vinyl group) Compounds having an active methylene group represented by the following general formula (61) undergo addition reactions with vinyl groups.

[0153] [ka] (In the formula, R 14 This represents an alkyl group with 50 or fewer carbon atoms. X is OR 14 (Represents a group or a hydrocarbon group with 5 or fewer carbon atoms)

[0154] The structure of the alkyl ester group described above is not particularly limited, but known ester groups such as methyl ester group, ethyl ester group, benzyl ester group, n-propyl ester group, isopropyl ester group, n-butyl ester group, isobutyl ester group, and sec-butyl ester group can be used.

[0155] Specific examples of compounds having such an active methylene group include malonic acid esters and acetoacetate esters. Compounds obtained by adding these compounds to vinyl compounds can be used.

[0156] Compounds containing an active methylene group can be added to a double bond via a Michael addition reaction. A typical Michael addition reaction involving such a compound containing an active methylene group is shown in the following formula.

[0157] [ka]

[0158] The compounds obtained by such reactions have a structure represented by general formula (61), and since these compounds have two or more alkyl ester groups, they can be used particularly suitably for the purposes of the present invention. In particular, when (meth)acrylic acid or a derivative thereof is used as the vinyl compound of the above general formula,

[0159] [ka] This will result in the following reaction. In the above general formula, R 14 This represents an alkyl group with 50 or fewer carbon atoms. R 20 This represents a hydrogen or methyl group. R 19 This is not particularly limited and can be any functional group depending on the purpose. The ester compounds obtained from such reactions are

[0160] [ka] The molecule will contain constituent units represented by this structure.

[0161] In the reaction described above, by using an acrylic acid derivative having two or more unsaturated bonds as a starting material, an ester compound having two or more structures represented by the general formula (64) described above in the molecule can also be obtained. That is, having the functional group,

[0162] [ka] Compounds having a structure represented by the general formula can be suitably used in the present invention. Such compounds are preferable because they exhibit high transesterification reactivity and possess many COOR groups in their molecules, resulting in good curability. In the above general formula, n is most preferably between 2 and 12. Furthermore, Y is not particularly limited as long as the molecular weight of the compound is 3000 or less, and represents a hydrocarbon group which may have any functional group such as a hydroxyl group, ester group, or ether group.

[0163] While many compounds have structures derived from compound esters containing active methylene groups, the above-mentioned compound is particularly preferable because the addition reaction between the malonic acid ester and the vinyl group proceeds easily, making synthesis simple, and the number of ester groups can be adjusted by selecting the starting materials, thus allowing for easy adjustment of curing performance and the performance of the cured resin. Specifically, dimethyl malonate, di-n-butyl malonate, and the like can be suitably used.

[0164] Such compounds are obtained by performing a Michael addition reaction with a compound having an active methylene group, using various (meth)acrylic acid derivatives having one or more unsaturated bonds as starting materials. The above-mentioned "(meth)acrylic acid derivatives having one or more unsaturated bonds" are not particularly limited, but examples include the following.

[0165] Examples of (meth)acrylates with one functional group include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, and the like.

[0166] Examples of (meth)acrylates with two functional groups 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, and neopentyl glycol di(meth)acrylate. This includes acrylates, neopentyl glycol di(meth)acrylate hydroxypivalate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, glycerin di(meth)acrylate, dimethylol-root tricyclodecane di(meth)acrylate (DCP-A), bisphenol A EO adduct diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.; light acrylate BP-4EA, BP-10EA), and bisphenol A PO adduct diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.; BP-4PA, BP-10PA, etc.). In particular, bisphenol A PO adduct diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.; BP-4PA), dimethylol-root tricyclodecane di(meth)acrylate (DCP-A), etc. can be preferably used.

[0167] Examples of (meth)acrylates with three functional groups include trimethylolmethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropaneethylene oxide-modified tri(meth)acrylate, trimethylolpropanepropylene oxide-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin propoxy tri(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, etc. Among these, trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate can be preferably used.

[0168] Examples of (meth)acrylates with four functional groups include dipentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethylene oxide-modified tetra(meth)acrylate, pentaerythritol propylene oxide-modified tetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate. Among these, ditrimethylolpropane tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate are preferably used.

[0169] Examples of (meth)acrylates with four or more functional groups include pentaerythritol tetra(meth)acrylate, pentaerythritol ethylene oxide-modified tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane penta(meth)acrylate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane hexa(meth)acrylate, and hexa(meth)acrylate of caprolactone-modified dipentaerythritol, among other polyfunctional (meth)acrylates.

[0170] Specific examples of compounds that fall under compound (3) as described above are shown below.

[0171] [ka] In the formula, R represents an alkyl group with 50 or fewer carbon atoms.

[0172] The above compound (3) preferably has three or more alkyl ester groups in its molecule that act as crosslinking sites. In other words, the more alkyl ester groups in the molecule there are, the higher the crosslinking density of the resin after curing, which is preferable because it results in good hardness of the cured product and a cured product with excellent physical properties. It is more preferable that there are five or more alkyl esters in the molecule.

[0173] Such compounds can be dissolved or dispersed in an aqueous medium by diluting them with a water-soluble solvent and adding them, or by emulsification and dispersion using an emulsifier. In this case, methods include emulsifying and dispersing with an emulsifier after mixing with other components used in combination, or preparing a dispersion by emulsifying and dispersing only the above compound with an emulsifier, and then mixing this with the other components. Equipment used for emulsification and dispersion includes homomixers, high-pressure homogenizers, disperser mixers, ribbon mixers, propeller mixers, and high-pressure emulsifiers.

[0174] (3-2) Alkyl esters of polyfunctional carboxylic acids Compounds obtained by the reaction of a polyfunctional carboxylic acid with an alcohol can also be used as compounds having an alkyl ester group according to the present invention. Such reactions can be represented by the following general formula.

[0175] [ka]

[0176] Furthermore, compounds having alkyl ester groups obtained by performing a similar reaction on carboxylic acid derivatives can also be used for the purposes of the present invention.

[0177] Various polyfunctional carboxylic acids are versatile raw materials that are widely and inexpensively available for use in polyester raw materials, polyamide raw materials, neutralizing agents, synthetic raw materials, and many other applications. Compounds obtained by alkyl esterifying such polyfunctional carboxylic acids by known methods can also be used in the present invention.

[0178] When such compounds are used as compounds having alkyl ester groups, they can be esterified inexpensively using known methods, and polyvalent ester groups can be introduced at a relatively low molecular weight. Furthermore, esterification improves their compatibility with organic solvents, making them suitable for use, which is a desirable advantage.

[0179] The polyfunctional carboxylic acid used here is not particularly limited; for example, one with 50 or fewer carbon atoms can be used. More specifically, aliphatic polycarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, brassic acid, octadecanediic acid, citric acid, and butanetetracarboxylic acid; alicyclic 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, and 1,3,5-cyclohexanetricarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid Examples include aromatic polycarboxylic acids such as cindicarboxylic acid, 4,4'-biphenyldicarboxylic acid, trimellitic acid, and pyromellitic acid; fatty acids such as coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, and safflower oil fatty acid; 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, and 10-phenyloctadecanoic acid; and hydroxycarboxylic acids such as lactic acid, 3-hydroxybutanoic acid, and 3-hydroxy-4-ethoxybenzoic acid.

[0180] In the present invention, the method for alkyl esterification of the above-mentioned polyfunctional carboxylic acid is not particularly limited, and known methods such as dehydration condensation with an alcohol can be applied. Further, methods for alkyl esterifying derivatives of polyfunctional carboxylic acids can also be mentioned.

[0181] The alkyl esterified product of the above polyfunctional carboxylic acid preferably has a molecular weight of 10,000 or less. By making it such, the molecules move easily and it is preferable in terms of the progress of curing. The molecular weight can also be made lower, such as 6,000 or less, 4,000 or less, 2,000 or less.

[0182] <…(3-3) A compound having two or more functional groups represented by the general formula (31) The compound having two or more functional groups represented by the above general formula (31) can also be used in the present invention.

[0183] Regarding the functional group represented by the general formula (31), it has been described in detail above. Such a functional group is formed by reacting a compound represented by the general formula (32) with a carboxylic acid. Therefore, when various known polycarboxylic acids are reacted with the compound represented by the above general formula (32), a compound having two or more functional groups represented by the above general formula (31) can be obtained. Further, when reacted with a hydroxycarboxylic acid having a hydroxyl group, it becomes a compound having a hydroxyl group and the general formula (32), and this can also be used as a component of a thermosetting resin composition that undergoes a curing reaction by transesterification.

[0184] [… For use in the thermosetting resin composition of the present invention, the above compound is preferably a compound having two or more functional groups, and polycarboxylic acids having two or more carboxyl groups, hydroxycarboxylic acids having a carboxyl group and a hydroxyl group, etc. can be used.

[0185] Various polycarboxylic acids are general-purpose raw materials that are widely and inexpensively provided for many applications such as polyester raw materials, polyamide raw materials, neutralizing agents, synthetic raw materials, and others. Compounds obtained by converting such polycarboxylic acids into the functional groups represented by the above general formula (32) by known methods can also be used in the present invention.

[0186] When such a compound is used as a compound having a functional group represented by the general formula (32), it can be esterified at low cost by a known method, and a polyvalent ester group can be introduced with a relatively low molecular weight. Further, it is preferable in that the compatibility with an organic solvent is improved by esterification and it can be suitably used.

[0187] The polycarboxylic acid used here is not particularly limited, and for example, those having 50 or less carbon atoms can be used. More specifically, aliphatic polyvalent carboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassilic acid, octadecanedioic acid, citric acid, butanetetracarboxylic acid, etc.; alicyclic polyvalent carboxylic 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, etc.; aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, trimellitic acid, pyromellitic acid, etc.; Fatty acids such as coconut oil fatty acids, cottonseed oil fatty acids, hemp seed oil fatty acids, rice bran oil fatty acids, fish oil fatty acids, tall oil fatty acids, soybean oil fatty acids, linseed oil fatty acids, tung oil fatty acids, rapeseed oil fatty acids, castor oil fatty acids, dehydrated castor oil fatty acids, and safflower oil fatty acids; 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, and 10-phenyloctadecanoic acid; hydroxycarboxylic acids such as lactic acid, 3-hydroxybutanoic acid, and 3-hydroxy-4-ethoxybenzoic acid; Examples include:

[0188] The compound obtained by substituting the carboxylic acid group of the above polycarboxylic acid with the structure represented by the above general formula (31) preferably has a molecular weight of 10,000 or less. This is preferable because the molecules are more mobile and the curing process proceeds more easily. The molecular weight can also be lower, such as 6,000 or less, 4,000 or less, or 2,000 or less.

[0189] As an example of such a compound, the general structure of the compound obtained when citric acid is used as the polycarboxylic acid and the above reaction is carried out is shown below.

[0190] [ka]

[0191] (3-4) Compounds having two or more functional groups represented by general formula (41) and / or general formula (42). Compounds having a functional group represented by general formula (41) and / or a functional group represented by general formula (42) can be obtained by the manufacturing method described above. Compounds having two or more such functional groups, or compounds having such functional groups and hydroxyl groups, can be suitably used as components of resin compositions in which transesterification is the curing reaction.

[0192] Compounds having a functional group represented by general formula (41) and / or a functional group represented by general formula (42) are used as curable functional groups in curable resin compositions. Therefore, it is preferable that the compound has two or more functional groups. More specifically, it may have two or more functional groups represented by general formula (41) and / or general formula (42), or it may have a hydroxyl group or the like in addition to the functional group represented by general formula (41) and / or general formula (42) described above.

[0193] As described above, the functional group represented by general formula (41) and / or the functional group represented by general formula (42) can be introduced into various epoxy compounds by carrying out the reaction represented by general formula (51) or general formula (54). Therefore, compounds obtained by carrying out the reaction represented by the above general formula (54) with known epoxy compounds can also be used in the present invention. The epoxy compounds that can be used in such reactions are not particularly limited, but examples include aliphatic polyfunctional liquid epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol derivative epoxy resins, naphthalene skeleton or alicyclic skeleton-containing novolac epoxy resins, and epoxy resins in which the oxirane ring is a glycidyl ether. The epoxy compounds are preferably compounds having two or more epoxy groups in one molecule.

[0194] Furthermore, as described above, epoxy compounds can be obtained by carrying out the reaction represented by general formula (53) with a carboxylic acid or its derivative. Then, by carrying out the reaction represented by general formula (51) and / or general formula (54) with the epoxy compound, a compound having a functional group represented by general formula (41) and / or a functional group represented by general formula (42) can be obtained. Therefore, by carrying out the above-described reaction with various polycarboxylic acids and hydroxycarboxylic acids, a compound having two or more such functional groups, or a compound having such a functional group and a hydroxyl group can be obtained.

[0195] The polycarboxylic acid that can be used as a starting material when obtaining a compound having a functional group represented by general formula (41) and / or a functional group represented by general formula (42) by the above reaction is not particularly limited, and for example, those with 50 or fewer carbon atoms can be used. More specifically, aliphatic polycarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, brassic acid, octadecanediic acid, citric acid, and butanetetracarboxylic acid; Alicyclic 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, and 1,3,5-cyclohexanetricarboxylic acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, trimellitic acid, and pyromellitic acid; Examples of fatty acids include coconut oil fatty acids, cottonseed oil fatty acids, hemp seed oil fatty acids, rice bran oil fatty acids, fish oil fatty acids, tall oil fatty acids, soybean oil fatty acids, linseed oil fatty acids, tung oil fatty acids, rapeseed oil fatty acids, castor oil fatty acids, dehydrated castor oil fatty acids, and safflower oil fatty acids; and 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, and 10-phenyloctadecanoic acid.

[0196] When using the above reaction to obtain a compound having a functional group represented by the general formula (41) and / or a functional group represented by the general formula (42), hydroxycarboxylic acids having a carboxyl group and a hydroxyl group that can be used as raw materials include hydroxycarboxylic acids such as glycolic acid, citric acid, lactic acid, 3-hydroxybutanoic acid, 3-hydroxy-4-ethoxybenzoic acid; etc. can be mentioned.

[0197] As specific examples of such compounds, for example, compounds having the structures shown below can be mentioned.

[0198]

Chemical formula

[0199] (3-5) Cyanuric acid ester compounds As the ester compounds having an alkyl ester group used in the present invention, for example, the cyanuric acid ester compounds exemplified below can be mentioned.

[0200] One of them is an ester compound having an isocyanuric acid ring represented by the following general formula (71).

[0201]

Chemical formula

[0202] The ester compound represented by the above general formula (71) has two or three alkyl ester groups and can be made particularly excellent in transesterification reactivity. For this reason, it is particularly preferable to obtain a resin composition in which the curing start temperature is 130°C or lower and the gel fraction when cured under conditions of baking at 150°C for 30 minutes is 80% or more.

[0203] The monomer represented by the above general formula (71) is more preferably one in which R3 has a primary or secondary alkyl ester group. Primary or secondary alkyl ester groups derived from such monomers readily react with hydroxyl groups, and for this reason, the objectives of the present invention can be fully achieved.

[0204] The alkyl ester group is not particularly limited, and known ester groups such as methyl ester group, ethyl ester group, benzyl ester group, n-propyl ester group, isopropyl ester group, n-butyl ester group, isobutyl ester group, and sec-butyl ester group can be used. It is preferable that the alkyl group has 50 or fewer carbon atoms. Since the alkyl group is preferably generated as an alcohol during the transesterification reaction and volatilizes, it is more preferable that the alkyl group has 20 or fewer carbon atoms, and even more preferable that it has 10 or fewer carbon atoms. Furthermore, it is preferable that the boiling point of the alcohol volatilized during the curing reaction is 300°C or lower, and even more preferable that it is 200°C or lower.

[0205] The method for producing the ester compound represented by the above general formula (71) is not particularly limited, but one example is the reaction of a halogenated carboxylic acid ester with cyanuric acid. This reaction can be expressed in general formula as follows.

[0206] [ka] (In the formula, R3 is an alkyl group having 50 or fewer carbon atoms.) R4 is an alkylene group with 50 or fewer carbon atoms. X is a halogen element.

[0207] Any known halogenated carboxylic acid ester can be used in the above-described reaction, for example, methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, isopropyl chloroacetate, methyl 2-chloropropionate, ethyl 2-chloropropionate, propyl 2-chloropropionate, isopropyl 2-chloropropionate, methyl 2-chlorobutyrate, ethyl 2-chlorobutyrate, propyl 2-chlorobutyrate, isopropyl 2-chlorobutyrate, methyl bromoacetate, ethyl bromoacetate, propyl bromoacetate, isopropyl bromoacetate, methyl 2-bromopropionate, ethyl 2-bromopropionate, 2-bromopropyl Examples include propyl ropionate, isopropyl 2-bromopropionate, methyl 2-bromobutyrate, ethyl 2-bromobutyrate, propyl 2-bromobutyrate, isopropyl 2-bromobutyrate, ethyl iodoacetate, propyl iodoacetate, isopropyl iodoacetate, methyl 2-iodopropionate, ethyl 2-iodopropionate, propyl 2-iodopropionate, isopropyl 2-iodopropionate, methyl 2-iodobutanoate, ethyl 2-iodobutanoate, propyl 2-iodobutanoate, and isopropyl 2-iodobutanoate. The above reaction is a well-known and common reaction, and its reaction conditions can be carried out under general conditions.

[0208] Another method for producing the ester compound represented by the above general formula (71) is to react an orthoformate ester with a carboxylic acid having an isocyanuric acid ring. This reaction can be represented by the following general formula.

[0209] [ka] (In the formula, R5 is a structure represented by hydrogen or R4-COOH.) R4 is an alkylene group with 50 or fewer carbon atoms. R6 is a hydrogen atom or a structure represented by R4-COOR3.

[0210] Examples of carboxylic acids having an isocyanuric acid ring used in the above-described reaction include tris(2-carboxyethyl) isocyanurate and bis(2-carboxyethyl) isocyanurate. Furthermore, examples of orthoformate esters used in the above-mentioned reaction include methyl orthoformate and ethyl orthoformate. The above reaction is a well-known and common reaction, and its reaction conditions can be carried out under general conditions.

[0211] The following are examples of specific chemical structures of ester compounds having an isocyanuric acid ring represented by the general formula (71) described above. However, the present invention is not limited to the compounds exemplified below.

[0212] [ka]

[0213] In addition to the above, other examples of cyanuric acid-based ester compounds used in the present invention include the following examples.

[0214] [ka] (In the formula, R 11 This refers to an alkylene group with 50 or fewer carbon atoms. R 12 (This refers to alkyl groups with 50 or fewer carbon atoms.)

[0215] The ester compound represented by the above general formula (72) can also be made particularly excellent in terms of transesterification reactivity. For this reason, it is particularly preferable to obtain a resin composition in which the curing start temperature is 130°C or lower and the gel fraction when cured under conditions of baking at 150°C for 30 minutes is 80% or more.

[0216] The method for producing the ester compound represented by the above general formula (72) is not particularly limited, but for example, one method is to react a hydroxycarboxylic acid ester with cyanuric acid chloride. This reaction can be expressed in general formula as follows.

[0217] [ka]

[0218] Furthermore, examples of hydroxy acid esters used in the above-mentioned reactions include methyl glycolate, ethyl glycolate, butyl glycolate, methyl hydroxypropionate, ethyl hydroxypropionate, butyl hydroxypropionate, methyl hydroxybutyrate, ethyl hydroxybutyrate, butyl hydroxybutyrate, methyl lactate, ethyl lactate, and butyl lactate.

[0219] When various cyanuric acid compounds are used in the present invention, they have the advantage of producing coating films that exhibit excellent film properties with high crosslink density even at low temperatures during curing. When such compounds are used as compounds having alkyl ester groups, they can be esterified inexpensively using known methods, and polyvalent ester groups can be introduced at a relatively low molecular weight.

[0220] (4) Low molecular weight polyols In addition, low molecular weight polyols (specifically, those with a molecular weight of 2,000 or less) may be used as compounds having at least two hydroxyl groups in the molecule. Examples of low molecular weight polyols include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,2-butanediol, 1,1,1-trimethylolpropane, and 2-butyl-2 -Ethyl-1,3-propanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-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- Examples include dihydric alcohols such as hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, neopentyl glycol hydroxypivalate, hydrogenated bisphenol A, hydrogenated bisphenol F, and dimethylolpropionic acid; polylactone diols obtained by adding lactone compounds such as ε-caprolactone to the above dihydric alcohols; ester diol compounds such as bis(hydroxyethyl) terephthalate; polyether diol compounds such as alkylene oxide adducts of bisphenol A, polyethylene glycol, polypropylene glycol, and polybutylene glycol; and trihydric or higher alcohols such as glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tris(2-hydroxyethyl)isocyanuric acid, sorbitol, and mannitol.

[0221] Such low molecular weight polyols are commonly known and inexpensive. Furthermore, low molecular weight polyols have high water solubility and can be suitably used as crosslinking agents when curing is required in an aqueous system.

[0222] The resin component (A) is preferably at least one compound selected from the group consisting of radical copolymer polymers, addition-condensation oligomers, and low molecular weight compounds. Specifically, it is preferable to use radical copolymer polymers such as acrylic resins, addition-condensation oligomers such as polyester resins, and low molecular weight compounds with a molecular weight of 6000 or less (more preferably 4000 or less, and even more preferably 2000 or less). Two or more of these may be used in combination. Furthermore, the curable resin composition of the present invention only needs to be in a resin state after curing, and even mixtures of low molecular weight compounds that can be cured into a resin are included.

[0223] Furthermore, it is preferable not to use compounds that have only one hydroxyl group or alkyl ester group. It is preferable to use compounds that have a total of two or more functional groups, including hydroxyl groups and alkyl ester groups, or compounds that have a (meth)acryloyl group and a hydroxyl group and / or an alkyl ester group. Compounds that have only one hydroxyl group or alkyl ester group as a functional group cannot form a chain structure and may hinder the curing reaction. Compounds having each functional group will be described in detail below. Note that the following description is illustrative, and the compounds used in the present invention are not limited to those described below.

[0224] The resin composition of the present invention may further contain a compound having a (meth)acryloyl group. Alternatively, a compound having an unsaturated group in the polymer as described above may be used. Such a composition can be obtained that possesses both thermosetting and energy ray curing properties. The compounds having a (meth)acryloyl group in such compositions will be described in detail below.

[0225] Compounds having a (meth)acryloyl group Many compounds known as energy-ray curable compounds can be used as compounds having a (meth)acryloyl group.

[0226] Examples of (meth)acrylates with one functional group include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, and the like.

[0227] Examples of (meth)acrylates with two functional groups 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, and neopentyl glycol di(meth)acrylate. This includes acrylates, neopentyl glycol di(meth)acrylate hydroxypivalate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, glycerin di(meth)acrylate, dimethylol-root tricyclodecane di(meth)acrylate (DCP-A), bisphenol A EO adduct diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.; light acrylate BP-4EA, BP-10EA), and bisphenol A PO adduct diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.; BP-4PA, BP-10PA, etc.). In particular, bisphenol A PO adduct diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.; BP-4PA), dimethylol-root tricyclodecane di(meth)acrylate (DCP-A), etc. can be preferably used.

[0228] Examples of (meth)acrylates with three functional groups include trimethylolmethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropaneethylene oxide-modified tri(meth)acrylate, trimethylolpropanepropylene oxide-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin propoxy tri(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, etc. Among these, trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate can be preferably used.

[0229] Examples of (meth)acrylates with four functional groups include dipentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethylene oxide-modified tetra(meth)acrylate, pentaerythritol propylene oxide-modified tetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate. Among these, ditrimethylolpropane tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate are preferably used.

[0230] Examples of (meth)acrylates with four or more functional groups include pentaerythritol tetra(meth)acrylate, pentaerythritol ethylene oxide-modified tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane penta(meth)acrylate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane hexa(meth)acrylate, and hexa(meth)acrylate of caprolactone-modified dipentaerythritol, among other polyfunctional (meth)acrylates.

[0231] Furthermore, compounds having a (meth)acryloyl group in the molecule and a viscosity of 100 Pa·s (25°C) or higher can also be used. Such compounds preferably have a number-average molecular weight exceeding 800.

[0232] While a great many types of such compounds are known, among them, (meth)acrylic esters of aromatic epoxides having hydroxyl groups in the molecule, and urethane acrylic resins (urethane prepolymers) having urethane groups in the molecule are preferred. More specifically, examples include (meth)acrylic acid adducts of bisphenol A diglycidyl ether (e.g., Epoxy Ester 3000A, manufactured by Kyoeisha Chemical Co., Ltd.), pentaerythritol tri(meth)acrylate hexamethylene diisocyanate urethane prepolymers (e.g., UA-306H, manufactured by Kyoeisha Chemical Co., Ltd.), acrylic acid adducts of bisphenol A PO2mol adduct diglycidyl ether (e.g., Epoxy Ester 3002A, manufactured by Kyoeisha Chemical Co., Ltd.), pentaerythritol triacrylate toluene diisocyanate urethane prepolymers (e.g., UA-306T, manufactured by Kyoeisha Chemical Co., Ltd.), pentaerythritol triacrylate isophorone diisocyanate urethane prepolymers (e.g., UA-306I, manufactured by Kyoeisha Chemical Co., Ltd.), UF-8001G, BPZA-66, etc.

[0233] Furthermore, compounds in which an unsaturated bond has been introduced to various polyol compounds, such as vinyl polymers having hydroxyl groups, by reacting them with a compound having an isocyanate group and an unsaturated bond can be used. in particular,

[0234] [ka]

[0235] Unsaturated group-containing compounds obtained by the reaction can also be used.

[0236] The compounds having an isocyanate group and a polymerizable unsaturated group that can be used in the above reaction are not particularly limited, and examples include compounds represented by the following general formula (72).

[0237] [ka] (In the formula, R 32 These are hydrocarbon groups with 1 to 20 carbon atoms. R 31 (H or methyl group)

[0238] More specifically, examples include 2-isocyanatoethyl acrylate, which is sold under the trade name Karens AOI (registered trademark) by Showa Denko Corporation.

[0239] The polyol compound is not particularly limited, and various hydroxyl group-containing compounds such as known acrylic polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, and polymers having polyvinyl alcohol units can be used.

[0240] Furthermore, compounds in which unsaturated groups have been introduced by reacting epoxy group-containing polymers with (meth)acrylic acid can also be used. Specifically,

[0241] [ka]

[0242] Unsaturated group-containing compounds obtained by the reaction can also be used. The epoxy-containing compounds that can be used in the above reaction are not particularly limited, and include various epoxy resins such as bisphenol-based epoxy resins and novolac-based epoxy resins, as well as acrylic polymers containing glycidyl (meth)acrylate as part of the monomer.

[0243] The resin or resin composition (X) having hydroxyl groups and alkyl ester groups is not particularly limited and may be a copolymer having both hydroxyl groups and alkyl ester groups, or a resin composition obtained by mixing a polymer having hydroxyl groups and a polymer having alkyl ester groups. Furthermore, the resin composition may contain all of the polymer having hydroxyl groups, the polymer having alkyl ester groups, and the resin having both hydroxyl groups and alkyl ester groups.

[0244] The resin or resin composition (X) is not particularly limited, and examples include a resin or resin composition having constituent units derived from the monomer represented by the general formula (4) above and constituent units derived from the hydroxyl group-containing monomer.

[0245] When comparing the solubility parameters of the thermosetting resin composition of the present invention with those of the resin composition (X) and the surface modifier described above, the solubility parameter of the surface modifier is smaller, and it is preferable that the difference is 3.0 or less. As described above, it is preferable that the surface modifier of the present invention is unevenly distributed in the coating film, near the surface of the coating film. From this viewpoint, if the resin composition (X) contains two or more components, it is preferable that each component has the difference in solubility parameters described above.

[0246] In the thermosetting resin composition of the present invention, if the solubility parameter of the surface modifier is higher than that of the resin composition (X), the surface modifier will not orient itself on the surface. Also, if the solubility parameter of the surface modifier is lower than that of the resin composition (X), and the difference is 3.0 or more, the compatibility becomes too poor, causing the surface modifier to aggregate and resulting in defects such as repulsion.

[0247] The thermosetting resin composition of the present invention further contains a transesterification catalyst (Z). The transesterification catalyst is not particularly limited and any known catalyst can be used.

[0248] In the thermosetting resin composition of the present invention, it is most preferable to use a metal compound catalyst as the transesterification catalyst (B). The transesterification reactivity of the metal compound catalyst can be obtained by selecting the type of metal or by using it in combination with other compounds. Furthermore, it is preferable in that the necessary performance can be obtained as appropriate by combining it with the resin composition.

[0249] The above metal compound catalyst is preferably a compound (B-1) containing at least one metal element selected from the group consisting of zinc, tin, titanium, aluminum, zirconium, and iron. Such compounds are preferred in that they have suitable transesterification reactivity. Among these, zinc and zirconium are particularly preferred in that they have excellent transesterification reactivity.

[0250] Among the compounds mentioned above, zirconium compounds are particularly preferred because they possess extremely excellent transesterification ability, and their use allows for the easy acquisition of the thermosetting resin compositions described above. Furthermore, when using a zirconium compound as a transesterification catalyst, it is preferable because a very high transesterification capacity can be obtained even without using compound (B-2), which is detailed below, in combination.

[0251] Using a zirconium compound as a transesterification catalyst in a thermosetting resin composition where transesterification is the curing reaction is a novel invention. Therefore, a thermosetting resin composition containing a resin component (A) having -COOR (where R is an alkyl group with 50 or fewer carbon atoms) and a hydroxyl group, and a zirconium compound as a transesterification catalyst (B), is also one of the present inventions.

[0252] Examples of the metal compound catalysts mentioned above include various metal compounds such as zinc acetate, zinc acrylate, zinc acetylacetonate, zinc trifluoromethanesulfonate, zinc oxide, aluminum isopropylate, iron chloride, zinc dithiocarbamate, tetraisopropyl titanate, dibutyltin dilaurate, dibutyltin dioctate, monobutylstainic acid, zirconium butoxide, zirconium acetylacetonate, and zirconia. Furthermore, zinc cluster catalysts (for example, ZnTAC24 (trade name) manufactured by Tokyo Chemical Industry Co., Ltd.) can also be used. In addition, two or more of the above-mentioned compounds may be used in combination.

[0253] As the above-mentioned metal compound catalyst, metal salt compounds are particularly preferred, and the use of metal acetylacetonate as the anionic component is preferred because it tends to yield better transesterification ability than the same type of metal compound. For example, zinc acetylacetonate and zirconium acetylacetonate can be used particularly favorably. In particular, zirconium acetylacetonate exhibits extremely good catalytic performance.

[0254] Furthermore, when using zinc oxide, it is preferable to use a form dispersed in acetylacetone. It is believed that zinc acetylacetonate is produced by dispersing zinc oxide in acetylacetone. The zinc oxide and acetylacetone mentioned above are preferably contained in a ratio of 1:0.5 to 1:10 (by weight). By blending them in this ratio, particularly favorable results can be obtained. The lower limit is more preferably 1:0.8, and even more preferably 1:1. The upper limit is more preferably 1:5, and even more preferably 1:3.

[0255] When using the above metal compounds as catalysts, it is more preferable to further use at least one compound (B-2) selected from the group consisting of organophosphorus compounds, urea, alkylated urea, thiourea, alkylated thiourea, sulfoxide compounds, quaternary ammonium compounds, quaternary phosphonium compounds, and pyridine, quinoline, isoquinoline, phenanthroline and their derivatives, as this improves catalytic performance. Using these compounds in combination to activate the metal compound is particularly preferable because it allows for obtaining the curing initiation temperature and gel fraction described above.

[0256] Although the mechanism by which these effects are obtained is not clear, it is presumed that the catalytic activity is improved by the coordination of compound (B-2) with the metal compound. Therefore, it is preferable to select a compound (B-2) that can coordinate with the metal compound.

[0257] By improving the catalytic activity of the transesterification reaction, it becomes possible to carry out the reaction at lower temperatures. Therefore, the reaction temperature can be lowered, improving energy efficiency. Furthermore, it can be used even when transesterifying compounds with low heat resistance.

[0258] Our research has revealed that the reactivity of conventional transesterification reactions decreases in the presence of carboxyl groups in the system. Therefore, when attempting to utilize transesterification reactions in aqueous curable resin compositions containing carboxyl groups, high-temperature curing was required.

[0259] Through our investigations, we have found that these problems can be significantly improved by using compound (B-2) in combination with the above-mentioned metal compound. Specifically, this improves catalytic activity, allowing the reaction to proceed in the range of 80 to 150°C. Furthermore, it enables the reaction to proceed even in systems where the reaction is difficult to proceed due to various factors. For example, it is preferable in that it can proceed the reaction even in systems where carboxyl groups are present. Therefore, it can be suitably used as a catalyst for transesterification reactions in aqueous thermosetting resin compositions.

[0260] Conventional thermosetting resin compositions that utilize transesterification as a thermosetting reaction were known to carry out the transesterification reaction using an acid catalyst. However, such thermosetting resin compositions had various problems due to the presence of acid.

[0261] For example, amine compounds are sometimes used as additives such as pigment dispersants. Furthermore, when making paints water-based, it is common practice to introduce acidic groups such as carboxylic acid groups and sulfonic acid groups into the resin and neutralize them with amine compounds to make them water-soluble. In this case, it was difficult to use in combination with an acidic catalyst. This was a problem that hindered the water-based production of thermosetting resin compositions that use transesterification catalysts as the curing reaction. Transesterification catalyst (B) is preferable because it can produce a good curing reaction without using an acidic catalyst, and therefore allows for the creation of thermosetting resin compositions with added basic compounds.

[0262] Furthermore, even when the thermosetting resin composition of the present invention is used as a solvent-based paint composition, it may be used in combination with an aqueous paint as one of the layers of a multilayer coating. In this case, when the multilayer coating is heated and cured simultaneously, amines, ammonia, etc., may be generated from the other layers forming the multilayer coating. The above-mentioned catalyst is preferable in that it can perform good curing even in such cases.

[0263] Furthermore, it is preferable that the transesterification catalyst according to the present invention be used as a catalyst in a transesterification reaction under normal pressure. Moreover, it is preferable to use it as a transesterification catalyst in a curable resin composition in which a transesterification reaction is used as the curing reaction.

[0264] As described above, the transesterification catalyst (B) preferably contains at least one compound (B-2) selected from the group consisting of organophosphorus compounds, urea, alkylated urea, thiourea, alkylated thiourea, sulfoxide compounds, quaternary ammonium compounds, quaternary phosphonium compounds, and pyridine, quinoline, isoquinoline, phenanthroline and their derivatives. These compounds will be described in detail below.

[0265] The above-mentioned organophosphorus compounds are not particularly limited and include, for example, phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphoniotic acid, organophosphine oxide, organophosphine compounds, and various esters, amides, and salts thereof. The esters may be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ether, aryl, and substituted aryl esters. The amides may be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ether, aryl, and substituted aryl amides.

[0266] Among these, it is particularly preferable that the compound be at least one selected from the group consisting of phosphonic acid esters, phosphate amides, and organophosphine oxide compounds. Using these organophosphorus compounds results in the best transesterification catalytic function. More specifically, organophosphine oxide compounds such as triphenylphosphine oxide, trioctylphosphine oxide, and tricyclohexylphosphine oxide; phosphate amide compounds such as hexamethyl phosphate triamide and tris(N,N-tetramethylene) phosphate triamide; organophosphine sulfide compounds such as triphenylphosphine sulfide, tributylphosphine sulfide, and trioctylphosphine sulfide can be suitably used.

[0267] The alkylated urea mentioned above is not particularly limited and can include urea, dimethylurea, dimethylpropylene urea, etc. It may also have a cyclic structure, such as dimethylpropylene urea.

[0268] The alkylated thiourea mentioned above is not particularly limited and can include dimethylthiourea, trimethylthiourea, tetramethylthiourea, diethylthiourea, dibutylthiourea, etc. The sulfoxide compound mentioned above can include dimethyl sulfoxide, diphenyl sulfoxide, etc.

[0269] As the above-mentioned quaternary ammonium compound, the compound represented by the following general formula (i) is preferably used. [ka] (However, in equation (i), R 41 ~R 44 Each of these independently represents a monovalent hydrocarbon group or a monovalent hydrocarbon group to which a reaction-inert functional group is attached, Y 1- R represents a monovalent anion. 41 ~R 44 These may be the same group or different groups.

[0270] R 41 ~R 44 When R is a hydrocarbon group, examples include alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, and aryl groups, with alkyl groups and aryl groups being preferred. 41 ~R 44 The number of carbon atoms in each atom is preferably 1 to 100, and more preferably 4 to 30.

[0271] R 41 ~R 44However, in the case of a monovalent hydrocarbon group to which a reaction-inert functional group is attached, the functional group is appropriately selected depending on the reaction conditions, but examples include halogen atoms, alkoxycarbonyl groups, acyloxy groups, nitrile groups, acyl groups, carboxyl groups, and alkoxyl groups.

[0272] In the above formula (i), the quaternary ammonium (R 41 R 42 R 43 R 44 N + Examples of these include tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetra-n-butylammonium, methyltri-n-octylammonium, n-dodecyltrimethylammonium, n-dodecyltri-n-butylammonium, cetyltrimethylammonium, trimethylbenzylammonium, triethylbenzylammonium, cetylbenzyldimethylammonium, trimethyl-2-hydroxyethaneaminium, cetylpyridinium, n-dodecylpyridinium, phenyltrimethylammonium, phenyltriethylammonium, N-benzylpicolinium, pentamethonium, and hexamethonium.

[0273] In the above general formula (i), Y 1- Examples of suitable ions include fluoride ions, chloride ions, bromide ions, iodide ions, sulfate ions, nitrate ions, phosphate ions, perchlorate ions, bisulfate ions, hydroxide ions, acetate ions, benzoate ions, benzenesulfonate ions, and p-toluenesulfonate ions. Fluoride ions, chloride ions, bromide ions, iodide ions, hydroxide ions, and acetate ions are preferred, fluoride ions, chloride ions, bromide ions, iodide ions, and hydroxide ions are more preferred, and chloride ions or bromide ions are even more preferred.

[0274] As for the compound represented by the above general formula (i), from the viewpoint of versatility and reactivity, the following quaternary ammonium (R 41 R 42 R 43 R 44 N +) and the following Y 1- A combination with quaternary ammonium (R 41 R 42 R 43 R 44 N + Tetramethylammonium, tetra-n-butylammonium, n-dodecyltrimethylammonium, n-dodecyltri-n-butylammonium, triethylbenzylammonium, trimethyl-2-hydroxyethaneaminium. Y 1- Fluoride ions, chloride ions, bromide ions, iodide ions, hydroxide ions, acetate ions.

[0275] The quaternary ammonium compound is preferably at least one selected from the group consisting of 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-hydroxyethaneaminium chloride (cholinchloride), in terms of reactivity, industrial availability, price, and ease of handling.

[0276] Examples of quaternary phosphonium compounds include those represented by the following general formula (ii). [ka] (However, in equation (ii), R 51 ~R 54 Each of these independently represents a monovalent hydrocarbon group, Y 2- R represents a monovalent anion. 51 ~R 54 These may be the same group or different groups.

[0277] R 51 ~R 54Examples of the hydrocarbon group in [it] include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, etc., and an alkyl group and an aryl group are preferred.

[0278] Examples of the quaternary phosphonium (R 51 R 52 R 53 R 54 P + ) in the above general formula (ii) include tetraethylphosphonium, tetra-n-butylphosphonium, ethyltri-n-octylphosphonium, cetyltriethylphosphonium, cetyltri-n-butylphosphonium, n-butyltriphenylphosphonium, n-amyltriphenylphosphonium, methyltriphenylphosphonium, benzyltriphenylphosphonium, tetraphenylphosphonium, etc.

[0279] Y 2- Examples of [it] include chloride ion, fluoride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, hydrogen sulfate ion, hydroxide ion, acetate ion, benzoate ion, benzenesulfonate ion, p-toluenesulfonate ion, etc., and fluoride ion, chloride ion, bromide ion, and hydroxide ion are preferred.

[0280] From the viewpoints of reactivity and industrial availability, it is preferably at least one selected from the group consisting of tetra-n-butylphosphonium hydroxide, tetrabutylphosphonium bromide, and tetrabutylphosphonium chloride.

[0281] Examples of the above pyridine derivative include dimethylaminopyridine, nicotinic acid ester, etc.

[0282] Examples of the above quinoline derivative include 8-hydroxyquinoline, 2-methyl-8-quinolinol, etc.

[0283] The transesterification catalyst preferably contains compound (B-1) and compound (B-2) in a ratio of (B-1):(B-2) = 100:1 to 1:100 (by weight). Particularly favorable results can be obtained by blending in such ratios. The lower limit of the above ratio is more preferably 50:1, and even more preferably 10:1. The upper limit of the above ratio is more preferably 1:50, and even more preferably 1:10.

[0284] The above compound (B-1) is preferably included in a proportion of 0.01 to 50% by weight relative to the amount of compounds involved in the reaction in the reaction system when the reaction occurs. The above compound (B-2) is preferably included in a proportion of 0.01 to 50% by weight relative to the amount of compounds involved in the reaction in the reaction system when the reaction occurs.

[0285] In the resin composition of the present invention, the above-mentioned physical properties can be particularly favorably obtained by using (1) a zirconium compound as the transesterification catalyst (B), or (2) the above-mentioned compound (B-1) and compound (B-2). By using the transesterification catalysts described in (1) and (2) above, and selecting a resin composition with particularly high transesterification reactivity, it is possible to obtain a resin composition having a curing start temperature of 130°C or lower and a gel fraction of 80% or more when cured under conditions of baking at 150°C or lower for 30 minutes.

[0286] Using the transesterification catalyst described in (2) above in a thermosetting resin composition in which transesterification is the curing reaction is a novel invention. Therefore, a thermosetting resin composition containing a resin component (A) having -COOR (where R is an alkyl group with 50 or fewer carbon atoms) and a hydroxyl group, and the transesterification catalyst described in (2) above as the transesterification catalyst (B), is also one of the present inventions.

[0287] Furthermore, by using zinc acetylacetonate as a transesterification catalyst and selecting a resin composition with particularly high transesterification reactivity, it is possible to obtain a resin composition having a curing initiation temperature of 100°C or lower and a gel fraction of 80% or more when cured under conditions of baking at 100°C or lower for 30 minutes.

[0288] Furthermore, among the transesterification catalysts containing compound (B-1) and compound (B-2) as described above, a transesterification catalyst containing compound (B-1) which includes at least one metal element selected from the group consisting of zinc, tin, titanium, aluminum, zirconium, and iron, and at least one compound (B-2) selected from the group consisting of organophosphorus compounds, urea, alkylated urea, thiourea, alkylated thiourea, sulfoxide compounds, quaternary ammonium compounds, quaternary phosphonium compounds, phenanthroline, and its derivatives, is a novel transesterification catalyst. Therefore, such a catalyst is also one of the present inventions.

[0289] The thermosetting resin composition of the present invention can be suitably used in fields such as thermosetting paints and thermosetting adhesives. Furthermore, it can also be used as an air-drying type curing resin composition.

[0290] When used as a thermosetting paint, in addition to the components mentioned above, additives commonly used in the paint industry may be used in combination. For example, leveling agents, defoamers, coloring pigments, extender pigments, lustrous pigments, pigment dispersants, rheology control agents, UV absorbers, and any combination thereof may be used in combination.

[0291] When using pigments, it is preferable that the total solid content of the resin components be in the range of 1 to 500% by weight, based on 100% by weight of the total solid content of the resin components. The lower limit is more preferably 3% by weight, and even more preferably 5 parts by weight. The upper limit is more preferably 400% by weight, and even more preferably 300% by weight.

[0292] Examples of the above-mentioned coloring pigments include titanium dioxide, zinc oxide, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, surene pigments, perylene pigments, dioxazine pigments, diketopyrrolopyrrole pigments, and any combination thereof.

[0293] Examples of the above-mentioned extender pigments include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, alumina white, etc., with barium sulfate and / or talc being preferred, and barium sulfate being more preferred.

[0294] Examples of the above-mentioned luminous pigments include aluminum (including vapor-deposited aluminum), copper, zinc, brass, nickel, aluminum oxide, mica, titanium oxide or iron oxide-coated aluminum oxide, mica coated with titanium oxide or iron oxide, glass flakes, holographic pigments, and any combination thereof. The above-mentioned aluminum pigments include non-leafing aluminum and leafing aluminum.

[0295] The above-mentioned coloring pigment is preferably dispersed in a pigment-dispersing resin and then incorporated into the thermosetting resin composition. The amount of coloring pigment may vary depending on the type of pigment, but generally, it is preferably in the range of about 0.1 to about 300 parts by weight, and more preferably about 1 to about 150 parts by weight, per 100 parts by weight of the solid content of the resin component contained in the pigment-dispersing resin.

[0296] The above-mentioned thermosetting paint may further contain, if desired, paint additives such as organic solvents, thickeners, ultraviolet absorbers, light stabilizers, defoamers, plasticizers, surface modifiers, anti-settling agents, dispersants, anti-separation agents, rheology control agents, leveling agents, substrate wetting agents, and slip agents.

[0297] Examples of the above-mentioned thickening agents include inorganic thickening agents such as silicates, metal silicates, montmorillonite, and colloidal alumina; polyacrylic acid-based thickening agents such as copolymers of (meth)acrylic acid and (meth)acrylic acid esters, and sodium polyacrylate; association-type thickening agents having a hydrophilic portion and a hydrophobic portion in one molecule, which exhibit a thickening effect in an aqueous medium by the hydrophobic portion adsorbing onto the surface of pigments or emulsion particles in the paint, or by the association of the hydrophobic portions; cellulose derivative-based thickening agents such as carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose; casein, sodium caseate, Examples include protein-based thickeners such as ammonium caseinate; alginate-based thickeners such as sodium alginate; polyvinyl-based thickeners such as polyvinyl alcohol, polyvinylpyrrolidone, and polyvinylbenzyl ether copolymers; polyether-based thickeners such as Pluronic® polyether, polyether dialkyl esters, polyether dialkyl ethers, and polyether epoxy modified products; maleic anhydride copolymer-based thickeners such as partial esters of vinyl methyl ether-maleic anhydride copolymers; polyamide-based thickeners such as polyamide amine salts, and any combination thereof.

[0298] The above-mentioned polyacrylic acid-based thickeners are commercially available, for example, "ACRYSOLASE-60," "ACRYSOLTT-615," and "ACRYSOLRM-5" (all product names) from Rohm & Haas, and "SN Thickener 613," "SN Thickener 618," "SN Thickener 630," "SN Thickener 634," and "SN Thickener 636" (all product names) from Sunnopco.

[0299] Furthermore, the above-mentioned association-type thickeners are commercially available, for example, "UH-420," "UH-450," "UH-462," "UH-472," "UH-540," "UH-752," "UH-756VF," and "UH-814N" (all product names) from ADEKA Corporation; "ACRYSOLRM-8W," "ACRYSOLRM-825," "ACRYSOLRM-2020NPR," "ACRYSOLRM-12W," and "ACRYSOLSCT-275" (all product names) from Rohm & Haas Corporation; and "SN Thickener 612," "SN Thickener 621N," "SN Thickener 625N," "SN Thickener 627N," and "SN Thickener 660T" (all product names) from Sunnopco Corporation.

[0300] As the pigment dispersion resin mentioned above, it is preferable to use an acrylic pigment dispersion resin. More specifically, for example, an acrylic resin obtained by polymerizing a polymerizable unsaturated monomer with a polymerization initiator in the presence of a hydrophilic organic solvent can be cited.

[0301] Examples of polymerizable unsaturated monomers include the compounds exemplified in the resin synthesis described above, and they can be used in appropriate combinations. The above-mentioned pigment dispersion resin is preferably a resin that is soluble in water or dispersible in water, and specifically has a hydroxyl value of preferably 10 to 100 mg KOH / g, more preferably 20 to 70 mg KOH / g, and an acid value of preferably 10 to 80 mg KOH / g, more preferably 20 to 60 mg KOH / g.

[0302] The thermosetting resin composition of the present invention preferably contains 5 to 70% by mass, and more preferably 7 to 61% by mass, of the pigment dispersion resin, based on the total solid content mass of the above resin and pigment dispersion resin. This range is preferred from the viewpoint of storage stability of the thermosetting resin composition and the finish, water resistance, and sandability of the colored coating film formed using the colored coating composition of the present invention.

[0303] The thermosetting resin composition of the present invention can also be an aqueous composition. The method of making it aqueous is not particularly limited, and it can be made aqueous by a general method using the components described above. Even when made aqueous, the transesterification reaction can be suitably carried out by using the transesterification catalyst of the present invention.

[0304] The materials to which the above thermosetting resin composition can be applied are not particularly limited, and various examples include the exterior panels of automobile bodies such as passenger cars, trucks, motorcycles, and buses; automobile parts; household electrical appliances such as mobile phones and audio equipment; building materials; furniture; adhesives; and coatings for films and glass. Furthermore, it can be used for pre-coated metals that form a coating film by high-temperature, short-time curing, and for painting metal cans. It can also be used for electrodeposition paints, adhesives, particleboard, and the like.

[0305] The above thermosetting resin composition can also be used as an electrodeposition coating composition. Examples of electrodeposition coatings include cationic electrodeposition coatings and anionic electrodeposition coatings, but either of these can be used.

[0306] The above-mentioned object to be coated may be a metal material or a metal surface such as a car body formed therefrom that has been subjected to a surface treatment such as phosphate treatment, chromate treatment, or composite oxide treatment, or it may be an object to be coated that has a coating film. Examples of objects to be coated with the above-mentioned coating include those in which a substrate has been optionally surface-treated and a primer coating has been formed thereon. In particular, a vehicle body in which a primer coating has been formed by electrodeposition paint is preferred, and a vehicle body in which a primer coating has been formed by cationic electrodeposition paint is more preferred.

[0307] The object to be coated may be the plastic material described above, or a plastic surface of an automobile part or the like molded from it, which may have been surface-treated, primed, or otherwise treated as desired. Alternatively, it may be a combination of the plastic material and the metal material described above.

[0308] The coating method for the thermosetting resin composition is not particularly limited and includes, for example, air spray coating, airless spray coating, rotary atomization coating, and curtain coating, with air spray coating and rotary atomization coating being preferred. Electrostatic application may be applied during coating if desired. A wet coating film can be formed from the aqueous paint composition using the above coating method.

[0309] The wet coating described above can be cured by heating. This curing can be carried out using known heating methods, such as a hot air furnace, electric furnace, or infrared induction heating furnace. The wet coating 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 preferably about 10 to about 60 minutes, and more preferably about 15 to about 40 minutes. It is also preferable in that it can accommodate low-temperature curing at 80 to 140°C.

[0310] 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, one example is a method in which a coating made of the thermosetting resin composition of the present invention is applied, and then another coating composition is applied on top of it without curing, and these two layers of coatings are baked simultaneously to form a multilayer coating. Furthermore, in such a coating method, a multilayer coating of three or more layers may be formed, with at least one of these layers being made of the thermosetting resin composition of the present invention.

[0311] When using the thermosetting resin composition of the present invention to form such a multilayer coating, the paint used in combination may be water-based or solvent-based. Furthermore, the curing system may be a curing system by transesterification reaction as described above, or it may be another curing system such as melamine curing or isocyanate curing.

[0312] Furthermore, when the thermosetting resin composition of the present invention is used in the field of coatings, it is necessary to have sufficient curing performance that includes properties such as smoothness, water resistance, and acid resistance. On the other hand, when used in fields such as adhesives and sealants, the high curing performance required for paints is not necessary. While the thermosetting resin composition of the present invention can be made to a level suitable for use as a paint, compositions that do not reach such a level may still be usable in fields such as adhesives and sealants.

[0313] A cured film is obtained by three-dimensional crosslinking of the thermosetting resin composition of the present invention. Such a cured film has sufficient performance to be used as a paint or adhesive. The above-mentioned cured film also includes the cured film formed by the multi-layer coating method described above. [Examples]

[0314] The present invention will be described in more detail below based on the following examples. However, the present invention is not limited to the following examples. In this text, "parts" refers to parts by weight.

[0315] The weight-average molecular weights of the copolymers were all measured using a gel permeation chromatography (GPC) analyzer (the column was manufactured by Tosoh Corporation and product name TSKGEL SUPERMULTIPORE HZ-M, and the elution solvent was THF (tetrahydrofuran)).

[0316] Examples of surface modifiers prepared using the present invention are shown below in Manufacturing Examples 1 to 7, and examples of surface modifiers prepared in which the present invention is not applicable are shown in Manufacturing Comparative Examples 1 to 6.

[0317] (Example 1 of manufacturing leveling agent) 1000 mL reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen gas inlet was charged with 100 parts by weight of xylene, and the temperature was raised to 115°C while introducing nitrogen gas. The dropping solution (a-1) shown in Table 1 below was added dropwise at a constant rate over 2 hours using the dropping funnel. After the addition was complete, the reaction was carried out for 4 hours while maintaining the temperature at 115°C to obtain a polymer. The copolymer was diluted with xylene to adjust the solid content to 30% to produce xylene solution (A-1). The weight-average molecular weight of this copolymer was 30,000, and the SP value was 8.3.

[0318] (Example 2 of leveling agent manufacturing) Leveling agent (A-2) was obtained by synthesizing a copolymer in the same manner as in Manufacturing Example 1, except that the dropper solution in Manufacturing Example 1 was changed to (a-2) in Table 1 below. The weight-average molecular weight of the obtained leveling agent was determined by gel permeation chromatography in the same manner as in Manufacturing Example 1, and it was found to be 15,000 in polystyrene equivalent and an SP value of 8.2.

[0319] (Example 3 of leveling agent manufacturing) Leveling agent (A-3) was obtained by synthesizing a copolymer in the same manner as in Manufacturing Example 1, except that the dropwise solution in Manufacturing Example 1 was changed to (a-3) in Table 1 below. The weight-average molecular weight of the obtained leveling agent was determined by gel permeation chromatography in the same manner as in Manufacturing Example 1, and it was found to be 10,000 in polystyrene equivalent and an SP value of 8.2.

[0320] (Example 4 of Leveling Agent Manufacturing) Leveling agent (A-4) was obtained by synthesizing a copolymer in the same manner as in Manufacturing Example 1, except that the dropwise solution in Manufacturing Example 1 was changed to (a-4) in Table 1 below. The weight-average molecular weight of the obtained leveling agent was determined by gel permeation chromatography in the same manner as in Manufacturing Example 1, and it was found to be 8,000 in polystyrene equivalent and an SP value of 8.1.

[0321] (Synthesis Example 1) 180 parts succinic anhydride and 173 parts methanol were placed in a four-necked flask and the succinic anhydride was dissolved at 60-70°C. After confirming that the succinic anhydride peak had disappeared by NMR, the excess methanol was removed under reduced pressure at over 60°C to synthesize monomethyl succinate. 190 parts monomethyl succinate, 204.6 parts glycidyl methacrylate, triethylbenzylammonium chloride, and a polymerization inhibitor were added and reacted at 90°C for more than 10 hours to obtain monomer A.

[0322] (Example 5 of manufacturing an antifoaming agent) 70 parts by weight of xylene was charged into a 1000 mL reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen gas inlet, and the temperature was raised to 105°C while introducing nitrogen gas. The dropping solution (b-1) shown in Table 1 below was added dropwise over 2 hours using the dropping funnel. After the addition was complete, the reaction was maintained at 105°C for 1 hour, then the temperature was raised to 115°C and the reaction was carried out for 4 hours to obtain the polymer. The copolymer was diluted with xylene to adjust the solid content to 30% to produce xylene solution (B-1). The weight-average molecular weight of this copolymer was 40,000, and the SP value was 8.0.

[0323] (Example 6 of manufacturing an antifoaming agent) Leveling agent (B-2) was obtained by synthesizing a copolymer in the same manner as in Manufacturing Example 5, except that the dropwise solution in Manufacturing Example 5 was changed to (b-2) in Table 1 below. The weight-average molecular weight of the obtained leveling agent was determined by gel permeation chromatography in the same manner as in Manufacturing Example 5, and it was found to be 35,000 in polystyrene equivalent and an SP value of 7.9.

[0324] (Example 7 of manufacturing an antifoaming agent) Except for changing the dropwise solution in Manufacturing Example 5 to (b-3) in Table 1 below, the copolymer was synthesized in the same manner as in Manufacturing Example 5 to obtain the antifoaming agent (B-3). The weight-average molecular weight of the obtained antifoaming agent was determined by gel permeation chromatography in the same manner as in Manufacturing Example 5, and it was found to be 33,000 in polystyrene equivalent and an SP value of 7.8.

[0325] [Table 1]

[0326] (Comparative example 1 of leveling agent manufacturing) 1000 mL reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen gas inlet was charged with 100 parts by weight of xylene, and the temperature was raised to 115°C while introducing nitrogen gas. The dropping solution (c-1) shown in Table 2 below was added dropwise at a constant rate over 2 hours using a dropping funnel. After the addition was complete, the reaction was carried out for 4 hours while maintaining the temperature at 115°C to obtain a polymer. The copolymer was diluted with xylene to adjust the solid content to 30% to produce xylene solution (C-1). The weight-average molecular weight of this copolymer was 33,000, and the SP value was 8.3.

[0327] (Comparative example 2 of leveling agent manufacturing) Leveling agent (C-2) was obtained by synthesizing a copolymer in the same manner as in Manufacturing Comparative Example 1, except that the dropper solution in Manufacturing Comparative Example 1 was changed to (c-2) in Table 2 below. The weight-average molecular weight of the obtained leveling agent was determined by gel permeation chromatography in the same manner as in Manufacturing Comparative Example 1, and was found to be 30,000 in polystyrene equivalent, with an SP value of 8.3.

[0328] (Comparative example 3 of leveling agent manufacturing) Leveling agent (C-3) was obtained by synthesizing a copolymer in the same manner as in Manufacturing Comparative Example 1, except that the dropper solution in Manufacturing Comparative Example 1 was changed to (c-3) in Table 2 below. The weight-average molecular weight of the obtained leveling agent was determined by gel permeation chromatography in the same manner as in Manufacturing Comparative Example 1, and was found to be 33,000 in polystyrene equivalent, with an SP value of 8.2.

[0329] (Comparative Example 4 of the Manufacturing of Antifoaming Agents) 70 parts by weight of xylene was charged into a 1000 mL reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen gas inlet, and the temperature was raised to 105°C while introducing nitrogen gas. The dropping solution (d-1) shown in Table 2 below was added dropwise over 2 hours using the dropping funnel. After the addition was complete, the reaction was maintained at 105°C for 1 hour, then the temperature was raised to 115°C and the reaction was carried out for 4 hours to obtain the polymer. The copolymer was diluted with xylene to adjust the solid content to 30% to produce xylene solution (D-1). The weight-average molecular weight of this copolymer was 35,000, and the SP value was 8.0.

[0330] (Comparative Example 5 of Antifoaming Agent Manufacturing) Except for changing the dropwise solution in Manufacturing Comparative Example 4 to (d-2) in Table 2 below, the copolymer was synthesized in the same manner as in Manufacturing Comparative Example 4 to obtain the defoaming agent (D-2). The weight-average molecular weight of the obtained defoaming agent was determined by gel permeation chromatography in the same manner as in Manufacturing Comparative Example 4, and it was found to be 40,000 in polystyrene equivalent and an SP value of 8.0.

[0331] (Comparative Example 6 of Antifoaming Agent Manufacturing) Except for changing the dropwise solution in Manufacturing Comparative Example 4 to (d-3) in Table 2 below, the copolymer was synthesized in the same manner as in Manufacturing Comparative Example 4 to obtain the antifoaming agent (D-3). The weight-average molecular weight of the obtained antifoaming agent was determined by gel permeation chromatography in the same manner as in Manufacturing Comparative Example 4, and it was found to be 42,000 in polystyrene equivalent and an SP value of 7.9.

[0332] [Table 2]

[0333] Two-component curable film-forming compositions were prepared using the formulation components for two-component curable film-forming compositions shown in Tables 3 and 4, along with the copolymer liquids (A-1) to (A-4) and (C-1) to (C-3) as leveling agents, and leveling tests were conducted.

[0334] [Table 3] *1) SP value of solids: 9.7 *2) Diluent: xylene / butyl acetate = 4 / 1

[0335] [Table 4] *) Diluent: xylene / butyl acetate = 4 / 1

[0336] (Preparation of two-component curable film-forming composition and creation of cured film) To the mixture of components for the two-component curable film-forming composition shown in Table 3, 0.5 parts by weight of leveling agents ((A-1) to (A-4) and (C-1) to (C-3)) were added, and the mixture was stirred at 2,000 rpm for 2 minutes in a labodies spar to prepare the two-component curable film-forming compositions of Examples 1 to 4 and Comparative Examples 1 to 3, respectively. A mixture consisting only of the components for the two-component curable film-forming composition was designated as Comparative Example 4. After the obtained test paints were allowed to stand and degassed, they were applied to a substrate using a #42 bar coater and immediately baked at 80°C for 20 minutes to cure and form a cured film.

[0337] Using these materials, performance tests were conducted to evaluate their smoothness and water resistance.

[0338] (Smoothness evaluation) The surface condition of the hardened painted area was visually observed and evaluated according to the following evaluation criteria. The results are shown in Table 5 below.

[0339] Evaluation criteria for leveling performance Good:○ Slight paint streaks from the bar coater remain: ○~△ Bar coater paint streaks are clearly visible: △ A bullet occurred: ×

[0340] (Water resistance evaluation) The coated plate obtained in the same manner as the smoothness evaluation was immersed in a warm water bath at 80°C for 1 hour, then the heating was stopped and it was gradually cooled until it reached room temperature. The coated plate was taken out of the water bath and dried at room temperature, and the whitening property of the water immersion part was visually observed. The results of the observation are shown in Table 5 below.

[0341] Criteria for water resistance evaluation Those that did not whiten at all: ○ Those that slightly whitened: △ Those that significantly whitened: ×

[0342]

Table 5

[0343] As is clear from Table 5, the film of the example in which the composition containing the leveling agent of the present invention was cured was superior in leveling property to the film of the comparative example in which the composition outside the application of the present invention was cured. Further, the leveling agent of the present invention was excellent in water resistance without peeling off from the film even under low-temperature curing conditions.

[0344] Using the compounding components for the two-component curable film-forming composition shown in Table 6 and Table 7, and the antifoaming agents of the copolymer solutions (B-1) to (B-3) and (D-1) to (D-3), a two-component curable film-forming composition was prepared and an antifoaming property test was conducted.

[0345]

Table 6

[0346]

Table 7

[0347] (Preparation of two-component curable film-forming composition) To the mixture of components for the two-component curable film-forming composition shown in Table 6, 0.5 parts by weight of the defoaming agents ((B-1) to (B-3) and (D-1) to (D-3)) shown in Table 7 were added, and the mixture was stirred at 2,000 rpm for 2 minutes using a labodiespar to prepare the two-component curable film-forming compositions of Examples 5 to 7 and Comparative Examples 5 to 7, respectively. A mixture consisting only of the components for the two-component curable film-forming composition was designated as Comparative Example 8.

[0348] (Evaluation of antifoaming properties) A two-component curing film-forming composition with an antifoaming agent was immediately poured into a 25 mL specific gravity cup after stirring, and the weight of the composition with the antifoaming agent immediately after stirring was measured. On the other hand, a two-component curing film-forming composition without an antifoaming agent was stirred, allowed to stand for several hours, and then poured into a specific gravity cup until no foam was present. The weight of the composition without the antifoaming agent after standing was measured. The weight of the composition with the antifoaming agent was calculated as the percentage of the weight of the composition with the antifoaming agent immediately after stirring, with the weight of the composition without the antifoaming agent after standing set to 100%.

[0349] Criteria for evaluating antifoaming properties Items with a percentage of 97% or higher: ○ Items with a percentage between 95% and 97%: △ Items with less than 95%: ×

[0350] (Water resistance evaluation) A test coating for defoaming evaluation was applied to a glass plate using a 125 μm applicator and immediately baked at 140°C for 30 minutes to cure and form a hardened film. The resulting coated plate was immersed in an 80°C hot water bath for 1 hour, then the heating was stopped and it was allowed to cool slowly to room temperature. The coated plate was removed from the water bath and dried at room temperature, and the whitening of the water-immersed area was visually observed. The observed results are shown in Table 6 below.

[0351] Criteria for evaluating water resistance Those that did not whiten at all: ○ Slightly bleached: △ Severely whitened: ×

[0352] [Table 8]

[0353] As is clear from Table 8, the coatings of the examples obtained by curing compositions containing the defoaming agent of the present invention exhibited superior water resistance and defoaming properties compared to the coatings of the comparative examples obtained by curing compositions not covered by the present invention.

[0354] Test paint compositions were prepared using the compounding components for the test paint compositions shown in Table 9, leveling agents (A-1) to (A-4) and (C-1) to (C-3) of the copolymer liquids, and defoaming agents (B-1) to (B-3) and (D-1) to (D-3) of the polymer liquids, and the long-term stability tests of the paints were conducted.

[0355] [Table 9] *) Diluent: xylene / butyl acetate = 4 / 1

[0356] (Evaluation of the long-term stability of test paints) The viscosity (using a B-type viscometer) of the prepared test paint was measured initially, and after storage at 40°C for 1 month and 2 months. The results are shown in Table 10 below.

[0357] [Table 10]

[0358] As is clear from Table 10, the test coatings of Examples 8-14 exhibit good stability over time and do not thicken or gel.

[0359] (Synthesis Example 2) A monomer mixture was prepared by dissolving 35 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd. product: Light Ester NB), 30 parts of methoxycarbonylmethyl methacrylate, 25 parts of 4-hydroxybutyl acrylate, and 10 parts of styrene. As an initiator, 5 parts of AIBN were dissolved in 20 parts of aromatic hydrocarbon (T-SOL100) to prepare an initiator solution. 80 parts of aromatic hydrocarbon (T-SOL100) were placed in a stirable flask, and the monomer solution and initiator solution were added dropwise while the flask was sealed with nitrogen. The polymerization temperature at this time was set to 100°C. The dropwise addition was carried out over 2 hours, and the mixture was then aged at 100°C for 4 hours to obtain a thermosetting resin composition polymer solution A, in which a transesterification reaction with a weight-average molecular weight of 9400 was used as the curing reaction.

[0360] (Synthesis Example 3) 60 parts of ethylene glycol monoacetate monomethacrylate, 48 parts of methyl acrylate, 43 parts of potassium carbonate, 3 parts of 18-crown-6 ether, and 108 parts of tetrahydrofuran were mixed and stirred at 50°C for 3 hours. After the reaction was complete, cyclohexane and water were added and washed with water. The organic layer was neutralized with saturated ammonium chloride aqueous solution, washed twice with water, and the resulting organic layer was concentrated under reduced pressure to obtain monomer B.

[0361] (Synthesis Example 4) A monomer mixture was prepared by dissolving 35 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd. product: Light Ester NB), 30 parts of monomer B, 25 parts of 4-hydroxybutyl acrylate, and 10 parts of styrene. As an initiator, 5 parts of AIBN were dissolved in 20 parts of aromatic hydrocarbon (T-SOL100) to prepare an initiator solution. 80 parts of aromatic hydrocarbon (T-SOL100) were placed in a stirable flask, and the monomer solution and initiator solution were added dropwise while the flask was sealed with nitrogen. The polymerization temperature at this time was set to 100°C. The dropwise addition was carried out over 2 hours, and the mixture was then aged at 100°C for 4 hours to obtain polymer solution B with a weight-average molecular weight of 10700 and a dispersion degree of 1.73.

[0362] (Synthesis Example 5) A monomer mixture was prepared by dissolving 35 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd. product: Light Ester NB), 30 parts of monomer A, 25 parts of 4-hydroxybutyl acrylate, and 10 parts of styrene. As an initiator, 5 parts of AIBN were dissolved in 20 parts of aromatic hydrocarbon (T-SOL100) to prepare an initiator solution. 80 parts of aromatic hydrocarbon (T-SOL100) were placed in a stirable flask, and the monomer solution and initiator solution were added dropwise while the flask was sealed with nitrogen. The polymerization temperature at this time was set to 100°C. The dropwise addition was carried out over 2 hours, and the mixture was then aged at 100°C for 4 hours to obtain polymer solution C with a weight-average molecular weight of 10300 and a dispersion degree of 2.00.

[0363] Examples 15-38, Comparative Examples 15-38 Each component shown in Tables 12-17 was mixed, and leveling, defoaming, and water resistance tests were conducted. The physical properties in the tables were measured by the following methods.

[0364] (Smoothness evaluation) After the mixed composition was allowed to stand and degass, it was applied to the substrate with a #42 bar coater and immediately baked at 80°C for 30 minutes to cure and form a cured film. The surface condition of the painted area after hardening was visually inspected. Evaluation criteria for leveling performance Good:○ Slight paint streaks from the bar coater remain: ○~△ Bar coater paint streaks are clearly visible: △ A bullet occurred: ×

[0365] (Evaluation of antifoaming properties) After stirring, the composition with the defoaming agent was immediately poured into a 25 mL specific gravity cup, and the weight of the composition with the defoaming agent immediately after stirring was measured. On the other hand, after stirring, the composition without the defoaming agent was allowed to stand for several hours until it contained no foam, and this composition was poured into a specific gravity cup, and the weight of the composition without the defoaming agent after standing was measured. When the weight of the composition without the defoaming agent after standing was set to 100%, the ratio of the weight of the composition with the defoaming agent immediately after stirring was calculated. Criteria for evaluating antifoaming properties Items with a percentage of 97% or higher: ○ Items with a percentage between 95% and 97%: △ Items with less than 95%: ×

[0366] (Water resistance evaluation) A composition containing a leveling agent or defoaming agent was applied to a glass plate using a 125 μm applicator and immediately baked at 80-200°C for 30 minutes to cure and form a hardened film. The resulting coated plate was immersed in an 80°C hot water bath for 1 hour, then the heating was stopped and it was allowed to cool slowly to room temperature. The coated plate was removed from the water bath and dried at room temperature, and the whitening of the water-immersed portion was visually observed. Criteria for evaluating water resistance Those that did not whiten at all: ○ Slightly bleached: △ Severely whitened: ×

[0367] [Table 11]

[0368] [Table 12]

[0369] [Table 13]

[0370] [Table 14]

[0371] [Table 15]

[0372] [Table 16]

[0373] A time-stable test was conducted using polymer solution A, leveling agents (A-1) to (A-4) and (C-1) to (C-3) of the copolymer solutions, and defoaming agents (B-1) to (B-3) and (D-1) to (D-3) of the polymer solutions. The formulations used in the time-stable test are shown in Table 18, and the test results are shown in Table 19.

[0374] [Table 17]

[0375] (Evaluation of stability over time) The viscosity of the prepared composition was measured initially and after storage at 40°C for 2 months (using a B-type viscometer). Evaluation Criteria No increase in viscosity after storage over time: ○ Increased viscosity or gelation after storage over time: ×

[0376] [Table 18]

[0377] As is clear from Tables 11-16 and 18, the coatings of the cured examples of compositions containing the defoaming agent and leveling agent of the present invention exhibit superior water resistance, defoaming properties, and leveling properties compared to the coatings of the comparative examples cured with compositions not covered by the present invention. Furthermore, the compositions of Examples 39-44 exhibit good stability over time and do not thicken or gel. [Industrial applicability]

[0378] The surface preparation agent of the present invention can be suitably used in thermosetting resin compositions that contain a hydroxyl group-containing compound as an essential component.

Claims

1. The following general formula (1) 【Chemistry 1】 (In the formula, R １ This represents an alkyl group having 1 to 24 carbon atoms. R ２ (This represents a hydrogen or methyl group.) A constituent unit (A) derived from at least one monomer selected from the group consisting of (meth)acrylic acid ester (A-1) represented by and alkyl vinyl ether (A-2) having 1 to 24 carbon atoms in the alkyl group, and the following general formula (4) 【Chemistry 2】 n １ :1~10 (wherein, R ４ , R ５ , R ６ are the same or different and are hydrogen, an alkyl group, a carboxyl group, an alkyl ester group or the following R ７ - [COOR ８ n １ represented structure. R ７ This refers to an aliphatic, alicyclic, or aromatic alkylene group having 50 or fewer atoms in its main chain, which may have one or more functional groups selected from the group consisting of ester groups, ether groups, amide groups, and urethanes in its main chain, and which may have a side chain. R ８ This refers to an alkyl group with 50 or fewer carbon atoms. The compound represented by the above general formula (4) is R ７ - [COOR ８ ]n １ The base may also be a lactone structure of the following general formula (41). 【Transformation 3】 (R x (A hydrocarbon group having 2 to 10 carbon atoms, which may have a branched chain.) The constituent unit (B) derived from the monomer represented by is an essential component, The solubility parameter is 7.6 to 12.

0. The above constituent unit (B) is included in a proportion of 1 to 30% by weight relative to the surface modifier. A surface modifier characterized by having a weight-average molecular weight of 3,000 to 500,000.

2. A resin or resin composition (X) having a hydroxyl group. The surface modifier according to claim 1 and Transesterification catalyst (Z) A thermosetting resin composition characterized by containing [a certain substance].

3. The thermosetting resin composition according to claim 2, wherein the solubility parameter of the surface modifier is smaller for the resin or resin composition (X) and the surface modifier, and the difference is 3.0 or less.

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