WO2020217320A1 - Composition de résine thermodurcissable, film durci, et particules de résine en dispersion non aqueuse - Google Patents

Composition de résine thermodurcissable, film durci, et particules de résine en dispersion non aqueuse Download PDF

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WO2020217320A1
WO2020217320A1 PCT/JP2019/017284 JP2019017284W WO2020217320A1 WO 2020217320 A1 WO2020217320 A1 WO 2020217320A1 JP 2019017284 W JP2019017284 W JP 2019017284W WO 2020217320 A1 WO2020217320 A1 WO 2020217320A1
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group
meth
parts
acrylate
acid
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PCT/JP2019/017284
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English (en)
Japanese (ja)
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佑也 森脇
耕資 浅田
克 呑海
直巳 竹中
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共栄社化学株式会社
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Priority to PCT/JP2019/017284 priority Critical patent/WO2020217320A1/fr
Priority to JP2021516175A priority patent/JP6989996B2/ja
Priority to PCT/JP2020/017385 priority patent/WO2020218372A1/fr
Publication of WO2020217320A1 publication Critical patent/WO2020217320A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to thermosetting resin compositions, cured films and non-aqueous dispersion resin particles.
  • NAD non-aqueous dispersion
  • Such a film property modifier examples include NAD (non-aqueous dispersion), block copolymer and the like. Further, it is widely practiced to add a polyester resin to a paint or an adhesive using an acrylic resin as a base resin. Such addition of the polyester resin is also performed to modify the physical properties of the film, and can be considered as one of the modifiers for the physical properties of the film.
  • NAD has a shell having a function as a dispersion stabilizer on the surface of a core made of insoluble resin particles.
  • an ultra-high molecular weight one or a three-dimensional crosslinked one can be introduced into the core portion.
  • the elongation rate is lowered, and when the film is softened, the breaking strength is lowered. Therefore, by coexisting three-dimensionally crosslinked resin particles such as NAD in the coating film, the physical properties of the film can be improved without lowering the breaking strength and the elongation rate.
  • Such non-aqueous dispersion resin particles are resins in a dispersed state rather than being dissolved in an organic solvent.
  • Such a resin has excellent performance in that it can be used as a paint using a weak solvent and that it can be made into a high solid because the viscosity can be easily controlled. It is widely manufactured and used in the field of.
  • the non-aqueous dispersion generally has a reactive functional group on the surface of the non-aqueous dispersion particles, and is often used by mixing the non-aqueous dispersion with a resin solution, a curing agent solution, or the like and curing the non-aqueous dispersion.
  • Patent Documents 1 to 4 and the like are known as such examples.
  • thermosetting resin When such non-aqueous dispersion particles are used in a curable resin composition such as a paint, many attempts have been made to obtain a composition in combination with a matrix resin or a curing agent. As a result, good properties can be obtained in many physical properties such as strength and durability that are generally required for the thermosetting resin.
  • the thermosetting reaction used is generally a melamine cross-linking, an isocyanate cross-linking or the like, or a reaction between a carboxylic acid and an epoxy group.
  • These curing agents are widely and generally used because they have good thermal reactivity and excellent properties of the obtained cured resin.
  • melamine resin since melamine resin generates formaldehyde during the curing reaction and is considered to be a cause of sick building syndrome, its use may be limited in recent years. Further, since the melamine resin does not have sufficient acid resistance, improvement in acid resistance is also required.
  • the polyisocyanate compound has a high curing reaction, it is not easy to handle due to its toxicity and is expensive. Furthermore, carboxylic acids and epoxy groups have problems in terms of storage stability.
  • Patent Document 5 describes that the transesterification reaction between a t-butyl ester group and a hydroxyl group is a curing reaction. However, this document does not disclose that a transesterification reaction occurs in the curing reaction between NAD and the resin.
  • Patent Document 6 a thermosetting resin composition in which a transesterification reaction is a curing reaction.
  • Patent Document 6 does not describe or suggest the use of NAD particles.
  • Japanese Unexamined Patent Publication No. 2001-40010 Japanese Unexamined Patent Publication No. 2001-261715 JP 2015-168693 Japanese Unexamined Patent Publication No. 10-298256 Japanese Unexamined Patent Publication No. 9-59543 Patent No. 6398026
  • thermosetting resin composition which has good curability, can be used in various applications, has a transesterification reaction, and has good physical properties. Is the purpose.
  • the present invention contains a resin component (A) containing at least one film property modifier (A-1) selected from the group consisting of non-aqueous dispersion resin particles, block copolymers and polyester resin as an essential component.
  • the resin component (A) is a thermosetting resin composition having an alkyl ester group and a hydroxyl group, and further containing an ester exchange catalyst (B).
  • thermosetting resin composition may be substantially free of melamine resin, isocyanate compound and epoxy group. It is preferable that at least a part of the non-aqueous dispersion resin particles has a skeleton derived from a monomer represented by the following general formula (1).
  • n 1 1 to 10 (Wherein, R 1, R 2, R 3 are the same or different, hydrogen, an alkyl group, a carboxyl group, an alkyl ester group or the following R 4 - represents a [COOR 5] structure represented by n 1.
  • R 4 has 50 or less atoms in the main chain, and may have one or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and urethane in the main chain.
  • An aliphatic, alicyclic or aromatic alkylene group which may have a side chain.
  • R 5 is an alkyl group having 50 or less carbon atoms.
  • the present invention is also a cured film, which is obtained by thermally curing the thermosetting resin composition.
  • the present invention is a non-aqueous dispersion resin particle having an alkyl ester group.
  • the alkyl ester group is also a non-aqueous dispersion resin particle characterized in that at least a part thereof is a skeleton derived from a monomer represented by the following general formula (1).
  • n 1 1 to 10 (Wherein, R 1, R 2, R 3 are the same or different, hydrogen, an alkyl group, a carboxyl group, an alkyl ester group or the following R 4 - represents a [COOR 5] structure represented by n 1.
  • R 4 has 50 or less atoms in the main chain, and may have one or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and urethane in the main chain.
  • An aliphatic, alicyclic or aromatic alkylene group which may have a side chain.
  • R 5 is an alkyl group having 50 or less carbon atoms.
  • thermosetting resin composition of the present invention is cured by a transesterification reaction between an alkyl ester group and a hydroxyl group, and further, by using a film property modifier, the physical properties are improved and excellent functions are obtained.
  • a thermosetting resin composition having the above can be obtained. Further, it is also preferable that a resin composition having a high solid content (high solidification) and a low VOC can be obtained.
  • the resin is cured by a transesterification reaction. Further, by blending a film property modifier, a thermosetting resin composition capable of forming an excellent coating film can be obtained.
  • the present invention requires the resin component (A), the resin component (A) has an alkyl ester group and a hydroxyl group, and the non-aqueous dispersion resin particles, block copolymer and block copolymer It is characterized in that it contains at least one film property modifier selected from the group consisting of polyester resins.
  • thermosetting resin composition in which the ester exchange reaction is a resin curing reaction, heat is generated by blending at least one component selected from the group consisting of non-aqueous dispersion resin particles, block copolymers and polyester resins. It is characterized by modifying the physical properties of the curable resin composition.
  • the film property modifier preferably has an alkyl ester group and / or a hydroxyl group. By having these functional groups, it is incorporated into the crosslinked structure formed by the resin component (A), and a cured product having more excellent physical properties can be obtained.
  • the resin component (A) in the present invention is a part of the film property modifier (A-1) and further contains another resin component (A-2).
  • the resin component (A) has an alkyl ester group and a hydroxyl group as a whole, but the above-mentioned "other resin component (A-2)" has at least one functional group of an alkyl ester group and a hydroxyl group. It is preferable to have.
  • the above “other resin component (A-2)” does not have both an alkyl ester group and a hydroxyl group, the “other resin component (A-2)” does not participate in the curing reaction. This is because good physical properties cannot be obtained in the cured product.
  • thermosetting resin composition of the present invention the addition of a transesterification catalyst is indispensable in order to cause a transesterification reaction.
  • a thermosetting resin composition in which non-aqueous dispersion resin particles having an alkyl ester group are used in combination with a matrix resin has been known.
  • the transesterification catalyst since the transesterification catalyst was not used in combination, the cross-linking reaction between the alkyl ester and the hydroxyl group did not sufficiently occur. Therefore, it is presumed that the cross-linking reaction as in the present invention does not occur in each composition of the cited documents described above.
  • (meth) acrylate means acrylate and / or methacrylate.
  • (Meta) acrylic acid means acrylic acid and / or methacrylic acid.
  • (meth) acryloyl means acryloyl and / or methacryloyl.
  • (meth) acrylamide means acrylamide and / or methacrylamide.
  • Non-aqueous dispersion resin particles used in the present invention preferably have an alkyl ester group. As a result, it is incorporated into the cross-linking reaction that occurs in the resin component (A) and becomes a part of the cured product. Further, the non-aqueous dispersion resin particles may have a hydroxyl group. Those having a hydroxyl group are also incorporated into the cross-linking reaction that occurs in the resin component (A) to form a part of the cured product. As a result, it exerts a function of modifying physical properties.
  • the non-aqueous dispersion resin particles mean a resin that is not dissolved in an organic solvent and is dispersed as particles. It is not particularly limited as long as it has such a form, but specifically, in a polymer obtained by using a polymerizable unsaturated monomer, a single amount of a dimer or more is partially used.
  • a crosslinked structure formed in the resin can be mentioned.
  • a crosslinking agent such as a polyvalent isocyanate, a melamine-based crosslinking agent, or an acid / epoxy may be used.
  • an ultra-high molecular weight substance can be used.
  • Examples of such a monomer include a compound having a structure represented by the following general formula (2).
  • R 6 , R 7 , and R 8 represent hydrogen, an alkyl group, a carboxyl group, and an alkyl ester group, which are the same or different.
  • R 9 represents an alkyl group having 50 or less carbon atoms
  • Examples of the compound represented by the general formula (2) include alkyl ester derivatives of known unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid.
  • the most typical monomer having an alkyl ester group represented by the general formula (2) and a polymerizable unsaturated bond is an ester of (meth) acrylic acid and an alcohol, for example, methyl (meth).
  • Acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, benzyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate , T-Butyl (meth) acrylate can be mentioned.
  • tertiary alkyl esters such as t-butyl (meth) acrylate are most preferable from the viewpoint of cross-linking reactivity.
  • t-butyl (meth) acrylate is an ester of a tertiary alkyl, the transesterification reaction rate is high, so that the curing reaction proceeds efficiently. Therefore, it is more excellent in cross-linking reactivity than the primary alkyl ester and the secondary alkyl ester, and is a very preferable raw material for providing an ester group that achieves the object of the present invention.
  • the monomer having an alkyl ester group may be a compound in which a polymerizable unsaturated bond and an ester group are bonded via a linking group.
  • n 1 1 to 10 (Wherein, R 1, R 2, R 3 are the same or different, hydrogen, an alkyl group, a carboxyl group, an alkyl ester group or the following R 4 - represents a [COOR 5] structure represented by n 1.
  • R 4 has 50 or less atoms in the main chain, and may have one or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and urethane in the main chain. , An aliphatic, alicyclic or aromatic alkylene group which may have a side chain.
  • R 5 is an alkyl group having 50 or less carbon atoms.
  • the one represented by the general formula of can be used.
  • an alkyl ester group is present from the acrylic resin main chain via a linking group. The preferred points of such a structure will be described in detail below.
  • R 10 is an H or methyl group.
  • R 11 is an alkylene group having a main chain having 48 or less atoms, 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 12 is an alkyl group having 50 or less carbon atoms.
  • An example is represented by.
  • Such a compound is a derivative of (meth) acrylic acid, and can be obtained by a known synthetic method using (meth) acrylic acid or a derivative thereof as a raw material.
  • the number of atoms in the main chain of R 11 is more preferably 40 or less, further preferably 30 or less, and further preferably 20 or less.
  • the atom that may be contained in the main chain of R 11 is not particularly limited, and may have an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or the like in addition to the carbon atom. More specifically, the main chain of R 11 has an ether group, an ester group, an amino group, an amide group, a thioether group, a sulfonic acid ester group, a thioester group, a siloxane group and the like in addition to the alkyl group. There may be.
  • Such a compound in which (meth) acrylic acid and an ester group are bonded via a linking group represented by R 11 is particularly preferable in that the reaction rate of transesterification tends to be high.
  • the reaction rate is increased because the side chain structure becomes a long chain and if an ester group is present at the end of the chain, the ester group can move easily and the degree of freedom increases, so that it can easily approach the hydroxyl group, thereby reacting. Is presumed to be promoted.
  • R 5, R 12 in the general formula (1), (3), a primary may be any of the tertiary. That is, in the case of a structure having a linking group R 4, R 11, even inherently reactive low alkyl ester group, it can be caused transesterification satisfactorily. Therefore, any of the primary, secondary, and tertiary ester groups can satisfactorily proceed with the cross-linking reaction by the transesterification reaction.
  • R 13 is an alkyl group having 1 to 50 carbon atoms.
  • R 14 is an alkylene group having a main chain having 44 or less atoms, 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 15 is an H or methyl group.
  • R 16 is an alkyl group having 50 or less carbon atoms.
  • R 17 is an H or methyl group.
  • n 3 is 0 or 1.
  • n 4 is 1 or 2.
  • the compound represented by the above general formula (4) is synthesized by reacting a compound that produces an active anion such as a malonic acid ester or an acetate acetate having an unsaturated bond in the molecule with an unsaturated compound having an alkyl ester group. It is an esterified compound.
  • malonic acid ester and acetoacetic ester have a methylene group sandwiched between carboxycarbons, and it is widely known that this methylene group is easily anionized and easily causes an anion reaction.
  • a compound having an unsaturated bond in the alkyl group of such a malonic acid ester or acetoacetic acid ester for example, malonic acid or acetoacetic acid and an unsaturated monosylate having a hydroxyl group described in detail below as a "hydroxyl-containing monomer"
  • the alkyl ester group can be easily changed by using a widely used raw material, and as a result, the curing reactivity can be easily adjusted. Further, it is particularly preferable in that the curing reactivity can be adjusted by changing the reaction rate to the active methylene group.
  • the compound that can be used as the "alkyl ester compound having an unsaturated group" used in the above reaction is not particularly limited, and is an (meth) acrylic acid alkyl ester, a methylenemalonic acid alkyl ester, or a lactone compound having an unsaturated group (for example, ⁇ ).
  • -Crotonolactone, 5,6-dihydro-2H-pyran-2-one) and the like can be used.
  • the reaction can be carried out under basic conditions, for example, by a reaction of an alkali metal salt in an organic solvent in the presence of crown theter.
  • An example of such a synthetic reaction is shown below.
  • n 1 1 to 10 Structure represented by [COOH] n 1 - (wherein, R 1, R 2, R 3 are the same or different, hydrogen, an alkyl group, a carboxyl group, an alkyl ester group or the following R 4.
  • R 4 has a main chain having 50 or less atoms, and has one or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and urethane in the main chain. It may also have an aliphatic, alicyclic or aromatic alkylene group which may have a side chain.
  • a known compound exists as a compound represented by the above general formula (1-2).
  • the unsaturated group-containing ester compound of the present invention can also be obtained by subjecting such a known compound to an ordinary esterification reaction (for example, a reaction with an alcohol corresponding to the alkyl group of the desired alkyl ester). ..
  • R represents an alkyl group.
  • One or more of such acrylic monomers having an alkyl ester group are used in the present invention by using them as a part of a resin raw material in any known method for producing a non-aqueous dispersion resin.
  • Particularly suitable non-aqueous dispersion resin particles can be used.
  • the method for producing such a non-aqueous dispersion tree is not particularly limited, but for example, a comb-shaped macromonomer is produced, and this is copolymerized with another monomer, and two or more unsaturated trees are produced during the polymerization.
  • a method for producing by using a monomer having a bond in combination can be mentioned.
  • a compound having an isocyanate group and a polymerizable unsaturated group is reacted with a polymer containing a hydroxyl group or a polymer having a hydroxyl group introduced at the terminal with a serial transfer agent (step 1).
  • a macromonomer as represented by the following general formula can be obtained.
  • a polymerization reaction is carried out in which the macromonomer represented by the general formula (5) is used in combination with an unsaturated polymerizable monomer (step 2). This gives a comb-shaped polymer. Even in such a lost polymer, if a hydroxyl group is introduced, a comb-type macromonomer can be obtained by reacting the polymer with the above-mentioned compound having an isocyanate group and a polymerizable unsaturated group (step 3). ). Further, NAD can be obtained by reacting the comb-type macromonomer obtained in this step 3 with an unsaturated group-containing monomer (step 4).
  • a monomer having two or more polymerizable unsaturated groups in combination in the polymerization reaction in the step 2 and / or the step 3.
  • a crosslinked chain is formed and the solubility of the resin in the solvent is reduced, so that a more suitable NAD can be obtained.
  • an unsaturated polymerizable monomer having an alkyl ester group in all or any of the steps 1 to 4.
  • the alkyl ester group needs to be one that easily causes a transesterification reaction.
  • an alkyl ester group as described above, (1) Tertiary alkyl ester group (2) Any of the ester groups having a long side chain as represented by the above-mentioned general formulas (1), (3) and (5) is preferable. Of these, an ester group having the long side chain of (2) is preferable. Further, it may be a monomer corresponding to any of (1) and (2), which is a tertiary alkyl ester group having a long side chain, or the monomer of (1) and the monomer of (2). A monomer may be used in combination.
  • the monomer having an alkyl ester group represented by the above (A-1) and (A-2) is used in the production at a ratio of 1 to 50% by weight based on the total amount of the raw material. It is preferable to use it. Further, it is more preferable to have an alkyl ester group on the outside of the core because it reacts with other components of NAD during thermosetting.
  • NAD is produced by the above-mentioned method
  • (B) an isocyanate group and a polymerizable unsaturated group It is required to use a compound having (C) a monomer having two or more polymerizable unsaturated groups.
  • a monomer having (D) a long-chain aliphatic side chain can also be used.
  • other unsaturated functional group-containing monomers may be used in combination.
  • the core portion does not have to be three-dimensionally crosslinked.
  • the dispersant / dispersion stabilizer does not have to react with the core portion, and there is no problem as long as the particles are stably present. Those that can be used as these monomers are illustrated below.
  • the amount of the (A) hydroxyl group-containing monomer used described above may be adjusted to be excessive, or the step which is the final step in the above method. It can be obtained by a method such as using a hydroxyl group-containing monomer in No. 4.
  • R 22 is a hydrocarbon group having 1 to 20 carbon atoms.
  • R 23 is an H or methyl group
  • (C) Monomer having 2 or more polymerizable unsaturated groups (C) Monomer having 2 or more polymerizable unsaturated groups is used in the steps (2) and / or (3) of the above production method. It is preferably used. By using such a monomer as a part, a crosslinked chain is appropriately formed in the molecule, which has an effect of reducing the solubility of the resin in a solvent.
  • the monomer having two or more polymerizable unsaturated groups for example, those exemplified below can be used.
  • Such a monomer preferably has a relatively low molecular weight of 180 to 800, and any compound having two or more (meth) acryloyl groups can be used. A large number of such compounds are known, but any of these can be used in the present application. Further, two or more of these can be used in combination. These specific ones are illustrated below.
  • Examples of (meth) acrylates having 2 functional groups are 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and ethylene glycol.
  • PO adduct diacrylate of bisphenol A manufactured by Kyoeisha Chemical Co., Ltd .; BP-4PA
  • DCP-A dimethylol-tricyclodecandi (meth) acrylate
  • DCP-A dimethylol-tricyclodecandi (meth) acrylate
  • Examples of (meth) acrylates having 3 functional groups include trimethylolmethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide-modified tri (meth) acrylate, and trimethylolpropane propylene oxide-modified tri (meth) acrylate.
  • trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate and the like can be preferably used.
  • Examples of (meth) acrylates having 4 functional groups are dipentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide-modified tetra (meth) acrylate, and pentaerythritol propylene oxide-modified tetra (meth) acrylate.
  • Ditrimethylol propanetetra (meth) acrylate and the like Ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like can be preferably used.
  • Examples of (meth) acrylates having 4 or more functional groups include pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide-modified tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol tetra (meth) acrylate.
  • the other ethylenically unsaturated monomer is not particularly limited, and for example, esters of acrylic acid or methacrylic acid such as cyclohexyl (meth) acrylate and benzyl methacrylate; Viscort 3F, 3MF, 8F, 8MF ( All of the above are manufactured by Osaka Organic Chemical Co., Ltd., trade name), fluorocyclohexyl (meth) acrylate, fluorovinyl-containing monomer such as vinyl fluoride; N, N-dimethylaminoethyl (meth) acrylate, N, N- Nitrogen-containing vinyl-based monomers such as diethylaminoethyl (meth) acrylate and N, N-diethylmethacrylate; Vinyl ether-based monomers such as vinyl ethyl ether and vinyl butyl ether; Fragrances such as styrene, ⁇ -methylstyrene and vinyltoluene Group vinyl mono
  • the organic solvent preferably dissolves the polymerizable unsaturated monomer to be polymerized, but substantially does not dissolve the polymer formed from the polymerizable unsaturated monomer, and preferably has a small polarity.
  • aliphatic or aromatic hydrocarbons with relatively low dissolving power such as VM & P naphtha, mineral spirit, solvent kerosene, aromatic naphtha, solvent naphtha; n-butane, n-hexane, n-heptane, n- Aliphatic hydrocarbons such as octane, isononan, n-decane and n-dodecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclobutane are used.
  • polar solvents such as ester-based, ether-based, ketone-based, and alcohol-based solvents can be used in combination in a small proportion.
  • a polymerization initiator is blended and the polymerization temperature is set to 30 to 150 ° C., preferably 50 to 110 ° C.
  • the polymerization time is usually preferably about 2 to 10 hours.
  • polymerization initiator examples include organic peroxides such as benzoyl peroxide, lauroyl peroxide, caproyl peroxide, t-butylperoctate, and diacetyl peroxide; azobisisobutyronitrile and azobisdimethylvaleronitrile. , Azo-based initiators such as dimethyl ⁇ , ⁇ '-azoisobutyrate; dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate; and redox initiators.
  • concentration of the polymerization initiator is preferably in the range of 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the polymerizable unsaturated monomer.
  • the content of the alkyl ester group is not particularly limited, and for example, it is preferably introduced at a ratio of 1 to 80 wt%. By introducing at such a ratio, it is preferable in that good curing performance can be obtained.
  • a block copolymer may be used as the film property modifier. Since the block copolymer has two or more polymers having different properties, it is excellent in the property of changing the physical properties of the film at the time of curing, and by using this as a part, the thermosetting resin of the present invention can be used. The physical properties of the cured product obtained by using the composition can be improved.
  • A has crosslinkability (reactivity), but B has no reactivity (and vice versa), and the part B is also designed with a very hard resin. Alternatively, it can be designed with a soft resin. It is also possible to have molecular weight, polarity, curability, and functionality. When it is blended in a large amount, it becomes a film property improving agent, but when it is mixed in a small amount, it can be used as an additive in various forms such as leveling property, defoaming property, and pigment dispersant.
  • the block copolymer of the present invention is preferably a polymer obtained by using a polymerizable unsaturated functional group.
  • the block polymer refers to a resin structure in which a structure composed of A and a structure composed of B appear alternately when a structural unit A having a specific resin composition and a structural unit B having another resin composition are used. These structures are not particularly limited, and any combination thereof can be obtained.
  • the block copolymer also contributes to the curing of the resin by the transesterification reaction. May be good.
  • the method for producing the block copolymer is not particularly limited.
  • the monomer constituting the constituent unit B is added in the state of a living polymer. And polymerize. After that, it can be obtained by repeating the steps of further adding the monomer constituting the structural unit A in the state of the living polymer and performing the polymerization.
  • the block copolymer can also have an alkyl ester group and a hydroxyl group.
  • the alkyl ester group is an ester having a long side chain as represented by the above-mentioned (1) tertiary alkyl ester group (2) and the above-mentioned general formulas (1), (3) and (5). It is preferably introduced by any of the groups.
  • the hydroxyl group-containing monomer those described above can be used.
  • the monomer constituting the block copolymer other unsaturated group-containing monomers described above may be used in combination.
  • polyester resin In the thermosetting resin composition of the present invention, a polyester resin may be blended as a film property modifier. When a polyester resin is blended, it is preferable in that it can be made into a high solid and the physical properties of the film can be modified. Polyester resin is generally soft, and when it is made into a cured film, it has good followability. In particular, it is particularly advantageous when processing after curing such as PMC.
  • the polyester resin can usually be produced by dehydration condensation or transesterification reaction of an acid component and an alcohol component.
  • the acid component include compounds usually used as the acid component in the production of polyester resin.
  • the acid component include aliphatic polybasic acids, alicyclic polybasic acids, aromatic polybasic acids, and anhydrides and esterified products thereof.
  • the aliphatic polybasic acid and its anhydrides and esterified products generally include an aliphatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aliphatic compound, and an ester of the aliphatic compound.
  • Aliphatics such as succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, octadecanedioic acid, citric acid, butanetetracarboxylic acid and the like.
  • Examples thereof include a group polyvalent carboxylic acid; an anhydride of the above aliphatic polyvalent carboxylic acid; an esterified product of a lower alkyl having about 1 to about 4 carbon atoms of the above aliphatic polyvalent carboxylic acid, and any combination thereof.
  • the aliphatic polybasic acid is preferably adipic acid and / or adipic acid anhydride from the viewpoint of smoothness of the obtained coating film.
  • the alicyclic polybasic acid, and its anhydrides and esterified products are generally compounds having one or more alicyclic structures and two or more carboxyl groups in one molecule, and acid anhydrides of the above compounds. And esterified compounds of the above compounds.
  • the alicyclic structure is mainly a 4- to 6-membered ring structure.
  • Examples of the alicyclic polybasic acid and its anhydrides and esters include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 4-cyclohexene-1.
  • the above alicyclic polybasic acids, and their anhydrides and esterified products include 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid anhydride, 1, from the viewpoint of smoothness of the obtained coating film.
  • 3-Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid anhydride are preferred, and 1,2-cyclohexanedicarboxylic acid and / Alternatively, 1,2-cyclohexanedicarboxylic acid anhydride is more preferable.
  • the aromatic polybasic acid, and its anhydrides and esters are generally an aromatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aromatic compound, and an ester of the aromatic compound. It is a compound, for example, an aromatic polyvalent carboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, trimellitic acid, pyromellitic acid; the above aromatic polyvalent carboxylic acid. Acid anhydrides; esterified products of lower alkyls having about 1 to about 4 carbon atoms of the aromatic polyvalent carboxylic acid, and any combination thereof. As the aromatic polybasic acid and its anhydrides and esterified products, phthalic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and trimellitic anhydride are preferable.
  • an acid component other than the aliphatic polybasic acid, the alicyclic polybasic acid and the aromatic polybasic acid for example, coconut oil fatty acid, cotton seed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid.
  • Thor oil fatty acid soybean oil fatty acid, flaxseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid and other fatty acids; Monocarboxylic acids such as acids, linoleic acids, linolenic acids, benzoic acids, p-tert-butyl benzoic acids, cyclohexanoic acids, 10-phenyloctadecanoic acids; lactic acids, 3-hydroxybutanoic acids, 3-hydroxy-4-ethoxybenzoic acids Hydroxycarboxylic acids such as, and any combination thereof.
  • the alcohol component includes polyvalent alcohols having two or more hydroxyl groups in one molecule, for example, ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4.
  • Esterdiol compounds Polyetherdiol compounds such as alkylene oxide adducts of bisphenol A, polyethylene glycols, polypropylene glycols, polybutylene glycols; glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1, 2, 6 -Trivalent or higher alcohols such as hexanetriol, pentaerythritol, dipentaerythritol, tris (2-hydroxyethyl) isocyanuric acid, sorbitol, and mannit; a lactone compound such as ⁇ -caprolactone is added to the above trivalent alcohol. Polylactone polyol compound; fatty acid esterified product of glycerin and the like.
  • an alcohol component other than the polyhydric alcohol for example, monoalcohol such as methanol, ethanol, propyl alcohol, butyl alcohol, stearyl alcohol, 2-phenoxyethanol; propylene oxide, butylene oxide, "Cadura E10" ( Examples thereof include alcohol compounds obtained by reacting an acid with a monoepoxy compound (trade name, glycidyl ester of synthetic highly branched saturated fatty acid, manufactured by HEXION Specialy Chemicals).
  • the polyester resin is not particularly limited and can be produced according to a usual method.
  • the acid component and the alcohol component are heated in a nitrogen stream at about 150 to about 250 ° C. for about 5 to about 10 hours to carry out a dehydration condensation or transesterification reaction between the acid component and the alcohol component. Therefore, a polyester resin can be produced.
  • the above-mentioned film property modifier (A-1) is used as a part of the resin composition, but it further contains another resin component (A-2).
  • the resin component (A) it is essential that the resin component (A) has an alkyl ester group and a hydroxyl group.
  • these functional groups may be present in the above-mentioned film property modifier (A-1) or in other resin components (A-2). .. More preferably, these functional groups are present in both the film property modifier (A-1) and the other resin component (A-2).
  • the film property modifier (A-1) is NAD particles, it preferably has an alkyl ester group as described above. Therefore, in this case, the other resin component (A-2) is preferably a resin containing at least a hydroxyl group.
  • the other resin component (A-2) is not particularly limited, and various hydroxyl group-containing resins widely used in the coating field can be used. Examples of the resin that can be used include, but the resin is not limited thereto.
  • Acrylic polyol for example, a hydroxyl group-containing polymerizable unsaturated monomer (a 1 ) and another polymerizable unsaturated monomer (a 2 ) copolymerizable with the above (a 1 ) can be used as a known method. It can be produced by copolymerizing with. More specifically, polymerization methods such as a solution polymerization method in an organic solvent, an emulsion polymerization method in water, a miniemulsion polymerization method in water, and an aqueous solution polymerization method can be mentioned.
  • the hydroxyl group-containing polymerizable unsaturated monomer (a 1 ) is a compound having one or more hydroxyl groups and one or more polymerizable unsaturated bonds in one molecule.
  • the hydroxyl group-containing polymerizable unsaturated monomer (a 1 ) is not particularly limited. Particularly representative examples of such hydroxyl group-containing vinyl monomers are shown below.
  • 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
  • Various hydroxyl group-containing vinyl ethers such as vinyl ethers; or addition reaction products of these various vinyl ethers listed above with ⁇ -caprolactone; 2-Hydroxyethyl (meth) allyl ether, 3-hydroxypropyl (meth) allyl ether, 2-hydroxypropyl (meth) allyl ether, 4-hydroxybutyl (meth) allyl ether, 3-hydroxybutyl (meth) allyl ether, Various hydroxyl group-containing allyl ethers, such as 2-hydroxy-2-methylpropyl (meth) allyl ether, 5-hydroxypentyl (meth) allyl ether or 6-hydroxyhe
  • the hydroxyl group-containing monomer as a monomer does not have a hydroxyl group at a position close to the unsaturated bond (specifically, the number of atoms between the hydroxyl group and the unsaturated bond is 2 or less).
  • the hydroxyl group When a hydroxyl group is formed via a connecting chain having 3 or more atoms and 50 or less atoms, the hydroxyl group easily moves in the resin, which is preferable in that an ester exchange reaction is likely to occur.
  • the hydroxyl group-containing monomer when it has a hydroxyl group via a connecting chain having 3 or more and 50 or less atoms, it has both this structure and a structure derived from the unsaturated group-containing ester compound of the present invention. By doing so, it becomes possible to obtain low-temperature curing performance. It is preferable to use the above-mentioned hydroxyl group-containing monomer from the viewpoint of obtaining such an unexpected effect. It is presumed that such an effect can be obtained by easily causing a transesterification reaction because both the alkyl ester group and the hydroxyl group have a high degree of freedom in the resin.
  • a hydroxyl group-containing monomer having a structure represented by the following general formula (7) for a part or all of the hydroxyl groups.
  • R 31, R 32, R 33 are the same or different, hydrogen, an alkyl group, a carboxyl group, an alkyl ester group or the following R 34 - represents the [OH] a structure represented by m1.
  • R 34 has a main chain having 3 or more and 50 or less atoms, and has 1 or 2 or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and urethane in the main chain. It may also have an aliphatic, alicyclic or aromatic alkylene group which may have a side chain.
  • the compound represented by the general formula (7) is preferably a derivative of (meth) acrylic acid represented by the following general formula (8).
  • R 35 is H or CH 3
  • R 36 has a main chain having 3 or more and 49 or less atoms, and has 1 or 2 or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and urethane in the main chain. It may also have an aliphatic, alicyclic or aromatic alkylene group which may have a side chain.
  • Such a main chain having a hydroxyl group via a connecting chain having a number of molecules of 3 or more and 50 or less are 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 1,4-cyclohexane.
  • (Meta) acrylates such as dimethanol mono (meth) acrylates, polyethylene glycol mono (meth) acrylates or polypropylene glycol mono (meth) acrylates; or the various (meth) acrylates listed above and ⁇ -caprolactone.
  • the main components of the addition reaction can be mentioned.
  • the other resin component (A-2) may have an alkyl ester group.
  • the alkyl ester group is preferably derived from the compound exemplified as being usable in the non-aqueous dispersion resin particles (A) described above. In particular, it is a structural unit that easily causes a transesterification reaction.
  • (1) Tertiary alkyl ester group (2) It is introduced by any of the ester groups having a long side chain as represented by the general formulas (1), (3) and (5) described above. Is preferable.
  • Examples of the other polymerizable unsaturated monomer (a 2 ) copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer (a 1 ) include the following monomers (i) to (xix) and any combination thereof. Can be mentioned.
  • Alkyl or cycloalkyl (meth) acrylate For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (Meta) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate,
  • (vi) Polymerizable unsaturated monomer having an alkoxysilyl group: Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, ⁇ - (meth) acryloyloxypropyltrimethoxysilane, ⁇ - (meth) acryloyloxypropyltriethoxysilane, etc.
  • (Vii) Polymerizable unsaturated monomer having an alkyl fluorinated group: Perfluoroalkyl (meth) acrylates such as perfluorobutylethyl (meth) acrylates and perfluorooctylethyl (meth) acrylates; polymerizable unsaturated monomers having photopolymerizable functional groups such as fluoroolefins (viii) maleimide groups (viii) ix) Vinyl compound: N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate, etc.
  • Epoxy group-containing polymerizable unsaturated monomer Glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate , Allyl glycidyl ether, etc.
  • (Xvii) Polymerizable unsaturated monomer with UV-absorbing functional group: 2-Hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- (3-) Methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H -Benzotriazole, etc.
  • UV-stable polymerizable unsaturated monomer 4- (Meta) acryloyloxy-1,2,2,6,6-pentamethylpiperidin, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4- (meth) ) Acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl- 4-Cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2, 2,6,6-tetramethylpiperidin, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidin, 1-crot
  • (Xix) Polymerizable unsaturated monomer having a carbonyl group: Acrolein, diacetone acrylamide, diacetone methacrylamide, acetacetoxyethyl methacrylate, formyl styrene, vinyl alkyl ketone having about 4 to about 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), etc.
  • polymerizable unsaturated group means an unsaturated group capable of radical polymerization or ionic polymerization.
  • examples of the polymerizable unsaturated group include a vinyl group and a (meth) acryloyl group.
  • the ratio of the hydroxyl group-containing polymerizable unsaturated monomer (a 1 ) in producing the acrylic polyol is preferably 0.5 to 50% by weight based on the total amount of the monomer components. Within such a range, an appropriate crosslinking reaction can be generated, and excellent coating film physical properties can be obtained.
  • the lower limit is more preferably 1.0% by weight, further preferably 1.5% by weight.
  • the upper limit is more preferably 40% by weight.
  • the hydroxyl value of the acrylic polyol is preferably 1 to 200 mgKOH / g from the viewpoint of water resistance of the formed coating film and the like.
  • the lower limit is more preferably 2 mgKOH / g, and even more preferably 5 mgKOH / g.
  • the upper limit is more preferably 180 mgKOH / g, and even more preferably 170 mgKOH / g.
  • an acrylic polyol a commercially available one can also be used.
  • the commercially available product is not particularly limited, and for example, Acrydic A-801-P, A-817, A-837, A-848-RN, A-814, 57-773, A-829 manufactured by DIC Corporation. , 55-129, 49-394-IM, A-875-55, A-870, A-871, A-859-B, 52-668-BA, WZU-591, WXU-880, BL-616, CL -1000, CL-408 and the like can be mentioned.
  • the ester group in the ester compound (A) can be arbitrarily blended with respect to the number of hydroxyl groups derived from the acrylic polyol, but it is 1 to 200% (number ratio). preferable.
  • the other resin component (A-2) is not limited to the above-mentioned resin, and a low molecular weight polyol (specifically, a molecular weight of 2,000 or less) should be used. You can also.
  • Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, and 2,3-.
  • Thermosetting resin compositions using such low molecular weight polyols are known as general-purpose products and can be obtained at low cost. Further, the low molecular weight polyol has strong water solubility and can be suitably used as a cross-linking agent for the purpose of curing in an aqueous system. In recent years, environmental problems have been called for, and it can be suitably used as a cross-linking agent which is very important for promoting the reduction of VOC.
  • an ester compound having two or more ester groups can also be used as the other resin component (A-2).
  • the ester compound is not particularly limited, and examples thereof include those exemplified below.
  • a compound obtained by an addition reaction between a compound having an active methylene group and a vinyl group A compound having an active methylene group represented by the following general formula (9) causes an addition reaction with a vinyl group.
  • R 40 represents a primary to tertiary alkyl group having 50 or less carbon atoms.
  • X represents an OR 40 group or a hydrocarbon group having 5 or less carbon atoms. When 2 R 40s are present in one molecule, these R 40s may be the same or different.
  • R 40 is not particularly limited, but is a methyl ester group, an ethyl ester group, a benzyl ester group, an n-propyl ester group, an isopropyl ester group, an n-butyl ester group, an isobutyl ester group, sec-. Those having a known ester group such as a butyl ester group can be used.
  • Specific examples of the compound having such an active methylene group include malonic acid ester and acetoacetic ester.
  • a compound obtained by adding these compounds to a vinyl compound can be used.
  • a compound represented by the following general formula (10-1) can also be obtained by causing a Michael reaction in both of the two hydrogens of the active methylene group.
  • the compound obtained by such a reaction has a structure represented by the general formula (10) and / or a structure represented by the general formula (10-1), which has two or more alkyl ester groups. Since it is a compound having, it can be particularly preferably used for the purpose of the present invention.
  • R 40 represents a primary to tertiary alkyl group having 50 or less carbon atoms.
  • R 45 represents a hydrogen or methyl group.
  • R 46 is not particularly limited and may be any functional group depending on the purpose.
  • a compound represented by the following general formula (12) can also be obtained by causing a Michael reaction in both of the two hydrogens of the active methylene group.
  • the compound represented by the general formula (12) can be obtained by adjusting the molar ratio of the (meth) acrylic acid ester to the active methylene compound in the formulation of the raw materials. Further, by adjusting these molar ratios, it can also be obtained as a mixture of the compound represented by the general formula (11) and the compound represented by the general formula (12).
  • the ester compound obtained by such a reaction is
  • the numerator has a structural unit represented by the structure of.
  • the structure represented by the above-mentioned general formula (13) and / or the structure represented by (14) can be molecularly formed. It can also be an ester compound having two or more in it. That is, it has the functional group.
  • a compound having a structure represented by the general formula of can be preferably used in the present invention.
  • Such a compound is preferable because it has high transesterification reactivity and has many COOR groups in the molecule, so that good curability can be obtained.
  • n 5 and n 6 in the above general formula are 2 to 12.
  • L and M are not particularly limited as long as they have a structure such that the molecular weight of the compound is 3000 or less, and have any functional group such as a hydroxyl group, an ester group, an ether group, a urethane group and an amide group. Represents a hydrocarbon group that may be present.
  • the above-mentioned "compound obtained by an addition reaction between a compound having an active methylene group and a vinyl group” is a compound using a compound having two or more unsaturated bonds in one molecule as a raw material, and the above general formula is used.
  • a molecule having two or more structures represented by (15) and / or a structure represented by the general formula (16) may be used.
  • the one obtained by adding Michael dimethylol tricyclodecane acrylate to diethyl malonate has a low viscosity, and the overall viscosity can be lowered by blending it with a thermosetting resin. This is preferable in that it aims at high solid differentiation (high solidification).
  • Such a compound is obtained by carrying out a Michael addition reaction with a compound having an active methylene group using various (meth) acrylic acid derivatives having two or more unsaturated bonds as raw materials.
  • the above-mentioned "(meth) acrylic acid derivative having one or more unsaturated bonds” is not particularly limited, and examples thereof include the following.
  • Examples of (meth) acrylates having 1 functional group are methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl ( Examples thereof include meta) acrylate and t-butyl (meth) acrylate.
  • Examples of (meth) acrylates having 2 functional groups are 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and ethylene glycol.
  • PO adduct diacrylate of bisphenol A manufactured by Kyoeisha Chemical Co., Ltd .; BP-4PA
  • DCP-A dimethylol-tricyclodecandi (meth) acrylate
  • DCP-A dimethylol-tricyclodecandi (meth) acrylate
  • Examples of (meth) acrylates having 3 functional groups include trimethylolmethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide-modified tri (meth) acrylate, and trimethylolpropane propylene oxide-modified tri (meth) acrylate.
  • trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate and the like can be preferably used.
  • Examples of (meth) acrylates having 4 functional groups are dipentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide-modified tetra (meth) acrylate, and pentaerythritol propylene oxide-modified tetra (meth) acrylate.
  • Ditrimethylol propanetetra (meth) acrylate and the like Ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like can be preferably used.
  • Examples of (meth) acrylates having 4 or more functional groups include pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide-modified tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol tetra (meth) acrylate.
  • R represents the same or different alkyl groups.
  • n 7 represents 1 to 10.
  • the above compound preferably has two or more alkyl esters serving as cross-linking points in the molecule. That is, the larger the number of alkyl ester groups in the molecule, the higher the crosslink density of the resin after curing, which is preferable in that the hardness of the cured product becomes good and a cured product having excellent physical properties can be obtained. It is more preferable that the above alkyl ester is 3 or more in the molecule.
  • a compound obtained by reacting a polyfunctional carboxylic acid or a derivative thereof with an alcohol can also be used as the ester compound (A1) of the present invention.
  • Such a reaction can be expressed by the following general formula.
  • polyfunctional carboxylic acids are general-purpose raw materials that are widely and inexpensively provided in many applications such as polyester raw materials, polyamide raw materials, neutralizers, synthetic raw materials and many other applications.
  • a compound obtained by alkyl esterifying such a polyfunctional carboxylic acid by a known method can also be used in the present invention. Esterification can be carried out by the above-mentioned alkyl group having 50 or less carbon atoms.
  • ester compound When such a compound is used as an ester compound, it can be esterified at low cost by a known method, and a multivalent ester group can be introduced with a relatively low molecular weight. Further, the esterification improves the compatibility with the organic solvent and can be preferably used. It is preferable in that.
  • the polyfunctional carboxylic acid used here is not particularly limited, and for example, one having 50 or less carbon atoms can be used. More specifically, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, octadecanedioic acid, citric acid, tartaric acid, An aliphatic polyvalent carboxylic acid such as butanetetracarboxylic acid; 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 Alicyclic polyvalent carboxylic acid phthalic acid such as -1,2-cyclohex
  • the above-mentioned compounds having two or more alkyl ester groups may be used in combination. Moreover, you may use the acid anhydride of these compounds as a raw material.
  • the above-mentioned method for alkyl esterifying a polyfunctional carboxylic acid is not particularly limited, and a known method such as dehydration condensation with an alcohol can be applied.
  • the ester compound preferably has a molecular weight of 10,000 or less. Such a structure is preferable in that the molecules move easily and the curing proceeds.
  • the molecular weight may be lower, such as 6,000 or less, 4,000 or less, and 2,000 or less.
  • the ester group in the non-aqueous dispersion resin particles can be arbitrarily blended with respect to the number of hydroxyl groups derived from the other resin component (A-2), but 1 to 200% (1 to 200%).
  • the number ratio) is preferable.
  • thermosetting resin composition of the present invention contains a transesterification catalyst (B). That is, the transesterification catalyst (B) is blended in order to efficiently generate a transesterification reaction between the ester group and the hydroxyl group and obtain sufficient thermosetting property.
  • transesterification catalyst (B) any compound known as capable of activating the transesterification reaction can be used.
  • various acidic compounds such as, for example, hydrochloric acid, sulfuric acid, nitrate, acetic acid, phosphoric acid or sulfonic acid, heteropolyacids; various basics such as LiOH, KOH or NaOH, amines, phosphines and the like.
  • Examples thereof include quaternary ammonium salts such as carbonate, tetrabutylphosphonium bromide, and phosphonium salts such as tetrabutylphosphonium hydroxide.
  • a photoresponsive catalyst and a thermal latent catalyst that generate an acid by light or heat can also be used.
  • a zinc cluster catalyst for example, ZnTAC24 (trade name) manufactured by Tokyo Chemical Industry Co., Ltd.
  • two or more kinds of the transesterification catalyst (B) described above may be used in combination.
  • the alkyl ester group is not limited. Further, in the thermosetting resin composition of the present invention, since a good curing reaction can be caused without using an acid catalyst, it is possible to prepare a thermosetting resin composition to which a basic compound is added. It is also preferable in that it can be done.
  • an amine compound may be used as an additive such as a pigment dispersant.
  • an acid group such as a carboxylic acid group or a sulfonic acid group into the resin and neutralize the acid group with an amine compound or the like to make the paint water-soluble.
  • an acidic catalyst This has been a problem that hinders the water-based conversion of the thermosetting resin composition in which the transesterification catalyst is used as the curing reaction.
  • the present invention since it can be cured even under basic conditions, it can be made water-based.
  • thermosetting resin composition of the present invention is used as a solvent-based coating composition
  • a water-based coating material may be used in combination as a part of the multilayer coating film.
  • amines, ammonia and the like may be generated from other layers forming the multilayer coating film. Even in such a case, it is preferable in that good curing can be performed.
  • the amount of the transesterification catalyst (B) used is 0.01 to 50% by weight based on the total weight of the film property modifier (A-1) and the other resin component (A-2). Is preferable. It is preferable that the content is within such a range because a good curing reaction can be performed at a low temperature.
  • thermosetting resin composition of the present invention may be used in combination with other cross-linking agents generally used in the field of paints and adhesives in addition to the above-mentioned components.
  • the cross-linking agent that can be used is not particularly limited, and examples thereof include isocyanate compounds, blocked isocyanate compounds, melamine resins, epoxy resins, and silane compounds.
  • vinyl ether, anionic polymerizable monomer, cationically polymerizable monomer, radically polymerizable monomer and the like may be used in combination.
  • a curing agent for accelerating the reaction of these combined cross-linking agents may be used in combination.
  • the amount used is preferably 30% by weight or less. That is, when the above-mentioned cross-linking agent is used, this may cause problems such as a decrease in storage stability, a sick house syndrome due to formaldehyde, and an increase in price due to the use of an isocyanate compound. In the present invention, stable curability can be ensured without causing these problems, and excellent coating film performance can also be obtained.
  • the amount used is more preferably 25% by weight or less, further preferably 22% by weight or less. It may not contain these substantially.
  • substantially not contained means that another cross-linking agent performs main cross-linking and determines the physical properties of the film, and when it is simply used as an auxiliary, it means outside the range.
  • thermosetting resin composition of the present invention can be suitably used in the fields of thermosetting paints, thermosetting adhesives and the like.
  • thermosetting resin composition of the present invention contains the above-mentioned film property modifier, it is also preferable in that high solid differentiation (high solidification) of the coating material can be achieved.
  • high solid differentiation high solidification
  • the viscosity is such that it can be applied to a general coating method such as spraying even if the solid content is increased. That is, in order to achieve high solid differentiation, it is necessary to have a low molecular weight, which causes deterioration of paint physical properties.
  • the film physical property adjusting agent as in the present invention is contained, the viscosity does not increase, and the film physical properties are maintained.
  • thermosetting resin composition of the present invention it is also preferable in that high solid differentiation can be performed while maintaining a low viscosity. Specifically, high solidification can be achieved by using such a film property modifier.
  • additives generally used in the paint field may be used in combination.
  • coloring pigments, extender pigments, brilliant pigments, etc., and any combinations thereof may be used in combination.
  • a pigment When a pigment is used, it is preferably contained in the range of 1 to 500% by weight in total, based on 100% by weight of the total solid content of the resin components.
  • the lower limit is more preferably 3% by weight, still more preferably 5% by weight.
  • the upper limit is more preferably 400% by weight, still more preferably 300% by weight.
  • coloring pigments examples include titanium oxide, zinc flower, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolin pigments, slene pigments, and perylene pigments. , Dioxazine pigments, diketopyrrolopyrrole pigments and the like, and any combinations thereof.
  • extender pigment examples include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, alumina white and the like, with barium sulfate and / or talc being preferable, and barium sulfate being more preferable.
  • the bright pigment examples include aluminum (including vapor-deposited aluminum), copper, zinc, brass, nickel, aluminum oxide, mica, titanium oxide or iron oxide-coated aluminum oxide, titanium oxide or iron oxide.
  • Examples include mica, glass flakes, hologram pigments, etc., and any combination thereof.
  • the aluminum pigments include non-leaving type aluminum and leaving type aluminum.
  • thermosetting paint may be added to paints such as thickeners, ultraviolet absorbers, light stabilizers, defoamers, plasticizers, organic solvents other than the hydrophobic solvents, surface conditioners, and sedimentation inhibitors. It may further contain an agent.
  • the thickener examples include inorganic thickeners such as silicate, metallic silicate, montmorillonite, and colloidal alumina; a copolymer of (meth) alginic acid and (meth) acrylic acid ester, and poly.
  • Polyacrylic acid-based thickeners such as sodium acrylate; have a hydrophilic part and a hydrophobic part in one molecule, and the hydrophobic part is adsorbed on the surface of pigments and emulsion particles in the paint in an aqueous medium.
  • An associative thickener that exhibits a thickening effect by associating the hydrophobic portions with each other; a fibrous derivative-based thickener such as carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose; casein, sodium casenate, ammonium caseate, etc.
  • Protein-based thickeners alginic acid-based thickeners such as sodium alginate; polyvinyl-based thickeners such as polyvinyl alcohol, polyvinylpyrrolidone, and polyvinylbenzyl ether copolymers; pluronic polyethers, polyether dialkyl esters, polyether dialkyl ethers, Polyether-based thickeners such as polyether epoxy modified products; Maleic anhydride copolymer-based thickeners such as partial esters of vinyl methyl ether-maleic acid copolymer; Polyamide thickeners such as polyamideamine salts Etc., as well as any combination thereof.
  • the polyacrylic acid-based thickeners are commercially available, and are, for example, "ACRYSOLASE-60”, “ACRYSOLTT-615”, “ACRYSOLRM-5" (hereinafter, trade names) manufactured by Roam and Hearth, and San Nopco. Examples thereof include “SN thickener 613”, “SN thickener 618”, “SN thickener 630”, “SN thickener 634", and “SN thickener 636" (hereinafter, product names).
  • association type thickeners are commercially available, and for example, "UH-420", “UH-450”, “UH-462”, “UH-472”, “UH-540” manufactured by ADEKA, Inc. "UH-752”, “UH-756VF”, “UH-814N” (above, trade name), “ACRYSOLRM-8W”, “ACRYSOLRM-825”, “ACRYSOLRM-2020NPR”, “ACRYSOLRM” manufactured by Roam & Hearth.
  • the object to be coated to which the above thermosetting paint can be applied is not particularly limited, and for example, the outer panel of an automobile body such as a passenger car, truck, motorcycle, or bus; automobile parts; mobile phones, audio equipment, etc.
  • an automobile paint it can be used for the effect of any layer such as an intermediate coating paint, a base paint, and a clear paint.
  • the object to be coated may be a metal surface such as the metal material and a vehicle body formed from the metal material, which may be subjected to surface treatment such as phosphate treatment, chromate treatment, composite oxide treatment, or the like. It may be an object to be coated having a coating film.
  • Examples of the object to be coated having the coating film include those obtained by subjecting a base material to a surface treatment as desired and forming an undercoat coating film on the substrate.
  • a vehicle body in which an undercoat film is formed by an electrodeposition paint is preferable, and a car body in which an undercoat film is formed by a cationic electrodeposition paint is more preferable.
  • the object to be coated may be a plastic material, a plastic surface of an automobile part molded from the plastic material, or the like, if desired, surface-treated, primer-coated, or the like. Further, the plastic material and the metal material may be combined.
  • the coating method of the heat-curable coating material is not particularly limited, and examples thereof include air spray coating, airless spray coating, rotary atomization coating, curtain coat coating, and the like, and air spray coating, rotary atomization coating, and the like are preferable. .. At the time of painting, electrostatic electricity may be applied if desired.
  • a wet coating film can be formed from the above water-based coating composition.
  • the wet coating film can be cured by heating.
  • the curing can be carried out by a known heating means, for example, a drying furnace such as a hot air furnace, an electric furnace, or an infrared induction heating furnace.
  • the wet coating is preferably at a temperature in the range of about 80 to about 180 ° C., more preferably about 100 to about 170 ° C., and even more preferably about 120 to about 160 ° C., preferably for about 10 to about 60 minutes. And more preferably, it can be cured by heating for about 15 to about 40 minutes. Further, it is preferable in that it can cope with low temperature curing at 80 to 140 ° C.
  • thermosetting resin composition of the present invention When used in the field of coating materials, it is required to have sufficient curing performance having performances such as smoothness, water resistance and acid resistance. On the other hand, when used in the fields of adhesives and adhesives, the high curing performance required for paints is not required.
  • the thermosetting resin composition of the present invention can be of a level that can be used as a paint, but even a composition that does not reach such a level is used in the fields of adhesives, adhesives, and the like. May be available.
  • the present invention is also a cured film characterized by being formed by curing the above-mentioned thermosetting resin composition.
  • a cured film has sufficient performance so that it can be used as a paint / adhesive.
  • the present invention is a non-aqueous dispersion resin particle having an alkyl ester group.
  • the alkyl ester group is also a non-aqueous dispersion resin particle characterized in that at least a part thereof is a skeleton derived from a monomer represented by the following general formula (1).
  • n 1 1 to 10 (Wherein, R 1, R 2, R 3 are the same or different, hydrogen, an alkyl group, a carboxyl group, an alkyl ester group or the following R 4 - [COOR 5]
  • R 4 representing a structure represented by n 1 Has a main chain having 50 or less atoms, and may have one or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and a urethane in the main chain.
  • An aliphatic, alicyclic or aromatic alkylene group which may have a chain.
  • R 5 is an alkyl group having 50 or less carbon atoms.
  • the non-aqueous dispersion resin is as described in detail as a film property modifier (A-1). Such non-aqueous dispersions are new. Further, it can be suitably used as a compounding component of the thermosetting resin composition of the present invention described above.
  • the part represents the weight part.
  • Synthesis example 1 150 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester NB), 150 parts of t-butyl acrylate (Kyoeisha Chemical Co., Ltd .: light acrylate TB), hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. product) : 150 parts of light ester HO-250) and 50 parts of styrene as a monomer mixture, and 25 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical V-65) as an initiator is aromatic. It was dissolved in hydrocarbon (T-SOL100) to prepare an initiator solution.
  • T-SOL100 hydrocarbon
  • T-SOL 100 aromatic hydrocarbon
  • propylene glycol monomethyl ether acetate 250 parts were placed in a stirable flask, and the monomer solution and the initiator solution were added dropwise while filling with nitrogen.
  • the polymerization temperature at this time was set to 130 ° C.
  • the dropping was carried out in 2 hours, and further aging at 130 ° C. for 4 hours to obtain a polymer solution A.
  • Synthesis example 2 240 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester NB), 105 parts of t-butyl acrylate (Kyoeisha Chemical Co., Ltd .: light acrylate TB), hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. product) : Light ester HO-250) 110 parts, styrene 30 parts, reactive emulsion (Daiichi Kogyo Chemicals: Aqualon KH-10) 15 parts, then mix 200 parts of ion-exchanged water and use a homomixer.
  • Emulsification was carried out at room temperature for 1 hour to prepare a monomer emulsion.
  • an initiator 15 parts of ammonium peroxodisulfite and 10 parts of sodium bisulfite were dissolved in ion-exchanged water to prepare an initiator solution.
  • 400 parts of ion-exchanged water was placed in a stirable flask, and a monomer solution and an initiator solution were added dropwise while filling with nitrogen to carry out polymerization.
  • the polymerization temperature at this time was 80 ° C.
  • the dropping was carried out in 2 hours, and further aging at 80 ° C. for 4 hours to obtain a polymer solution B.
  • Synthesis example 3 54 parts of ethylene glycol monoacetacetate monomethacrylate, 58 parts of t-butyl acrylate, 38 parts of potassium carbonate, 2 parts of 18-crown-6 ether and 112 parts of tetrahydrofuran were mixed and stirred at 50 ° C. for 3 hours. After completion of the reaction, cyclohexane and water were added and washed with water. The organic layer was neutralized with saturated aqueous ammonium chloride solution, washed twice with water, and the obtained organic layer was concentrated under reduced pressure to obtain Monomer A.
  • Synthesis example 4 54 parts of ethylene glycol monoacetacetate monomethacrylate, 40 parts of methyl acrylate, 38 parts of potassium carbonate, 2 parts of 18-crown-6 ether and 112 parts of tetrahydrofuran were mixed and stirred at 50 ° C. for 3 hours. After completion of the reaction, cyclohexane and water were added and washed with water. The organic layer was neutralized with saturated aqueous ammonium chloride solution and washed twice with water, and the obtained organic layer was concentrated under reduced pressure to obtain Monomer B.
  • Synthesis example 5 N-Butyl methacrylate (Kyoeisha Chemical Co., Ltd. product: Light Ester NB) 150 parts, monomer A 150 parts, hydroxyethyl methacrylate (Kyoei Co., Ltd. product: Light ester HO-250) 150 parts, styrene 50 parts monomer A mixed solution was prepared, and 25 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical V-65) as an initiator was dissolved in aromatic hydrocarbon (T-SOL100) to prepare an initiator solution. ..
  • T-SOL 100 aromatic hydrocarbon
  • propylene glycol monomethyl ether acetate 250 parts were placed in a stirable flask, and the monomer solution and the initiator solution were added dropwise while filling with nitrogen.
  • the polymerization temperature at this time was 110 ° C.
  • the dropping was carried out in 2 hours, and further aging at 110 ° C. for 4 hours to obtain a polymer solution C.
  • Synthesis example 6 N-Butyl methacrylate (Kyoeisha Chemical Co., Ltd. product: Light Ester NB) 150 parts, monomer B 150 parts, hydroxyethyl methacrylate (Kyoei Co., Ltd. product: Light ester HO-250) 150 parts, styrene 50 parts monomer A mixed solution was prepared, and 25 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical V-65) as an initiator was dissolved in aromatic hydrocarbon (T-SOL100) to prepare an initiator solution. ..
  • Synthesis example 7 250 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester NB), 175 parts of hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester HO-250), and 75 parts of styrene were used as a monomer mixture.
  • As an initiator 25 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries V-65) was dissolved in aromatic hydrocarbon (T-SOL100) to prepare an initiator solution.
  • Synthesis example 8 24 parts of t-butyl acrylate, 40 parts of di-t-butyl malonic acid, 28 parts of potassium carbonate, 1.5 parts of 18-crown-6 ether and 64 parts of tetrahydrofuran were mixed and stirred at 50 ° C. for 1 hour. After completion of the reaction, cyclohexane and water were added and washed with water. The organic layer was neutralized with saturated aqueous ammonium chloride solution, washed twice with water, and the obtained organic layer was concentrated under reduced pressure to obtain ester compound A.
  • Synthesis example 9 80 parts of trimethylolpropane triacrylate, 37 parts of di-t-butyl malonic acid, 56 parts of potassium carbonate, 1.5 parts of 18-crown-6 ether and 117 parts of tetrahydrofuran were mixed and stirred at 50 ° C. for 3 hours. After completion of the reaction, cyclohexane and water were added and washed with water. The organic layer was neutralized with saturated aqueous ammonium chloride solution, washed twice with water, and the obtained organic layer was concentrated under reduced pressure to obtain ester compound B.
  • Synthesis example 10 31 parts of 1,6-hexanediol diacrylate, 37 parts of dimethyl malonate, 42 parts of potassium carbonate, 1.1 parts of 18-crown-6 ether and 91 parts of tetrahydrofuran were mixed and stirred at 50 ° C. for 3 hours. After completion of the reaction, cyclohexane and water were added and washed with water. The organic layer was neutralized with saturated aqueous ammonium chloride solution, washed twice with water, and the obtained organic layer was concentrated under reduced pressure to obtain ester compound C.
  • Synthesis example 11 80 parts of trimethylolpropane triacrylate, 23 parts of dimethyl malonate, 56 parts of potassium carbonate, 1.5 parts of 18-crown-6 ether and 117 parts of tetrahydrofuran were mixed and stirred at 50 ° C. for 3 hours. After completion of the reaction, cyclohexane and water were added and washed with water. The organic layer was neutralized with saturated aqueous ammonium chloride solution, washed twice with water, and the obtained organic layer was concentrated under reduced pressure to obtain ester compound D.
  • Synthesis example 12 Stearyl methacrylate (Kyoeisha Chemical Co., Ltd. Product: Light ester S) 120 parts, n-lauryl methacrylate (Kyoei company chemical company product: Light ester L) 120 parts, tertiary butyl methacrylate (Kyoei company chemical company product) : Light ester TB) 60 parts and 9 parts of 2-mercaptoethanol were used as a monomer mixture, and 3 parts of azobisisobutyronitrile as an initiator was dissolved in toluene to prepare an initiator solution. 300 parts of toluene was placed in a stirable flask, and the monomer solution and the initiator solution were added dropwise while filling with nitrogen.
  • the polymerization temperature at this time was set to 85 ° C.
  • the dropping was carried out in 2 hours, and further aging at 85 ° C. was carried out for 4 hours.
  • 18 parts of 2-isocyanatoethylacryllate (Showa Denko KK Karens AOI) and 0.15 dibutyltin dilaurate were added and reacted at 60 ° C. for 4 hours to obtain a macromonomer solution A.
  • Synthesis example 13 120 parts of stearyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester S), 120 parts of n-lauryl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester L), 60 parts of Monomer A, 9 parts of 2-mercaptoethanol A monomer mixed solution was prepared, and 3 parts of azobisisobutyronitrile as an initiator was dissolved in toluene to prepare an initiator solution. 300 parts of toluene was placed in a stirable flask, and the monomer solution and the initiator solution were added dropwise while filling with nitrogen. The polymerization temperature at this time was set to 85 ° C.
  • Synthesis example 14 120 parts of stearyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester S), 120 parts of n-lauryl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester L), 60 parts of Monomer B, 9 parts of 2-mercaptoethanol A monomer mixed solution was prepared, and 3 parts of azobisisobutyronitrile as an initiator was dissolved in toluene to prepare an initiator solution. 300 parts of toluene was placed in a stirable flask, and the monomer solution and the initiator solution were added dropwise while filling with nitrogen. The polymerization temperature at this time was set to 85 ° C.
  • Synthesis example 15 Stearyl methacrylate (Product of Kyoeisha Chemical Co., Ltd .: Light ester S) 40 parts, n-lauryl methacrylate (Product of Kyoeisha Chemical Co., Ltd .: Light ester L) 40 parts, Monomer B 20 parts, Hydrocarbon methacrylate Kyoeisha Chemical Co., Ltd. ) Product: Light ester HO-250) 20 parts ⁇ -methylstyrene dimer (Nichiyu Co., Ltd. product: Nofmer MSD) 3 parts is a monomer mixture, and 3 parts of tertiary butyl peroxyoctate is aromatic as an initiator.
  • T-SOL100 hydrocarbon
  • T-SOL100 aromatic hydrocarbon
  • the polymerization temperature at this time was set to 130 ° C.
  • the dropping was carried out in 2 hours, and further aging at 130 ° C. was carried out for 4 hours.
  • a macromonomer solution D was obtained.
  • Synthesis example 16 A monomer mixture of 60 parts of macromonomer solution A, 35 parts of methyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester M), and 5 parts of 2-hydroxymethacrylate (Kyoeisha Chemical Co., Ltd .: light ester HO-250).
  • an initiator 0.7 part of azobisisobutyronitrile was dissolved in toluene to prepare an initiator solution. 100 parts of toluene was placed in a stirable flask, and the monomer solution and the initiator solution were added dropwise while filling with nitrogen. The polymerization temperature at this time was set to 85 ° C. The dropping was carried out in 2 hours, and further aging at 85 ° C.
  • Synthesis example 17 60 parts of macromonomer solution B, 35 parts of methyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester M), and 5 parts of 2-hydroxymethacrylate (Kyoeisha Chemical Co., Ltd .: light ester HO-250) are mixed with a monomer.
  • As an initiator 0.7 part of azobisisobutyronitrile was dissolved in toluene to prepare an initiator solution. 100 parts of toluene was placed in a stirable flask, and the monomer solution and the initiator solution were added dropwise while filling with nitrogen. The polymerization temperature at this time was set to 85 ° C.
  • Synthesis example 18 60 parts of macromonomer solution C, 50 parts of methyl acrylate, 4 parts of 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd .: light acrylate HOA) were used as a monomer mixture, and 0.7 part of azobisisobutyronitrile was used as an initiator. It was dissolved in an aromatic hydrocarbon (T-SOL100) to prepare an initiator solution. 95 parts of aromatic hydrocarbon (T-SOL100) was placed in a stirable flask, and the monomer solution and the initiator solution were added dropwise while filling with nitrogen. The polymerization temperature at this time was 80 ° C. The dropping was carried out in 2 hours, and further aging at 80 ° C. was carried out for 4 hours.
  • T-SOL100 aromatic hydrocarbon
  • Synthesis example 19 60 parts of macromonomer solution D, 50 parts of methyl acrylate, and 4 parts of 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd .: light acrylate HOA) were used as a monomer mixture, and 0.7 part of azobisisobutyronitrile was used as an initiator. It was dissolved in an aromatic hydrocarbon (T-SOL100) to prepare an initiator solution. 95 parts of aromatic hydrocarbon (T-SOL100) was placed in a stirable flask, and the monomer solution and the initiator solution were added dropwise while filling with nitrogen. The polymerization temperature at this time was 80 ° C. The dropping was carried out in 2 hours, and further aging at 80 ° C. was carried out for 4 hours.
  • T-SOL100 aromatic hydrocarbon
  • Synthesis example 20 Macromonomer solution A 30 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd .: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts and 0.4 parts of ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd .: light ester EG) are used as a monomer mixture, and 0.7 parts of azobisisobutyronitrile is dissolved in heptane as an initiator. It was made into a solution.
  • Synthesis example 21 Macromonomer solution B 30 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd .: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts and 0.4 parts of ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd .: light ester EG) are used as a monomer mixture, and 0.7 parts of azobisisobutyronitrile is dissolved in heptane as an initiator. It was made into a solution.
  • Synthesis example 22 Macromonomer solution C 30 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd .: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts and 0.4 parts of ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd .: light ester EG) are used as a monomer mixture, and 0.7 parts of azobisisobutyronitrile is dissolved in heptane as an initiator. It was made into a solution.
  • Synthesis example 24 Macromonomer solution E 30 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd .: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts and 0.4 parts of ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd .: light ester EG) are used as a monomer mixture, and 0.7 parts of azobisisobutyronitrile is dissolved in heptane as an initiator. It was made into a solution.
  • Synthesis example 26 Macromonomer solution G 30 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd .: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts and 0.4 parts of ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd .: light ester EG) are used as a monomer mixture, and 0.7 parts of azobisisobutyronitrile is dissolved in heptane as an initiator. It was made into a solution.
  • Synthesis example 27 Macromonomer solution H 30 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd .: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts and 0.4 parts of ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd .: light ester EG) are used as a monomer mixture, and 0.7 parts of azobisisobutyronitrile is dissolved in heptane as an initiator. It was made into a solution.
  • Synthesis example 28 160 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester NB), 100 parts of t-butyl acrylate (Kyoeisha Chemical Co., Ltd .: light acrylate TB), hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. product) : Light ester HO-250) 100 parts, styrene 50 parts, tetraethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd.
  • Synthesis example 29 90 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester NB), 90 parts of t-butyl acrylate (Kyoeisha Chemical Co., Ltd .: light acrylate TB), hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. product) : 90 parts of light ester HO-250) and 30 parts of styrene were used as a monomer mixture, and 15 parts of tertiary butylperoxyoctate was dissolved in aromatic hydrocarbon (T-SOL100) as an initiator solution to prepare an initiator solution.
  • T-SOL100 aromatic hydrocarbon
  • the polymerization temperature at this time was set to 130 ° C.
  • the dropping was carried out in 2 hours, and further aging was carried out at 130 ° C. for 2 hours.
  • hydroxyethyl methacrylate Keroeisha Chemical Co., Ltd.
  • Product 90 parts of light ester HO-250) and 30 parts of styrene were used as a monomer mixed solution, and 15 parts of tertiary butyl peroxyoctate was added dropwise as an initiator.
  • the polymerization temperature at this time was set to 130 ° C.
  • the dropping was carried out in 2 hours, and further aging at 130 ° C. for 2 hours to obtain a polymer solution G.
  • Synthesis example 30 100 parts of hexahydroxyphthalic anhydride, 200 parts of adipic acid, 55 parts of trimethylolpropane and 200 parts of 1,6, -hexanediol were mixed in a stirable flask and reacted at 200 ° C. for 5 hours. At this time, the water that came out during the reaction was removed with a fractional distillation tube. Then, the aromatic hydrocarbon (T-SOL 100) was diluted with 110 parts and 110 parts of propylene glycol monomethyl ether propionate to obtain a polymer solution H.
  • Synthesis example 31 2-Ethylhexyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester EH) 120 parts, stearyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester S) 120 parts, n-butyl acrylate 120 parts, monomer A 60 parts, 60 parts of hydroxyacrylate (Light Ester HOA manufactured by Kyoeisha Chemical Co., Ltd.) and 120 parts of styrene were used as a monomer mixture, and 18 parts of azobisisobutyronitrile was dissolved in xylene as an initiator to prepare an initiator solution.
  • Synthesis example 32 2-Ethylhexyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester EH) 120 parts, stearyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester S) 120 parts, n-butyl acrylate 120 parts, monomer B 60 parts, 60 parts of hydroxyacrylate (Light Ester HOA manufactured by Kyoeisha Chemical Co., Ltd.) and 120 parts of styrene were used as a monomer mixture, and 18 parts of azobisisobutyronitrile was dissolved in xylene as an initiator to prepare an initiator solution.
  • the film obtained in the example was dissolved in acetone reflux for 30 minutes using Soxhlet, and the residual weight% of the film was measured as the gel fraction.
  • the gel fraction was set to 0 to 40% as x because it could not withstand practical use.
  • the gel fraction was set to ⁇ with a gel fraction of 40 to 60% assuming that constant curing was observed.
  • a gel fraction of 60 to 80% was rated as ⁇ as it could withstand practical use.
  • a gel fraction of 80 to 100% was rated as ⁇ as having excellent performance.
  • the breaking stress was taken as the maximum stress at the time of breaking from the stress-strain test of the obtained film.
  • the value at which the breaking stress was judged to be 0 to 20 MPaS was defined as ⁇ .
  • the value at which the breaking stress was judged to be 20 to 30 MPaS was defined as +.
  • the value at which the breaking stress was judged to be 30 ⁇ MPaS was defined as ++.
  • thermosetting resin composition of the present invention had good curing performance, and the obtained cured film had good breaking strength and elongation.
  • thermosetting resin composition of the present invention can be used as various coating compositions, adhesive compositions, and pressure-sensitive adhesive compositions.

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Abstract

L'invention fournit une composition de résine thermodurcissable qui présente des propriétés de durcissement satisfaisantes, qui peut être mise en œuvre dans diverses applications, dans laquelle une réaction de transestérification sert de réaction de durcissement, et qui présente des propriétés physiques satisfaisantes. Cette composition de résine thermodurcissable comprend un composant résine (A) ayant pour composant essentiel au moins une sorte de modificateur de propriétés physiques de film (A-1) choisie dans un groupe constitué de particules de résine en dispersion non aqueuse, d'un copolymère séquencé, et d'une résine de polyester. Le composant résine (A) possède un groupe alkylester, et un groupe hydroxyle. En outre, cette composition de résine thermodurcissable comprend un catalyseur de transestérification (B).
PCT/JP2019/017284 2019-04-23 2019-04-23 Composition de résine thermodurcissable, film durci, et particules de résine en dispersion non aqueuse WO2020217320A1 (fr)

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