Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/14—Polycondensates modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/02—Polycondensates containing more than one epoxy group per molecule
  • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
  • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
  • C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
  • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
  • C08G63/183—Terephthalic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/91—Polymers modified by chemical after-treatment
  • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/916—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

• the present invention relates to a modified epoxy resin, a method for producing a modified epoxy resin, a curable resin composition containing the modified epoxy resin, and a cured product of the curable resin composition.
• the present invention also relates to a paint, an adhesive, a powder coating composition, a can coating composition and a prepreg containing the curable resin composition; a coating film, a fiber-reinforced plastic and a laminate containing the cured product; and a can member and a can having the coating film.
• Epoxy resins are used in many applications, mainly in the paint, civil engineering, and electrical fields, due to their excellent electrical properties, adhesiveness, and heat resistance.
• bisphenol A-type epoxy resins are widely used because they are readily available, inexpensive, and have well-balanced mechanical properties.
• Cured coating films containing high-molecular-weight bisphenol A-type epoxy resins have high adhesion, coating film hardness, point impact resistance, flex resistance, stability in hot water, and retort resistance, and are widely used for coating the inner surface of food cans.
• US Pat. No. 6,200,401 discloses an aqueous food or beverage can coating composition suitable for use in forming food contact coatings on metal food or beverage cans, the coating composition comprising an aqueous carrier and a resin system comprising a water-dispersible polymer and an emulsion polymerized ethylenically unsaturated monomer component.
• a water-dispersible polymer an aromatic polyether polymer substantially free of each of bisphenol A, bisphenol F, and bisphenol S (including their epoxides) can be preferably used.
• Patent Document 2 discloses a copolymer of a diglycidyl ether of an aliphatic diol and an acid-terminated polyester.
• the coating composition described in Patent Document 1 is insufficient in properties such as corrosion resistance, flexibility and toughness on metal substrates.
• epoxy resins other than the bisphenol A type epoxy resin described in Patent Document 2 use a diglycidyl ether of an aliphatic diol, so they exhibit very high flexibility, but there is still room for improvement from the viewpoint of mechanical properties. Therefore, the development of epoxy resins with well-balanced flexibility and mechanical properties is desired.
• the present invention has been devised in view of the above-mentioned prior art, and an object of the present invention is to provide a modified epoxy resin having a structure different from that of bisphenol A type epoxy resins, and to provide a cured product or a cured coating film having adhesion, coating film hardness, cupping resistance, point impact resistance, flex resistance, and hot water resistance equal to or higher than those of cured products of conventional high molecular weight bisphenol A type epoxy resins.
• Another object of the present invention is to provide a method for producing a modified epoxy resin, a curable resin composition containing the modified epoxy resin, and a cured product of the curable resin composition containing the modified epoxy resin.
• the present inventor found that the above problems can be solved by using a modified epoxy resin containing a structural unit derived from an epoxy compound and a structural unit derived from an acid-terminated polyester, having a weight average molecular weight of 1,500 to 50,000 and an epoxy equivalent of 500 to 10,000 g/eq, as the epoxy resin, and completed the present invention. That is, the gist of the present invention resides in the following [1] to [17].
• [1] including a structural unit derived from an epoxy compound and a structural unit derived from an acid-terminated polyester, a weight average molecular weight of 1,500 to 50,000, The epoxy equivalent is 500 to 10,000 g / eq, A modified epoxy resin represented by the following formula (1).
• n is the average value of the number of repeating units and is a number of 1 to 30;
• X is a structural unit derived from an epoxy compound and is a divalent group represented by the following formula (2);
• Y is a structural unit derived from an acid-terminated polyester and is a divalent group represented by the following formula (3); multiple Xs may be the same or different; multiple Ys may be the same or different.
• p is the average number of repeating units and is a number of 0 to 10;
• R 1 is a direct bond or an alkylene group having 1 to 15 carbon atoms;
• R 2 is an alkyl group having 1 to 4 carbon atoms;
• r is an integer of 1 to 4;
• multiple R 1 may be the same or different;
• multiple R 2 may be the same or different;
• R 3 is a hydrocarbon group having 2 to 40 carbon atoms which may have a heteroatom;
• R 4 is a hydrocarbon group having 2 to 40 carbon atoms which may
• a method for producing a modified epoxy resin comprising a reaction step of reacting an epoxy compound (A) represented by the following formula (4) with an acid-terminated polyester (B) represented by the following formula (5).
• an epoxy compound (A) represented by the following formula (4) with an acid-terminated polyester (B) represented by the following formula (5).
• p, r, R1 and R2 have the same meanings as p, r, R1 and R2 in formula (2) above.
• R 3 , R 4 and q have the same meanings as R 3 , R 4 and q in formula (3) above.
• the method for producing a modified epoxy resin according to [3] wherein the modified epoxy resin has a weight average molecular weight of 1,500 to 50,000.
• a curable resin composition comprising the modified epoxy resin according to [1] or [2] and a curing agent.
• a paint comprising the curable resin composition according to [6].
• An adhesive comprising the curable resin composition according to [6].
• a coating composition for powder coating comprising the curable resin composition according to [6].
• a coating composition for cans comprising the curable resin composition according to [6].
• [13] [12] A coating film comprising the cured product of [12]. [14] A fiber-reinforced plastic comprising the cured product of [12]. [15] [12] A laminate comprising the cured product of [12]. [16] A can member comprising a can substrate and the coating film according to [13] disposed on the surface of the can substrate. [17] A can using the can member according to [16].
• a modified epoxy resin having a structure different from that of a bisphenol A type epoxy resin and giving a cured product or a cured coating film having adhesion, coating film hardness, cupping resistance, point impact resistance, flex resistance, and hot water resistance equivalent to or higher than those of a cured product of a conventional high molecular weight bisphenol A type epoxy resin. Further, according to the present invention, it is possible to provide a method for producing a modified epoxy resin, a curable resin composition containing the modified epoxy resin, and a cured product of the curable resin composition containing the modified epoxy resin.
• the present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention.
• a numerical value or a physical property value is sandwiched before and after the " ⁇ "
• it is used to include the values before and after it.
• the terms "bifunctional” and “bivalent” of a compound refer to substantially bifunctional compounds, and trifunctional or higher compounds may be included as long as they do not induce gelation during the production of the modified epoxy resin, i.e., 5% by weight or less.
• the lower limit and upper limit of a numerical range are described separately, the numerical range may be a combination of any lower limit and any upper limit.
• a modified epoxy resin (hereinafter simply referred to as a modified epoxy resin) according to the first embodiment of the present invention is a modified epoxy resin represented by the following formula (1) including structural units derived from an epoxy compound and structural units derived from an acid-terminated polyester.
• the modified epoxy resin according to this embodiment has a weight average molecular weight of 1,500 to 50,000 and an epoxy equivalent of 500 to 10,000 g/eq.
• an epoxy compound shall be a concept including an epoxy resin.
• n is the average number of repeating units and is a number from 1 to 30.
• X is a structural unit derived from an epoxy compound and is a divalent group represented by the following formula (2), and multiple X's may be the same or different.
• Y is a structural unit derived from an acid-terminated polyester and is a divalent group represented by the following formula (3), and multiple Y's may be the same or different.
• the epoxy compound-derived structural unit represented by X and the acid-terminated polyester-derived structural unit represented by Y may be referred to as structural unit (X) and structural unit (Y), respectively.
• R 1 is a direct bond or an alkylene group having 1 to 15 carbon atoms, and multiple R 1s may be the same or different.
• R 2 is an alkyl group having 1 to 4 carbon atoms, and multiple R 2 may be the same or different.
• r is an integer of 1 to 4, and multiple r's may be the same or different.
• R 3 is a hydrocarbon group having 2 to 40 carbon atoms which may have a heteroatom, and multiple R 3 may be the same or different.
• R 4 is a hydrocarbon group having 2 to 40 carbon atoms which may have a heteroatom, and a plurality of R 4 may be the same or different.
• q is the average number of repeating units and is a number from 1 to 50;
• X in the above formula (1) is a structural unit derived from a bifunctional epoxy compound, specifically a divalent group represented by the above formula (2).
• p is the average number of repeating units and ranges from 0 to 10, preferably from 0.1 to 8, more preferably from 0.2 to 5, from the viewpoint of enhancing flexibility. Multiple X's may be the same or different.
• R 1 is a direct bond or an alkylene group having 1 to 15 carbon atoms, which enhances the intermolecular stacking property of the modified epoxy resin and improves the point impact strength and cupping resistance of the cured product. From this viewpoint, it is preferably a direct bond or an alkylene group having 1 to 10 carbon atoms, more preferably a direct bond or an alkylene group having 1 to 3 carbon atoms.
• the alkylene group includes a linear alkylene group, a branched alkylene group, and a cycloalkylene group.
• the alkylene group is preferably a linear alkylene group or a branched alkylene group, more preferably a methylene group or an isopropylidene group, and particularly preferably a methylene group, from the viewpoint of making the molecular structure of the modified epoxy resin compact and improving the stacking property between the modified epoxy resin molecules.
• Multiple R 1 's may be the same or different.
• R 2 is an alkyl group having 1 to 4 carbon atoms.
• the alkyl group include linear alkyl groups and branched alkyl groups.
• R 2 is preferably a linear alkyl group from the viewpoint of achieving a planar molecular structure and improving the stacking property between modified epoxy resin molecules.
• Specific linear alkyl groups include n-butyl, n-propyl, ethyl and methyl groups.
• R 2 is preferably a methyl group from the viewpoint of increasing the flatness of the molecule and improving the mechanical properties of the modified epoxy resin. Multiple R 2 may be the same or different.
• r is an integer of 1 to 4, preferably an integer of 1 to 2, and particularly preferably 2 from the viewpoint of availability.
• the substitution position of R 2 is preferably a position represented by the following formula (6).
• r is 2, it is preferably at the position shown in the following formula (7). This is because by arranging a substituent in the vicinity of the oxygen atom, it is possible to inhibit the hydrogen bond derived from the oxygen atom, and by improving the appropriate stacking property derived from the aromatic skeleton, the mechanical properties of the modified epoxy resin are improved.
• X in formula (1) most preferably has a skeleton derived from tetramethylbisphenol F (4,4'-methylenebis(2,6-dimethylphenol)), as shown in formula (8) below.
• the modified epoxy resin is preferably produced without using bisphenol A, which is an endocrine disrupting substance, as a raw material. That is, it is preferable that R1 is not an isopropylidene group, and that all R2 of the benzene ring bonded to the isopropylidene group are not hydrogen atoms. However, as will be described later, there is a possibility that a trace amount of bisphenol A may be mixed into the reaction system for manufacturing reasons.
• R 1 is not an isopropylidene group, and all R 2 of the benzene rings bonded to the isopropylidene group are not hydrogen atoms
• R 2 means substantially free of groups derived from bisphenol A (50,000 ppm or less relative to the total weight of the modified epoxy resin). does not mean that there are none.
• R 3 is a hydrocarbon group having 2 to 40 carbon atoms which may have a heteroatom
• R 4 is a hydrocarbon group having 2 to 40 carbon atoms which may have a heteroatom
• q is the average number of repeating units and is a number of 1 to 50.
• the hydrocarbon group for R 3 is not particularly limited, and examples thereof include a straight-chain or branched aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, etc., preferably a straight-chain or branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group.
• the number of carbon atoms in the hydrocarbon group of R 3 is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, particularly preferably 6 or more, and preferably 35 or less, more preferably 25 or less, still more preferably 20 or less, and particularly preferably 15 or less.
• the hydrocarbon group for R 4 is not particularly limited, but includes, for example, a linear or branched aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, etc., preferably an aromatic hydrocarbon group or a linear aliphatic hydrocarbon group, more preferably an aromatic hydrocarbon group.
• the number of carbon atoms in the hydrocarbon group of R 4 is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, particularly preferably 6 or more, and preferably 35 or less, more preferably 25 or less, still more preferably 20 or less, and particularly preferably 15 or less.
• the structural units (X) and structural units (Y) constituting the modified epoxy resin can be adjusted to a specific ratio.
• the proportion of the structural unit (X) can be calculated from the weight ratio of the epoxy compound (A) and the acid-terminated polyester (B) at the time of production by a modified epoxy resin manufacturer.
• a user of a modified epoxy resin can perform a decomposition reaction of the modified epoxy resin as necessary, perform qualitative analysis and quantitative analysis using a nuclear magnetic resonance device, a mass spectrometer and a chromatograph, and analyze the weight ratio of the constituent components.
• the proportion of the structural unit (X) is more than 0% by weight, but the lower limit is preferably 1% by weight or more, more preferably 3% by weight or more, even more preferably 5% by weight or more, and particularly preferably 10% by weight or more. If the proportion of the structural unit (X) is at least the above lower limit, the proportion of the structural unit (Y) relative to the structural unit (X) is not too large when producing the modified epoxy resin, which tends to facilitate a uniform reaction and provide excellent production stability.
• the upper limit of the proportion of the structural unit (X) is preferably 80% by weight or less, more preferably 70% by weight or less, even more preferably 60% by weight or less, even more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
• the ratio of the structural unit (X) is equal to or less than the above upper limit value, appropriate flexibility can be ensured without excessively reflecting the properties of the structural unit (X) in the properties of the modified epoxy resin.
• the ratio of structural units (Y) in the modified epoxy resin is represented by the following formula (II).
• Ratio (% by weight) of structural unit (Y) (weight of structural unit (Y)) ⁇ 100)/weight of modified epoxy resin (II)
• the proportion of the structural unit (Y) can be calculated by a modified epoxy resin manufacturer from the weight ratio of the epoxy compound (A) and the acid-terminated polyester (B) charged at the time of production.
• a user of a modified epoxy resin can perform a decomposition reaction of the modified epoxy resin as necessary, perform qualitative analysis and quantitative analysis using a nuclear magnetic resonance device, a mass spectrometer and a chromatograph, and analyze the weight ratio of the constituent components.
• the proportion of the structural unit (Y) is less than 100% by weight, but the upper limit is preferably 99% by weight or less, more preferably 97% by weight or less, and even more preferably 95% by weight or less. If the proportion of the structural unit (Y) is equal to or less than the above upper limit, the proportion of the structural unit (X) relative to the structural unit (Y) is not too small when producing the modified epoxy resin, which tends to facilitate a uniform reaction and provide excellent production stability.
• the lower limit of the proportion of the structural unit (Y) is preferably 20% by weight or more, more preferably 30% by weight or more, even more preferably 40% by weight or more, even more preferably 50% by weight or more, and particularly preferably 60% by weight or more.
• the proportion of the structural unit (Y) is at least the above lower limit, the properties of the modified epoxy resin do not reflect excessively the properties of the structural unit (X), and appropriate flexibility can be ensured.
• the lower limit of the epoxy equivalent of the modified epoxy resin is 500 g/eq or more, preferably 750 g/eq or more, more preferably 1,000 g/eq or more, still more preferably 1,500 g/eq or more, and particularly preferably 2,000 g/eq or more.
• Tg glass transition temperature
• the glass transition temperature (Tg) of the cured product and the cured coating film obtained by curing the modified epoxy resin (hereinafter, the cured product and/or the cured coating film may be simply referred to as the cured product) can also be improved.
• the upper limit of the epoxy equivalent of the modified epoxy resin is 10,000 g/eq or less, preferably 8,000 g/eq or less, more preferably 6,000 g/eq or less, still more preferably 4,000 g/eq or less.
• the softening point being too high, specifically, the need to raise the temperature during melt-kneading, for example, the inconvenience that the latent curing agent species that can be selected when kneading with the latent curing agent is reduced.
• the epoxy equivalent is equal to or less than the above upper limit, the melt viscosity of the resin does not become too high during heat curing, so the surface accuracy of the cured coating film obtained by curing the modified epoxy resin can be improved.
• the epoxy equivalent of the modified epoxy resin is measured by the method described in the Examples section below.
• the lower limit of the midpoint glass transition temperature (Tmg) of the modified epoxy resin is preferably 40°C or higher, more preferably 50°C or higher, even more preferably 55°C or higher, and particularly preferably 60°C or higher. This is because, if the midpoint glass transition temperature (Tmg) is at least the above lower limit, blocking resistance that can withstand practical use can be ensured, and workability is improved. Furthermore, when the cured coating film containing the modified epoxy resin comes into contact with hot water, abnormalities are less likely to occur.
• the upper limit of the midpoint glass transition temperature (Tmg) of the modified epoxy resin is preferably 150°C or less, more preferably 120°C or less, even more preferably 100°C or less, and particularly preferably 75°C or less.
• Tmg midpoint glass transition temperature
• the lower limit of the weight average molecular weight (Mw) of the modified epoxy resin is preferably 1,500 or more, more preferably 3,000 or more, even more preferably 5,000 or more, and particularly preferably 10,000 or more.
• the weight average molecular weight is at least the above lower limit, the glass transition temperature (Tg) is improved and blocking can be suppressed. If the weight-average molecular weight of the modified epoxy resin is too small, the distance between the cross-linking points becomes narrow, which may cause problems such as brittleness of the cured product obtained by curing and deterioration of the mechanical properties of the cured coating film.
• the weight-average molecular weight of the modified epoxy resin is too small, depending on the structural unit (X) and the structural unit (Y) that constitute the modified epoxy resin, the amount of unreacted residual components tends to increase at the time of production, resulting in stronger blocking than expected from the glass transition temperature (Tg); unreacted components volatilize during baking; On the other hand, if the weight average molecular weight of the modified epoxy resin is at least the above lower limit, the occurrence of such problems can be avoided.
• the upper limit of the weight average molecular weight (Mw) of the modified epoxy resin is 50,000 or less, preferably 45,000 or less, more preferably 40,000 or less, and even more preferably 20,000 or less. If the weight average molecular weight of the modified epoxy resin is too large, the softening point becomes high, and the melting temperature must be increased during melt kneading, or the surface accuracy of the cured coating film is impaired due to the high melt viscosity.
• the weight average molecular weight of the modified epoxy resin is too large, the formation of a network composed of the curing agent and the modified epoxy resin does not proceed smoothly when the curable resin composition containing the modified epoxy resin is cured, and the resulting coating film may have poor mechanical properties or poor solvent resistance.
• the weight average molecular weight of the modified epoxy resin is equal to or less than the above upper limit, the occurrence of such problems can be avoided.
• the upper limit of the molecular weight distribution (Mw/Mn) is preferably 20.0 or less, more preferably 10.0 or less, even more preferably 8.0 or less, and particularly preferably 5.0 or less.
• melt-kneading is performed from relatively low-molecular-weight components, so by reducing the viscosity difference and polarity difference between the curing agent to be melt-kneaded and other epoxy resins, it is possible to efficiently melt-knead.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) of the epoxy resin can be measured by gel permeation chromatography (GPC method). More detailed method examples are described in the Examples section below.
• Bisphenol A is most preferably below the detection limit.
• bisphenol A may be unintentionally mixed in the modified epoxy resin for manufacturing reasons during the production of the epoxy compound (A) and the acid-terminated polyester (B), which are raw materials, and during the production of the modified epoxy resin.
• a structure derived from bisphenol A may be incorporated into the modified epoxy resin.
• the modified epoxy contains substantially no bisphenol A. That is, the content of bisphenol A is preferably 50,000 ppm or less based on the total weight of the modified epoxy resin.
• a method for producing a modified epoxy resin which is a second embodiment of the present invention, includes a reaction step of reacting an epoxy compound (A) represented by the following formula (4) with an acid-terminated polyester (B) represented by the following formula (5).
• the epoxy compound (A) represented by the following formula (4) and the acid-terminated polyester (B) represented by the following formula (5) are reacted in the presence of a catalyst at a suitable feed ratio.
• the modified epoxy resin produced by the production method according to this embodiment is preferably the modified epoxy resin according to the first embodiment of the present invention.
• p, r, R1 and R2 have the same meanings as p, r, R1 and R2 in the above formula (2).
• R 3 , R 4 and q have the same meanings as R 3 , R 4 and q in formula (3) above.
• Epoxy compound (A) The epoxy compound (A) represented by the above formula (4) is a substance in which some or all of the hydrogen atoms bonded to the benzene ring of bisphenols or biphenols are substituted with alkyl groups having 1 to 4 carbon atoms and two glycidyl ether groups in the molecule.
• Examples of the epoxy compound (A) include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, bisphenol Z diglycidyl ether, bisphenol AP diglycidyl ether, bisphenol AP diglycidyl ether, bisphenol acetophenone diglycidyl ether, bisphenol trimethylcyclohexane diglycidyl ether, bisphenol fluorenediglycidyl ether, etc., in which some or all of the hydrogen atoms bonded to the benzene ring are methyl, ethyl, propyl, or isopropyl groups; A compound substituted with a butyl group, an isobutyl group, or a t-butyl group; a compound in which some or all of the hydrogen atoms bonded to the benzene ring of the biphenol diglycidyl ether are substituted with a methyl group, an ethyl group,
• the epoxy compound (A) is not particularly limited as long as it satisfies the conditions of formula (4), but a structure in which the hydrogen atoms of the benzene rings are substituted with small alkyl groups and the cross-linking sites between the benzene rings are small improves the intermolecular stacking and improves the point impact strength and cupping resistance of the cured product.
• dimethylbisphenol A type epoxy resin also referred to as bisphenol C type epoxy resin
• tetramethylbisphenol A type epoxy resin dimethylbisphenol F type epoxy resin
• tetramethylbisphenol F type epoxy resin dimethylbiphenol type epoxy resin
• tetramethylbiphenol type epoxy resin dimethylbiphenol type epoxy resin
• dimethylbisphenol A type epoxy resin dimethylbisphenol A type epoxy resin, tetramethylbisphenol A type epoxy resin, tetramethylbisphenol F type epoxy resin, and tetramethylbiphenol type epoxy resin are more preferable, and tetramethylbisphenol F type epoxy resin is particularly preferable.
• tetramethylbisphenol F type epoxy resin is particularly preferable. This is because the moderately broadened planar structure derived from the alkylbenzene and the moderate flexibility of the crosslinked portion improve the point impact resistance and the cupping resistance when formed into a cured coating film.
• the epoxy compounds (A) listed above can be used alone or in any combination and ratio, and can be set in consideration of the required performance such as the glass transition temperature (Tg), softening point, point impact strength, cupping resistance, and flex resistance of the desired modified epoxy resin or its cured product, and the required performance according to the application.
• Tg glass transition temperature
• softening point point impact strength
• cupping resistance cupping resistance
• flex resistance of the desired modified epoxy resin or its cured product
• the acid-terminated polyester (B) represented by the formula (8) is a carboxylic acid-terminated polyester resin produced by polycondensation of a dihydric carboxylic acid and a dihydric alcohol.
• the terms "difunctional” and “divalent” of the compound refer to substantially bifunctional, and trifunctional or higher functional compounds may be included as long as they do not induce gelation during the production of the modified epoxy resin, i.e., 5% by weight or less.
• R 3 in the above formula (3) corresponds to a repeating structural unit derived from a dihydric alcohol described later
• R 4 corresponds to a repeating unit derived from a divalent carboxylic acid described later in the acid-terminated polyester (B).
• divalent carboxylic acids are usually used in the form of free acids, they can also be used as derivatives such as alkyl esters having about 1 to 4 carbon atoms, halides, and alkali metal salts of these divalent carboxylic acids.
• these divalent carboxylic acids and their derivatives are collectively referred to as "divalent carboxylic acid components".
• divalent carboxylic acid is not particularly limited, isophthalic acid, terephthalic acid, isomers of naphthalene dicarboxylic acid (specifically 1,4-, 1,5-, 1,6-, 1,7-, 2,5-, 2,6-, 2,7-, 2,8-), aromatic dicarboxylic acids such as furandicarboxylic acid; succinic acid, sebacic acid, isodecylsuccinic acid, dodecenylsuccinic acid, maleic acid, adi Aliphatic dicarboxylic acids such as pinic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, thapsic acid, heptadecanedioic acid, dipropylmalonic acid, 3-e
• the trivalent or higher carboxylic acid component is not particularly limited, examples thereof include trimellitic acid, pyromellitic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, and derivatives thereof.
• polyvalent carboxylic acids may be used alone, or multiple types may be used in any combination and ratio. If a trivalent or higher carboxylic acid component is used as the divalent carboxylic acid component, it may cause gelation during the reaction with the epoxy compound (A), causing problems in production, or the molecular weight distribution may become excessively wide, which may cause variations in physical properties when formed into a coating film.
• dihydric alcohol is not particularly limited, the following can be used.
• Diols consisting only of a chain structure such as ethylene glycol, polyethylene glycol, neopentyl glycol, propylene glycol, polypropylene glycol, 1,4-butanediol, polytetramethylene glycol, 1,5-pentanediol, polypentamethylene glycol, 1,6-hexanediol, polyhexamethylene glycol, 1,7-heptanediol, polyheptamethylene glycol, 1,8-octanediol, 1,10-decanediol, dimer diol, 1,4-cyclohexanedimethanol, iso Examples include diols having an alicyclic structure such as sorbide and anhydroerythritol. Among these, the dihydric alcohol is preferably selected from ethylene glycol, propylene glycol, neopentyl glycol and 1,4
• the trihydric or higher alcohol is not particularly limited, but includes trimethylolpropane, pentaerythritol, xylitol, sucrose, glucose and the like.
• polyhydric alcohols may be used alone, or multiple types may be used in any combination and ratio. If a trihydric or higher alcohol is used as the dihydric alcohol, it may cause gelation during the reaction with the epoxy compound (A), causing problems in production, or the molecular weight distribution may become excessively broadened, causing variations in physical properties when used as a coating film.
• the method for producing the acid-terminated polyester (B) is not particularly limited, and it can be produced by a known method. For example, a monomer mixture containing a dihydric carboxylic acid component, a dihydric alcohol component, etc. is put into a reaction vessel, heated to raise the temperature, an esterification reaction or a transesterification reaction is performed, and the water or dihydric alcohol component generated in the reaction is removed. Subsequently, the polycondensation reaction is carried out. At this time, the pressure inside the reactor is gradually reduced, and the polycondensation is carried out while distilling off the dihydric alcohol component under a vacuum of 150 mmHg (20 kPa) or less, preferably 15 mmHg (2 kPa) or less.
• the catalysts used for the esterification reaction, transesterification reaction, and polycondensation reaction include titanium-based catalysts, calcium acetate, calcium acetate hydrate, dibutyltin oxide, tin acetate, tin disulfide, tin oxide, tin-based catalysts such as 2-ethylhexanetin, zinc acetate, antimony trioxide, and germanium dioxide.
• titanium-based catalysts are preferred because of their good reactivity.
• titanium-based catalysts include titanium alkoxide compounds having an alkoxy group, titanium carboxylate compounds, titanyl carboxylates, titanyl carboxylate salts, and titanium chelate compounds.
• titanium alkoxide compounds having an alkoxy group examples include tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetrapentoxytitanium, and tetraoctoxytitanium.
• titanium carboxylate compounds include titanium formate, titanium acetate, titanium propionate, titanium octanoate, titanium oxalate, titanium succinate, titanium maleate, titanium adipate, titanium sebacate, titanium hexanetricarboxylate, titanium isooctanetricarboxylate, titanium octanetetracarboxylate, titanium decanetetracarboxylate, titanium benzoate, titanium phthalate, titanium terephthalate, titanium isophthalate, titanium 1,3-naphthalenedicarboxylate, 4,4 titanium-biphenyldicarboxylate, titanium 2,5-toluenedicarboxylate, titanium anthracene dicarboxylate, titanium trimellitate, titanium 2,4,6-naphthalenetricarboxylate, titanium pyromellitic acid, and titanium 2,3,4,6-naphthalenetetracarboxylate.
• Titanium-based catalysts may be used singly, or two or more may be used in any combination and ratio.
• the reaction temperature for the esterification reaction, transesterification reaction, and polycondensation reaction is preferably 150 to 300°C. If the reaction temperature is 150°C or higher, productivity tends to be good, and if it is 300°C or lower, decomposition of the obtained acid-terminated polyester (B) can be suppressed.
• the lower limit of the reaction temperature is more preferably 180°C or higher, and the upper limit is more preferably 280°C or lower.
• the amount of the catalyst used is preferably 10 ppm to 10000 ppm with respect to the total weight of the divalent carboxylic acid component and the dihydric alcohol component from the viewpoint of ensuring polymerization reactivity.
• the lower limit of the weight average molecular weight (Mw) of the acid-terminated polyester (B) is preferably 1,000 or more, more preferably 1,500 or more, and particularly preferably 2,000 or more.
• the upper limit of the weight average molecular weight (Mw) is preferably 10,000 or less, more preferably 9,000 or less, and particularly preferably 8,000 or less.
• the molecular weight distribution (Mw/Mn) is preferably 10.0 or less, more preferably 5.0 or less, and 4.3 or less is particularly preferable in terms of forming a three-dimensional network structure as designed and improving the mechanical properties of the coating film.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) of the acid-terminated polyester (B) can be measured by gel permeation chromatography (GPC method).
• GPC method uses polystyrene as a standard polymer. A specific measuring method is as described in the section of Examples below.
• Tg glass transition temperature of the acid-terminated polyester (B)
• Tg is preferably 0°C or higher, more preferably 5°C or higher, even more preferably 10°C or higher, and particularly preferably 20°C or higher from the viewpoint of heat resistance.
• the Tg is preferably 100° C. or lower, more preferably 95° C. or lower, even more preferably 90° C. or lower, and particularly preferably 80° C. or lower from the viewpoint of synthetic handling.
• the hydroxyl value of the acid-terminated polyester (B) is not particularly limited, the hydroxyl value is preferably 0.001 mgKOH/g or more, more preferably 0.005 mgKOH/g or more, and particularly preferably 0.01 mgKOH/g or more from the viewpoint of raw material availability. Further, the hydroxyl value of the acid-terminated polyester (B) is preferably 60 mgKOH/g or less, more preferably 50 mgKOH/g or less, more preferably 40 mgKOH/g or less, and particularly preferably 30 mgKOH/g or less from the viewpoint of allowing the polymerization reaction with the epoxy compound (A) to proceed smoothly.
• the acid value of the acid-terminated polyester (B) is not particularly limited, but the acid value is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more. Also, the acid value is preferably 100 mgKOH/g or less, more preferably 90 mgKOH/g or less, and even more preferably 80 mgKOH/g or less.
• the proportion of the epoxy compound (A) in the modified epoxy resin can be adjusted, and excellent mechanical properties can be imparted to the resulting cured product or cured coating film.
• Tg glass transition temperature
• hydroxyl value hydroxyl value
• acid value of the acid-terminated polyester (B) are as described in Examples below.
• Only one type of acid-terminated polyester (B) may be used, or a plurality of types of acid-terminated polyesters (B) having different types of divalent carboxylic acid components and/or dihydric alcohols, or a plurality of types of acid-terminated polyesters (B) having different physical properties may be used in any combination and ratio.
• a catalyst (C) may be used in the reaction step.
• the catalyst (C) is not particularly limited as long as it is usually used as a catalyst for the advance method in the production of epoxy resins.
• Examples of the catalyst (C) include alkali metal compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles and the like.
• alkali metal compounds include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide; alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride and potassium chloride; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; alkali metal hydrides such as alkali metal phenoxide, sodium hydride and lithium hydride; alkali metal salts of organic acids such as sodium acetate and sodium stearate;
• organic phosphorus compounds include triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri-2,4-xylylphosphine, tri-2,5-xylylphosphine, tri-3,5-xylylphosphine, tris(p-tert-butylphenyl)phosphine, tris(p-methoxyphenyl)phosphine, tris(p-tert-butoxyphenyl)phosphine, tri(pn -octylphenyl)phosphine, tri(pn-nonylphenyl)phosphine, triallylphosphine, tributylphosphine, trimethylphosphine, tribenzylphosphine, triisobutylphosphine, tri-tert-butylphosphine, tri-n-oct
• tertiary amines include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, N,N-dimethylbenzylamine and the like.
• quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributyl ammonium chloride, phenyltrimethylammonium chloride and the like.
• cyclic amines include 1,8-diazabicyclo(5,4,0)-7-undecene and 1,5-diazabicyclo(4,3,0)-5-nonene.
• imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like.
• a tertiary amine having a boiling point equal to or higher than the reaction temperature as the catalyst (C), in that a narrow molecular weight distribution can be produced.
• the catalyst (C) listed above may be used alone, or two or more thereof may be used in any combination and ratio.
• the amount used is usually 10000 ppm by weight or less, for example 10 to 5000 ppm by weight, relative to the amount of the epoxy compound (A) used.
• reaction solvent (D) A reaction solvent (D) may be used in the reaction step.
• any solvent can be used as long as it dissolves the raw materials, but it is usually an organic solvent.
• organic solvents examples include aromatic solvents, ketone solvents, amide solvents, glycol ether solvents, and the like.
• aromatic solvents include benzene, toluene, and xylene.
• ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclopentanone, cyclohexanone, and acetylacetone.
• amide solvents include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone and the like.
• glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, and propylene glycol monomethyl ether acetate.
• reaction solvents (D) listed above may be used alone, or two or more thereof may be used in any combination and ratio.
• the reaction solvent (D) can be further added to continue the reaction.
• reaction conditions The reaction between the epoxy compound (A) and the acid-terminated polyester (B) can be carried out under normal pressure, increased pressure, or reduced pressure.
• the reaction temperature is usually 60-240°C, preferably 80-220°C, more preferably 100-200°C. It is preferable that the reaction temperature is equal to or higher than the above lower limit because the reaction can easily proceed. Further, when the reaction temperature is equal to or lower than the above upper limit, the side reaction hardly progresses, which is preferable from the viewpoint of obtaining a high-purity modified epoxy resin.
• reaction time is not particularly limited, it is usually 0.5 to 24 hours, preferably 1 to 22 hours, more preferably 1.5 to 20 hours. When the reaction time is equal to or less than the upper limit, it is preferable from the viewpoint of improving production efficiency.
• a diluent solvent (E) may be added to the modified epoxy resin after completion of the reaction in order to adjust the solid content concentration.
• the diluting solvent (E) any solvent can be used as long as it dissolves the modified epoxy resin, but it is usually an organic solvent.
• the organic solvent the same ones as those mentioned above as the reaction solvent (D) can be used.
• solvent and “solvent” are used during the reaction as “solvent” and after the reaction is completed as “solvent”, but the same type or different type may be used.
• a curable resin composition according to the third embodiment of the present invention contains at least the modified epoxy resin according to the first embodiment of the present invention and a curing agent.
• the curable resin composition according to the present embodiment may optionally contain epoxy compounds other than the modified epoxy resin according to the first embodiment of the present invention (hereinafter also referred to as other epoxy compounds), curing accelerators, other components, and the like.
• the curing agent used in the curable resin composition according to this embodiment is a substance that contributes to the cross-linking reaction and/or chain extension reaction between epoxy groups of the epoxy resin.
• a substance is usually called a "curing accelerator”, it is regarded as a curing agent as long as it contributes to the cross-linking reaction and/or chain lengthening reaction between the epoxy groups of the epoxy resin.
• the curing agent is preferably at least one selected from the group consisting of polyfunctional phenols, polyisocyanate compounds, amine compounds, acid anhydride compounds, acid-terminated polyester resins, imidazole compounds, amide compounds, cationic polymerization initiators, organic phosphines, phosphonium salts, and tetraphenylboron salts.
• polyfunctional phenols include bisphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol AD, bisphenol Z, and tetrabromobisphenol A; biphenyl skeleton-containing biphenols such as 4,4'-biphenol, 3,3',5,5'-tetramethyl-4,4'-biphenol; dihydroxybenzenes such as catechol, resorcin, and hydroquinone; dihydroxynaphthalenes; substituted with non-interfering substituents such as organic substituents containing heteroatoms such as groups, alkyl groups, aryl groups, ether groups, ester groups, sulfur, phosphorus, silicon and the like;
• polyfunctional phenols novolacs, resoles, etc.
• monofunctional phenols such as phenol, cresol, and alkylphenol, and aldehydes.
• polyisocyanate-based compounds include tolylene diisocyanate, methylcyclohexane diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dimer acid diisocyanate, trimethylhexamethylene diisocyanate, and lysine triisocyanate.
• polyisocyanate-based compounds amino groups, hydroxyl groups, carboxyl groups, polyisocyanate compounds obtained by reaction with a compound having at least two active hydrogen atoms such as water, tri- to pentamers of the polyisocyanate compounds can be mentioned.
• amine compounds include primary aliphatic amines, secondary aliphatic amines, tertiary aliphatic amines, primary aromatics, secondary aromatic amines, tertiary aromatic amines, cyclic amines, guanidines, and urea derivatives.
• Specific amine compounds include triethylenetetramine, diaminodiphenylmethane, diaminodiphenyl ether, metaxylenediamine, dicyandiamide, 1,8-diazabicyclo(5,4,0)-7-undecene, 1,5-diazabicyclo(4,3,0)-5-nonene, dimethylurea, guanylurea, and the like.
• acid anhydride compounds include phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, and condensates of maleic anhydride and unsaturated compounds.
• acid-terminated polyester resins include polycondensates obtained by reacting dihydric carboxylic acids and dihydric alcohols listed in the section of acid-terminated polyester (B). It preferably contains more than 0 mol % of trivalent or higher carboxylic acid and/or trihydric or higher alcohol mentioned in the section of acid-terminated polyester (B) in order to promote network structure formation during curing.
• imidazole compounds include 1-isobutyl-2-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and benzimidazole.
• the imidazole compound also functions as a curing accelerator, which will be described later, it is classified as a curing agent in this embodiment.
• amide compounds include dicyandiamide, dicyandiamide derivatives, and polyamide resins.
• Cationic polymerization initiators generate cations upon exposure to heat or active energy rays, and include aromatic onium salts and the like.
• aromatic onium salts include compounds composed of an anion component such as SbF 6 ⁇ , BF 4 ⁇ , AsF 6 ⁇ , PF 6 ⁇ , CF 3 SO 3 2 ⁇ , B(C 6 F 5 ) 4 ⁇ and an aromatic onium component containing atoms such as iodine, sulfur, nitrogen, and phosphorus, and diaryliodonium salts and triarylsulfonium salts are particularly preferred.
• organic phosphines examples include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine.
• Examples of phosphonium salts include tetraphenylphosphonium/tetraphenylborate, tetraphenylphosphonium/ethyltriphenylborate, and tetrabutylphosphonium/tetrabutylborate.
• tetraphenylboron salts examples include 2-ethyl-4-methylimidazole/tetraphenylborate and N-methylmorpholine/tetraphenylborate.
• the content of the curing agent in the curing resin composition according to the present embodiment is preferably 0.1 or more, more preferably 0.5 or more, more preferably 1,000 portions or more, and more preferably 1,000 parts or more, compared to 100 parts by weight of the modified epoxy resin according to the first embodiment of the present invention. It is less than the weight part, more preferably 100 or less, more preferably, 80 or less, especially preferably 60 parts or less.
• the content of the curing agent is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, still more preferably 1 part by weight or more, preferably 1,000 parts by weight or less, more preferably 100 parts by weight or less, still more preferably 80 parts by weight or less, and particularly preferably 60 parts by weight, based on 100 parts by weight of the total epoxy component as a solid content. It is below.
• a more preferable amount of the curing agent is as described below, depending on the type of curing agent.
• the equivalent ratio of the functional group in the curing agent to the total epoxy groups of the curable resin composition is preferably in the range of 0.8 to 1.5.
• the number of isocyanate groups in the polyisocyanate-based compound to the number of hydroxyl groups in the curable resin composition is preferably used in an equivalent ratio of 1:0.01 to 1:1.5.
• an imidazole compound When used, it is preferably used in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of all epoxy components as solid content in the curable resin composition.
• an amide-based compound When an amide-based compound is used, it is preferably used in a range of 0.1 to 20% by weight based on the total weight of all the epoxy components and the amide-based compound as solid content in the curable resin composition.
• a cationic polymerization initiator When a cationic polymerization initiator is used, it is preferably used in the range of 0.01 to 15 parts by weight with respect to 100 parts by weight of all epoxy components as solid content in the curable resin composition.
• the total weight of all epoxy components and organic phosphines, phosphonium salts, and tetraphenylboron salts as solids in the curable resin composition is preferably in the range of 0.1 to 20% by weight.
• the "solid content” means the component excluding the solvent, and includes not only solid epoxy resins or epoxy compounds, but also semi-solid and viscous liquid substances. Further, “total epoxy component” means the sum of the modified epoxy resin according to the first embodiment of the present invention and other epoxy compounds.
• mercaptan-based compounds for example, mercaptan-based compounds, organic acid dihydrazides, halogenated boron amine complexes, and the like can also be used as curing agents for the curable resin composition according to the present embodiment.
• Epoxy compounds (other epoxy compounds) other than the modified epoxy resin according to the first embodiment of the present invention can be used in the curable resin composition according to the present embodiment.
• epoxy compounds include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, tetrabromobisphenol A type epoxy resin, other glycidyl ether type aromatic epoxy resins such as polyfunctional phenol type epoxy resin; epoxy resin obtained by hydrogenating the aromatic ring of the above glycidyl ether type aromatic epoxy resin; glycidyl ester type epoxy resin; glycidylamine type epoxy resins; linear aliphatic epoxy resins; alicyclic epoxy resins; epoxy compounds such as heterocyclic epoxy resins; In addition to these, resins having glycidyl groups such as polymers containing glycidyl (meth)acrylate; triglycidyl isocyanurate; and the like can also be used as other epoxy compounds.
• the other epoxy compounds listed above may be used alone, or two
• the proportion of the other epoxy compounds in the total epoxy component as solid content in the curable resin composition is preferably 1% by weight or more, more preferably 5% by weight or more, and is preferably 99% by weight or less, and more preferably 95% by weight or less.
• the proportion of the other epoxy compound is at least the above lower limit, it is possible to sufficiently obtain the effect of improving physical properties by blending the other epoxy compound.
• the ratio of the other epoxy compound is equal to or less than the above upper limit value, the effect of improving the impact strength and bending resistance of the modified epoxy resin according to the first embodiment of the present invention can be obtained.
• the curable resin composition according to the present embodiment may be mixed with and diluted with a solvent in order to appropriately adjust the viscosity of the curable resin composition during handling such as coating film formation.
• the solvent is used to ensure handleability and workability in molding the curable resin composition, and there is no particular limitation on the amount used.
• the terms "solvent” and “solvent” are used separately depending on the usage pattern, but the same type or different types may be used independently.
• the solvent that the curable resin composition according to the present embodiment may contain, one or more of the organic solvents exemplified as the reaction solvent (D) used for producing the modified epoxy resin according to the first embodiment of the present invention can be used.
• the curable resin composition according to this embodiment may contain other components in addition to the components listed above.
• Other components include, for example, curing accelerators (excluding those corresponding to the above curing agents), coupling agents, flame retardants, antioxidants, light stabilizers, plasticizers, reactive diluents, pigments, inorganic fillers, organic fillers, and the like.
• the other components listed above can be used in appropriate combination depending on the desired physical properties of the curable resin composition.
• a cured product can be obtained by curing the curable resin composition according to the present embodiment.
• the term "curing” as used herein means intentionally curing the epoxy resin with heat and/or light. The degree of curing may be controlled according to desired physical properties, applications, and the like.
• the curing method for curing the curable resin composition according to the present embodiment to obtain a cured product varies depending on the ingredients and amounts in the curable resin composition, the shape of the compound, etc., but usually includes heating conditions of 50 to 200° C. for 5 seconds to 180 minutes. This heating is performed in a two-step process of primary heating at 50 to 160° C. for 5 seconds to 30 minutes and secondary heating at 90 to 200° C., which is 40 to 120° C. higher than the primary heating temperature, for 1 minute to 150 minutes.
• the curing reaction of the curable resin composition should proceed to such an extent that the shape can be maintained by heating or the like.
• the curable resin composition contains a solvent, most of the solvent is removed by heating, depressurization, air-drying, etc. However, 5% by weight or less of the solvent may remain in the semi-cured product.
• the inclusion of the modified epoxy resin according to the first embodiment of the present invention in the cured product can be confirmed by identifying the modified epoxy resin of the present invention from the cured product by infrared spectroscopy of the cured product.
• the modified epoxy resin according to the first embodiment of the present invention has a structure different from that of the bisphenol A type epoxy resin, and can provide a cured product, a cured coating film, etc. having adhesion, coating film hardness, cupping resistance, point impact resistance, flex resistance, and hot water resistance equivalent to or higher than those of a cured product of a conventional high molecular weight bisphenol A type epoxy resin.
• the modified epoxy resin, the curable resin composition containing the modified epoxy resin, and the cured product of the curable resin composition according to the first embodiment of the present invention are excellent in electrical properties, adhesiveness, heat resistance, etc., and can be used in many applications, mainly in the fields of paints, civil engineering, and electrical engineering.
• the modified epoxy resin can be suitably used as, among others, binders for paints such as powder coating compositions and can coating compositions; binders for adhesives; base materials for prepregs; base materials for laminates; base materials for fiber-reinforced plastics (FRP);
• a coating film containing the cured product can be suitably used for a can member and a can using the same by forming it on the surface of a can substrate.
• the present invention will be described more specifically based on examples, but the present invention is not limited by the following examples.
• Various production conditions and values of evaluation results in the following examples have the meaning of preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range may be a range defined by a combination of the above-mentioned upper limit or lower limit value and the value of the example below or the values between the examples.
• A-1 High molecular weight bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation jER (registered trademark) 1009F, epoxy equivalent: 1993 g / eq, solid)
• A-2 Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation jER (registered trademark) 828US, epoxy equivalent: 186 g / eq)
• A-3 Hydrogenated bisphenol A type epoxy resin (Shin Nippon Rika HBE-100, epoxy equivalent 215 g/eq)
• A-4 1,6-hexanediol type epoxy resin (epoxy equivalent: 116 g/eq)
• A-5 Tetramethylbisphenol F type epoxy resin (epoxy equivalent: 193 g/eq)
• A-6 Tetramethylbiphenol type epoxy resin (Mitsubishi Chemical Corporation jER (registered trademark) YX4000, epoxy equivalent: 186 g
• [Acid-terminated polyester (B)] B-1 to B-2 shown in Table 1 were used as the acid-terminated polyester (B). All of them are obtained by reacting the dihydric carboxylic acid and the dihydric alcohol shown in Table 1 with the charging composition shown in Table 1.
• Table 1 abbreviations of dihydric carboxylic acids, dihydric alcohols and catalysts are as follows.
• TPA terephthalic acid
• IPA isophthalic acid
• EG ethylene glycol
• NPG neopentyl glycol
• CHDM 1,4-cyclohexanedimethanol
• TBT tetrabutoxy titanium
• the methods for producing B-1 and B-2 and the methods for measuring the acid value, acid equivalent, hydroxyl value, glass transition temperature, weight average molecular weight and number average molecular weight of the obtained acid-terminated polyester (B) are as follows.
• the viscosity of the reaction system increased with the reaction, and the stirring was stopped when the torque of the stirring blade reached a predetermined torque. Thereafter, the reaction system was returned to normal pressure, pressurized with nitrogen, and the reactants were taken out to obtain B-1 to B-2.
• the acid value of the acid-terminated polyester (B) was measured by the following procedure. About 0.2 g of acid-terminated polyester (B) was precisely weighed (X (g)) in a side-armed Erlenmeyer flask, 10 mL of benzyl alcohol was added, and the mixture was heated under a nitrogen atmosphere with a heater at 230° C. for 15 minutes to obtain a solution. After allowing the resulting solution to cool to room temperature, 10 mL of benzyl alcohol, 20 mL of chloroform, and several drops of phenolphthalein solution were added to the solution to obtain a sample for titration.
• ⁇ Hydroxyl value> The hydroxyl value of the acid-terminated polyester (B) was measured by the following procedure. About 5 g of acid-terminated polyester (B) was precisely weighed (Q (g)) in a side-armed Erlenmeyer flask, added with 50 mL of THF, and completely dissolved to obtain "solution 1". 30 mL of a dimethylaminopyridine THF solution prepared by dissolving 5 g of N,N-dimethylaminopyridine in 500 mL of THF was added to "Solution 1" to obtain "Solution 2". An acetic anhydride THF solution was prepared by adding 200 mL of THF to 22 mL of acetic anhydride.
• GPC Model HLC-8020GPC (manufactured by Tosoh) Column: Three TSKgelGMHXL (column size: 7.8 mm (ID) ⁇ 30.0 cm (L)) connected in series (manufactured by Tosoh) Detector: RI (manufactured by Tosoh) Eluent: Tetrahydrofuran (1 mL/min, 40°C) Sample: 0.04% tetrahydrofuran solution (100 ⁇ injection) Calibration curve: standard polystyrene (manufactured by Tosoh)
• Tg Glass transition temperature
• ⁇ Number average molecular weight (Mn) and weight average molecular weight (Mw)> The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) of the modified epoxy resin were measured by gel permeation chromatography (GPC).
• the apparatus and measurement conditions used for GPC measurement are as follows.
• GPC Model HLC-8120GPC (manufactured by Tosoh)
• Column TSKGEL HM-H + H4000 + H4000 + H3000 + H2000 (manufactured by Tosoh)
• Detector UV-8020 (manufactured by Tosoh), 254 nm
• Eluent Tetrahydrofuran (0.5 mL/min, 40° C.)
• Sample 1% tetrahydrofuran solution (10 ⁇ injection)
• Calibration curve standard polystyrene (manufactured by Tosoh)
• ⁇ Glass transition temperature (Tg)> The glass transition temperature (Tg) of the modified epoxy resin was measured by using a differential scanning calorimeter "DSC7020" manufactured by SII Nanotechnology Co., Ltd. and increasing the temperature from -50 to 200°C at a rate of 10°C/min.
• the extrapolated glass transition start temperature (Tig) is the temperature at the intersection of a straight line obtained by extending the base line on the low temperature side to the high temperature side and a tangent line drawn at the point where the gradient of the curve of the stepwise change portion of the glass transition is maximized.
• the midpoint glass transition temperature (Tmg) was taken as the temperature at the point where a straight line equidistant from the extended straight line of each base line intersects the curve of the stepwise change portion of the glass transition. Based on this result, when the midpoint glass transition temperature is 45 ° C. or higher, the resin particles do not fuse (block) with each other at normal temperature, and the storage stability is excellent.
• ⁇ Paint film hardness test> The resulting coating film was tested according to JIS K5600-5-4:1999 (established on April 20, 1999) using a pencil hardness tester (manufactured by Daiyu Kizai Co., Ltd.) and evaluated according to the following criteria. In the case of evaluation A, it was determined that the coating film hardness was good.
• B Abnormality (cracking, peeling) of the coating film occurred at an indentation depth of 5 mm or more and less than 9 mm.
• C Abnormality (cracking, peeling) of the coating film occurred at an indentation depth of less than 5 mm.
• ⁇ Point impact resistance test> The resulting coating film was subjected to a weight drop test (DuPont impact test) in accordance with JIS K5600-5-3:1999 (established on April 20, 1999). A primary test was performed as a moderate load and a secondary test as a heavy load. Primary test: A 1 kg weight was dropped from a height of 500 mm using a striking core with a tip radius of 1/8 inch. Secondary test: A 1 kg weight was dropped from a height of 200 mm using a striking center with a tip radius of 1/16 inch. The state of the coating film after the test was visually confirmed and evaluated according to the following criteria. If the evaluation was B or higher, it was judged to be practical level, and if the evaluation was A, it was judged that the point impact resistance was particularly excellent.
• the obtained coating film was fixed by sandwiching 1/3 of the long side of the coating plate with a table vise fixed to the workbench, and the surface on the coating film side was bent at 90 ° over a period of about 1 second, and the bent portion was visually observed and evaluated according to the following criteria. If the evaluation was A, it was judged to be of a practical level.
• a modified epoxy resin containing a structural unit (X) derived from an epoxy compound and a structural unit (Y) derived from an acid-terminated polyester and having a weight-average molecular weight and an epoxy equivalent within a specific range, and having a structural unit (X) within a specific range exhibits excellent coating film performance.

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