WO2023182522A1 - Résine époxy, corps durci de celle-ci et procédé de production de résine époxy - Google Patents

Résine époxy, corps durci de celle-ci et procédé de production de résine époxy Download PDF

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WO2023182522A1
WO2023182522A1 PCT/JP2023/012033 JP2023012033W WO2023182522A1 WO 2023182522 A1 WO2023182522 A1 WO 2023182522A1 JP 2023012033 W JP2023012033 W JP 2023012033W WO 2023182522 A1 WO2023182522 A1 WO 2023182522A1
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epoxy resin
formula
hydrogen atom
group
compound
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PCT/JP2023/012033
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Japanese (ja)
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世吾 小野
勇司 江口
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積水化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
    • C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
    • C07D301/30—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with carboxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
    • 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
    • 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
    • C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
    • 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
    • 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
    • C08G59/32—Epoxy compounds containing three or more epoxy groups

Definitions

  • the present invention relates to an epoxy resin having a truxylate structure and a cured product thereof.
  • Non-Patent Document 1 a bifunctional epoxy resin obtained using ferulic acid, which can be obtained by depolymerizing lignin, has a higher glass transition temperature and excellent tensile strength than conventional bisphenol A epoxy resins. It has been disclosed that it exhibits strength, and it has also been shown that performance is improved by compounding glycidyl ether of furfuryl alcohol.
  • microorganisms In addition, in recent years, consideration has been given to producing valuable materials using microorganisms. For example, using microorganisms to produce compounds with a hydroxycinnamic acid structure such as p-coumaric acid from biomass-derived compounds such as L-tyrosine. known to be synthesized. Generally, microbial reactions are highly efficient and can be carried out in a mild environment.
  • an epoxy resin is synthesized by reacting epichlorohydrin with p-hydroxycinnamic acid, and the obtained epoxy resin is cured with a curing agent together with glycidyl furfuryl ether, thereby achieving a high glass transition temperature and It is disclosed that it has excellent mechanical strength.
  • an object of the present invention is to provide an epoxy resin that is a compound that can be obtained from biomass, can be easily produced, and has good thermal performance.
  • the present inventors have discovered that an epoxy resin obtained from dihydroxytruxylic acid, which is a dimer of paracoumaric acid that can be easily produced by microorganisms, can solve the above problems, and have completed the present invention.
  • the present invention provides the following [1] to [13].
  • R 4 and R 5 are each independently a hydrogen atom, an alkoxy group, or -OG. * may be a binding site with another structure.
  • G represents a glycidyl group.
  • R 1 and R 3 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a heteroatom, or a glycidyl group, and R 2 is It is a divalent hydrocarbon group having 2 to 20 carbon atoms that may have a heteroatom.
  • R 4 and R 5 is a hydrogen atom
  • the other is a hydrogen atom, -OCH 3 or -OG.
  • n is an integer from 0 to 100.
  • R 1 and R 3 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a hetero atom, or a glycidyl group, and R 2 is It is a divalent hydrocarbon group having 2 to 20 carbon atoms that may have a heteroatom.
  • n is an integer from 0 to 100.
  • R 11 and R 13 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom.
  • R 12 is a divalent hydrocarbon group having 2 to 20 carbon atoms which may have a heteroatom.
  • one of R 14 and R 15 is a hydrogen atom, and the other is a hydrogen atom, -OCH 3 or -OH.
  • m is an integer from 0 to 100.
  • R 14 and R 15 are a hydrogen atom, and the other is a hydrogen atom, -OCH 3 or -OH.
  • R 16 is a hydrogen atom or -COOR 11
  • R 17 is a hydrogen atom or -COOR 13 .
  • R 11 and R 13 are each independently a hydrogen atom or an alkyl group.
  • the present invention can provide an epoxy resin that is a compound that can be obtained from biomass, is easily produced, and has good thermal performance.
  • Example 1 shows a 1 H-NMR spectrum of dimethyl 4,4'-dihydroxytruxylate synthesized in Example 1.
  • 1 shows a 1 H-NMR spectrum of the epoxy resin synthesized in Example 1.
  • the epoxy resin of the present invention has a skeleton represented by the following formula (1).
  • the epoxy resin having the skeleton of the following formula (1) is a compound that can be obtained from biomass, it can be easily produced and has good thermal performance.
  • R 4 and R 5 are each independently a hydrogen atom, an alkoxy group, or -OG. * may be a binding site with another structure.
  • G represents a glycidyl group.
  • the alkoxy groups of R 4 and R 5 may be, for example, alkoxy groups having 1 to 4 carbon atoms, such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group. , sec-butoxy group, tert-butoxy group, etc. Among these, methoxy group (-OCH 3 ) is preferred.
  • R 4 and R 5 in each benzene ring may be the same or different, but in each benzene ring, either one of R 4 and R 5 independently It is preferable that one is a hydrogen atom and the other is a hydrogen atom, an alkoxy group, or -OG.
  • R 4 and R 5 in one molecule is preferably the same group.
  • either one of R 4 and R 5 is a hydrogen atom, it can be easily produced using coumaric acid or a compound obtained from coumaric acid by reaction using an enzyme, as described below.
  • * becomes a bonding site it may be bonded to another skeleton shown in formula (1) via a linking group (for example, -COO-R 2 -COO-, which will be described later), or it may be bonded to another functional group.
  • a linking group for example, -COO-R 2 -COO-, which will be described later
  • functional groups represented by -COOR 1 and -COOR 3 which will be described later.
  • it may serve as a site that bonds to two hydrogen atoms.
  • the epoxy resin of the present invention is preferably a compound having a structure represented by the following formula (1-1).
  • R 1 and R 3 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a hetero atom, or a glycidyl group, and R 2 is a hetero atom. It is a divalent hydrocarbon group having 2 to 20 carbon atoms which may have .
  • n is an integer from 0 to 100.
  • G represents a glycidyl group.
  • R 4 and R 5 are the same as above.
  • one of R 4 and R 5 is a hydrogen atom, and the other is one of a hydrogen atom, -OCH 3 and -OG.
  • the other of R 4 and R 5 in one molecule is the same group.
  • both R 4 and R 5 are preferably hydrogen atoms from the viewpoint of easy synthesis from biomass. Therefore, the epoxy resin of the present invention preferably has a structure represented by the following formula (1-2).
  • R 1 and R 3 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a hetero atom, or a glycidyl group
  • R 2 is It is a divalent hydrocarbon group having 2 to 20 carbon atoms that may have a heteroatom.
  • n is an integer from 0 to 100.
  • G represents a glycidyl group.
  • the monovalent hydrocarbon group having 1 to 20 carbon atoms in R 1 and R 3 may be an aliphatic hydrocarbon group or an aromatic ring. It may be an aromatic hydrocarbon group having These may or may not have heteroatoms. Further, examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a halogen atom, and a phosphorus atom. Heteroatoms include, but are not particularly limited to, oxygen atoms forming ether bonds, ester bonds, keto groups, alkoxy groups, etc., sulfur atoms forming sulfonyl groups, thiol bonds, etc., and hydrogen atoms substituted for hydrocarbon groups. Examples include halogen atoms.
  • the monovalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms.
  • the aliphatic hydrocarbon group in R 1 and R 3 may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group, and examples thereof include an alkyl group and an alkenyl group.
  • the monovalent hydrocarbon group in R 1 and R 3 is preferably an alkyl group because it is easy to manufacture and tends to improve thermal stability.
  • the alkyl group may be linear, have a branched structure, or have a cyclic structure.
  • alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, and various heptyl groups. group, and various octyl groups.
  • “various” means various isomers including sec-, tert-, iso-, etc. in addition to linear (n-), and the same applies below.
  • the alkyl group may have a cyclic structure such as a cyclohexyl group.
  • the alkyl groups in R 1 and R 3 each independently preferably have 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms, and most preferably both are methyl groups. preferable.
  • n is 0 to 100 as described above, preferably 0 to 50, more preferably 0 to 10, still more preferably 0 to 5, particularly preferably It is 0.
  • the divalent hydrocarbon group having 2 to 20 carbon atoms in R 2 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group having an aromatic ring. These may or may not have a heteroatom. Details of the heteroatom are as described for R 1 and R 3 .
  • the aliphatic hydrocarbon group in R 2 may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group, but a saturated hydrocarbon group is preferable.
  • the saturated hydrocarbon group in R 2 may be linear, have a branched structure, or have a cyclic structure. As mentioned above, the saturated hydrocarbon group may or may not have a heteroatom, but it is preferable that it does not have a heteroatom.
  • the number of carbon atoms in the divalent hydrocarbon group in R 2 is preferably 2 to 10, more preferably 2 to 6, and still more preferably 2 to 4.
  • the aliphatic hydrocarbon group which may have a heteroatom in R 2 is also preferably a hydroxypropylene group.
  • a hydroxypropylene group is a functional group obtained by removing two hydrogen atoms bonded to a carbon atom from hydroxypropane, and is also called a hydroxypropanediyl group.
  • the hydroxypropylene group is a structural unit derived from epihalohydrin, which will be described later.
  • the position of the hydrogen atom to be removed and the position of the hydroxyl group are arbitrary, but typically it is a 2-hydroxypropane-1,3-diyl group (-CH 2 CHOHCH 2 -).
  • the compounds represented by formulas (1-1) and (1-2) each have a 2-hydroxypropane-1,3-diyl group in which R 2 is a 2-hydroxypropane-1,3-diyl group.
  • R 2 is a 2-hydroxypropane-1,3-diyl group.
  • it can be easily synthesized from compounds shown in formulas (2-4) to (2-6).
  • the plurality of R 2 in one molecule may be the same or different.
  • R 2 is preferably a hydroxypropylene group.
  • both R 1 and R 3 are preferably glycidyl groups.
  • Epoxy resins in which both R 1 and R 3 are glycidyl groups make it easier to obtain an epoxy cured product with a high crosslinking density.
  • R 2 and n are as described above in the epoxy resin having the structures shown in formulas (1-1) and (1-2), respectively. Therefore, in the epoxy resin in which both R 1 and R 3 are glycidyl groups, it is particularly preferable that n is 0.
  • both R 1 and R 3 are monovalent hydrocarbon groups which may have a heteroatom.
  • R 2 and n are as described above, and even if R 1 and R 3 have a heteroatom, Preferred embodiments of the monovalent hydrocarbon group are also as described above. Therefore, in this embodiment, R 1 and R 3 are both preferably alkyl groups, and the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. most preferably both R 1 and R 3 are methyl groups. Also in this embodiment, n is particularly preferably 0 as described above. The epoxy resin in this embodiment makes it easier to obtain a cured epoxy product with relatively excellent flexibility.
  • n is preferably 0 as described above, and therefore, it is also preferably a compound having the structure shown in the following formula (1-3).
  • R 6 is a hydrogen atom or -COOR 1
  • R 7 is a hydrogen atom or -COOR 3 .
  • R 1 , R 3 , R 4 and R 5 are as described above.
  • R 4 and R 5 Details of preferred embodiments of R 4 and R 5 are as described above. Therefore, in formula (1-3), in each benzene ring, one of R 4 and R 5 is a hydrogen atom, and the other is one of a hydrogen atom, -OCH 3 , and -OG. is preferable, and in this case, it is more preferable that the other of R 4 and R 5 in one molecule is the same functional group. More preferably, both R 4 and R 5 are hydrogen atoms. Further, preferred embodiments of R 1 and R 3 are also as described above.
  • R 6 is a hydrogen atom, -COOG, or -COOR 1
  • R 7 is a hydrogen atom, -COOG, or -COOR 3
  • R 1 and R 3 are preferably alkyl groups.
  • R 6 and R 7 are both a hydrogen atom, -COOG, or -COOR.
  • compounds having the structures represented by the following formulas (1-4) to (1-10) are preferable, and among them, compounds having the structure represented by the formula (1-4) are preferred. More preferred are compounds exhibiting the following structure.
  • Compounds having structures represented by the following formulas (1-4) to (1-10) are coumaric acid, ferulic acid obtained by enzymatic conversion of coumaric acid, caffeic acid, or caffeic acid obtained by enzymatic conversion of coumaric acid. , and can be easily synthesized from 4-vinylphenol obtained by decarbonizing reaction, so it can be easily produced from biomass raw materials.
  • R is an alkyl group. Details of the alkyl group are as above.
  • the epoxy resin of the present invention can be synthesized by reacting a compound having a skeleton represented by the following formula (2) (hereinafter also referred to as a raw material compound) with epihalohydrin.
  • R 14 and R 15 are each independently a hydrogen atom, an alkoxy group, or -OH. * may be a binding site with another structure.
  • the alkoxy groups of R 14 and R 15 are the same as the alkoxy groups of R 4 and R 5 described above, and are preferably methoxy groups.
  • R 14 and R 15 in each benzene ring may be the same or different, but in each benzene ring, either one of R 14 and R 15 is independently selected. is a hydrogen atom, and the other is preferably a hydrogen atom, an alkoxy group such as a methoxy group, or -OH. Note that the other of R 14 and R 15 in one molecule is preferably the same group.
  • R 11 and R 13 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom.
  • R 12 is a divalent hydrocarbon group having 2 to 20 carbon atoms which may have a heteroatom. The details of the monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom and the divalent hydrocarbon group having 2 to 20 carbon atoms which may have a hetero atom are as described above. be.
  • the divalent hydrocarbon group having 2 to 20 carbon atoms which may have a heteroatom is usually a structural unit derived from a dihydroxy compound described below, and therefore is usually other than a hydroxypropylene group, for example, A saturated hydrocarbon group having no heteroatom or a saturated hydrocarbon group having an ether bond as a heteroatom is preferred.
  • R 14 and R 15 are as described above.
  • m is an integer of 0 to 100, preferably 0 to 50, more preferably 0 to 10, still more preferably 0 to 5, particularly preferably 0.
  • both R 14 and R 15 are preferably hydrogen atoms. Therefore, the raw material compound preferably has a structure represented by the following formula (2-2).
  • R 11 , R 12 , R 13 and m are as described above.
  • m is preferably 0 as described above, and therefore, it is also preferably a compound having the structure shown in the following formula (2-3).
  • R 16 is a hydrogen atom or -COOR 11
  • R 17 is a hydrogen atom or -COOR 13 .
  • R 11 , R 13 , R 14 and R 15 are as described above.
  • R 14 and R 15 are as described above. Therefore, in formula (2-3), in each benzene ring, one of R 14 and R 15 is a hydrogen atom, and the other is one of a hydrogen atom, -OCH 3 , and -OH. is preferable, and in this case, it is more preferable that the other of R 14 and R 15 is the same functional group. More preferably, both R 14 and R 15 are hydrogen atoms. Further, preferred embodiments of R 11 and R 13 are also as described above. Also in formula (2-3), R 16 is a hydrogen atom or -COOR 11 , and R 17 is a hydrogen atom or -COOR 13 . R 11 and R 13 are each independently a hydrogen atom or an alkyl group. Among these, it is more preferable that R 16 and R 17 are both a hydrogen atom, -COOH, or -COOR (R is an alkyl group).
  • the raw material compound is preferably dihydroxytruxylic acid represented by the following formula (2-4) or an ester compound thereof.
  • Dihydroxytruxylic acid represented by the above formula (2-4) is a paracoumaric acid dimer, and can be obtained by dimerizing paracoumaric acid.
  • the method of dimerizing paracoumaric acid is not particularly limited, but examples include a method of dimerizing paracoumaric acid by light irradiation such as ultraviolet irradiation.
  • Paracoumaric acid is dimerized by the double bond at the beta position of paracoumaric acid being cleaved by UV irradiation and the molecules recombining with each other, and paracoumaric acid dimer having the structure shown in the above formula (2-4). You can get a body.
  • the raw material compound may be a compound represented by any of the following formulas (2-5) to (2-7), or an ester compound of a compound represented by (2-5) or (2-6).
  • the compounds of formulas (2-5) to (2-7) below can be obtained by dimerizing ferulic acid, caffeic acid, and 4-vinylphenol, respectively.
  • the method of dimerization is not particularly limited, but may include a method of dimerization by light irradiation such as ultraviolet irradiation, similar to paracoumaric acid.
  • Ferulic acid, caffeic acid, and 4-vinylphenol are obtained by enzymatic conversion reaction of coumaric acid, or by enzymatic conversion of coumaric acid and decarbonization reaction, so the formula (2-4) Similar to dihydroxytruxylic acid shown in , it can be easily produced from biomass raw materials.
  • the ester compound of dihydroxytruxylic acid shown in the above formula (2-4) is preferably a compound having the structure shown in the following formula (2-8), which is obtained by esterifying the above dihydroxytruxylic acid with a monohydroxy compound. can be mentioned.
  • R 18 and R 19 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom. Details of the monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a heteroatom are as described above. Therefore, R 18 and R 19 are each independently preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, even more preferably a carbon alkyl group. It is an alkyl group of number 1 to 3, and R 18 and R 19 are most preferably both methyl groups.
  • ester compound of the compound represented by the above formula (2-5) or formula (2-6) preferably a compound having the structure represented by formula (2-9) or a structure represented by formula (2-10) is used.
  • Examples include compounds having the following.
  • R 18 and R 19 are as described in the above formula (2-8).
  • the paracoumaric acid ester compound represented by formula (2-4) may be a compound obtained by esterifying the above-mentioned dihydroxytruxylic acid with a dihydroxy compound, or a dihydroxy compound and a monohydroxy compound.
  • the compound esterified with at least a dihydroxy compound in this way is a compound in which m is 1 or more in formula (2-1) or formula (2-2).
  • dihydroxytruxylic acid may be esterified with a dihydroxy compound and then further esterified with a monohydroxy compound, or after esterification with a monohydroxy compound, it may be esterified with a dihydroxy compound.
  • esterification with a dihydroxy compound and esterification with a monohydroxy compound may be performed in parallel.
  • m is 1 or more in formula (2-1) or (2-2), and at least one of R 11 and R 13 may have a hetero atom.
  • R 11 and R 13 may have a hetero atom.
  • it is a monovalent hydrocarbon group, it is preferable that both R 11 and R 13 are monovalent hydrocarbon groups that may have a heteroatom.
  • the method of esterifying dihydroxytruxylic acid with a hydroxy compound is not particularly limited, but includes a method of condensing a carboxylic acid and a hydroxy compound with an acid catalyst, a method of esterifying dihydroxytruxylic acid with a hydroxy compound, Examples include, but are not limited to, a method in which an acid halide such as an acid chloride is reacted with a hydroxy compound.
  • the monohydroxy compound used in the above esterification may be an aromatic monohydroxy compound or an aliphatic monohydroxy compound, but an aliphatic monohydroxy compound is preferable, and an alkyl monoalcohol is more preferable among them.
  • the alkyl monoalcohol may be a straight-chain alcohol, but may also have a branched structure or a cyclic structure.
  • the alkyl monoalcohols include methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, various pentanols, various hexanols, various heptanols, various octanols, Examples include various nonanol, various decanol, cyclopentanol, cyclohexanol, methylcyclohexanol, cyclohexane methanol, and among these, metal is particularly preferred.
  • the dihydroxy compound used for esterification may be an aromatic dihydroxy compound or an aliphatic dihydroxy compound, but aliphatic dihydroxy compounds are preferable, and among them, alkyl diols are more preferable.
  • the aliphatic dihydroxy compound may be a straight-chain alcohol, but may also have a branched structure or a cyclic structure. Specific examples of aliphatic dihydroxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl.
  • neopentyl glycol 1,4 -cyclohexanediol, 1,4-cyclohexanedimethanol and the like.
  • ethylene glycol is preferred.
  • the ester compound of the compound represented by formula (2-5) or formula (2-6) can be used as a dihydroxy compound, or a dihydroxy compound and It may also be a compound esterified with a monohydroxy compound.
  • the compound esterified with at least a dihydroxy compound in this way is a compound in which m is 1 or more in formula (2-1) or formula (2-2). Details of the compound obtained by esterifying the compound represented by formula (2-5) or formula (2-6) with a dihydroxy compound, or a dihydroxy compound and a monohydroxy compound are the same as those for the compound represented by formula (2-4). Therefore, the explanation will be omitted.
  • Epihalohydrins that can be used in the synthesis of epoxy resins include epifluorohydrin, epichlorohydrin, epibromohydrin, and epiiodohydrin, and among these, epichlorohydrin is preferred in terms of reactivity and economy.
  • the epoxy resin of the present invention can be obtained by reacting a compound having the skeleton shown in formula (2) with epihalohydrin.
  • a compound having the skeleton shown in formula (2) and epihalohydrin are preferably mixed and reacted, for example, in a reactor.
  • the amount of epihalohydrin added to the compound having the skeleton shown in formula (2) in the reaction system is preferably 1 equivalent or more.
  • the compound represented by formula (1) can be synthesized.
  • the term “equivalent” refers to the molar equivalent to the functional groups (hydroxyl group and carboxy group) possessed by the compound having the skeleton shown in formula (2), and the same applies below.
  • the amount of epihalohydrin added is in large excess. Specifically, it is preferably 2 equivalents or more, more preferably 5 equivalents or more, and still more preferably 8 equivalents or more.
  • the amount of epihalohydrin added is preferably 50 equivalents or less with respect to the functional group of the compound shown in formula (2), It is more preferably 30 equivalents or less, still more preferably 20 equivalents or less, even more preferably 15 equivalents or less.
  • formula (2-1), formula (2-2) or formula (2-3) (however, in formula (2-3), R 16 and R 17 are -COOR 11 and -COOR 13 , respectively) ), R 11 and R 13 are hydrogen atoms (especially when using any of the compounds of formulas (2-4) to (2-6) as raw materials), and n
  • the amount of epihalohydrin added may be reduced, for example, 2 equivalents or less.
  • R 11 and R 13 are hydrogen atoms, if the amount of epihalohydrin added is reduced, oligomerization of the compound having the skeleton shown in formula (2) and epihalohydrin will proceed more easily.
  • -1) or the compound represented by formula (1-2) can be easily obtained.
  • the reaction between the compound having the skeleton shown in formula (2) above and epihalohydrin is preferably carried out in the presence of a catalyst.
  • the catalyst include quaternary ammonium salts such as benzyltriethylammonium chloride, benzyltriethylammonium bromide, tetrabutylammonium fluoride, and tetrabutylammonium bromide.
  • One type of catalyst may be used alone, or two or more types may be used in combination.
  • the amount of the catalyst added is preferably 0.01 to 2 mol, more preferably 0.05 to 1 mol, and still more preferably 0.1 to 0.0 mol, per mol of the compound having the skeleton shown in formula (2). It is 5 moles.
  • the above reaction may be carried out in the presence of a solvent, or may be carried out without a solvent.
  • the compound having the skeleton shown in formula (2) can be appropriately diluted with epihalohydrin by using a large excess of epihalohydrin as described above, and the above reaction can be carried out appropriately even if the reaction is carried out without a solvent or with a small amount of solvent. can proceed.
  • As the reaction solvent aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogen solvents, ester solvents, ether solvents, etc. can be used.
  • the reaction in the presence of the above catalyst is carried out at, for example, 40 to 150°C, preferably 60 to 120°C, for example, for 30 minutes to 24 hours, preferably for 2 to 12 hours.
  • a basic compound to the reaction system in addition to the above catalyst.
  • a basic compound By adding a basic compound, dehydrohalogenation progresses more easily, making it possible to improve the yield of the desired epoxy resin.
  • the basic compound is reacted for a certain period of time in the presence of the above-mentioned catalyst, then added to the reaction system, and further reacted for a certain period of time.
  • the reaction after addition of the basic compound is carried out at, for example, -10 to 30°C, preferably 0 to 15°C, for example, 10 minutes to 24 hours, preferably 30 minutes to 12 hours.
  • the basic compound used is not particularly limited as long as it functions as a base. Specifically, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium hydride, sodium hydride, potassium hydride, lithium carbonate, sodium carbonate. , potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, lithium alkoxide, sodium alkoxide, potassium alkoxide, and other metal bases. Among these, it is preferable to use at least one of sodium hydroxide and potassium hydroxide in terms of economy and availability.
  • the basic compound is not particularly limited, but may be added to the reaction system, for example, in the form of an aqueous solution. The amount of the basic compound added may be, for example, more than 1 equivalent, preferably 1.5 to 20 equivalents, and more preferably It is 2 to 15 equivalents.
  • the target epoxy resin is purified by distilling off epihalohydrin, distilling off the reaction solvent used as necessary, and extracting the target epoxy resin and water-soluble mixture using water and a hydrophobic solvent.
  • General unit operations such as separation of chemical compounds, distillation of extraction solvent, distillation, etc., or a suitable combination of these can be carried out.
  • the raw materials can be produced from biomass, and an epoxy resin with a high biomass ratio can be obtained.
  • dihydroxytruxylic acid represented by formula (2-4) is obtained by obtaining paracoumaric acid from a biomass-derived compound such as L-tyrosine through microbial synthesis, and photodimerizing paracoumaric acid as described above. Obtainable.
  • the compounds represented by formulas (2-5) to (2-7) can also be produced from biomass as described above. Therefore, the skeleton represented by formula (1) of the present invention can be derived from biomass, particularly from a compound synthesized by microorganisms.
  • the structural unit derived from dihydroxytruxylic acid in formula (1-2) be derived from biomass, particularly from a compound synthesized by microorganisms.
  • the method for obtaining paracoumaric acid by microbial synthesis has stereoselectivity and can obtain paracoumaric acid in high yield, and the subsequent dimerization and epoxidation are also relatively simple.
  • the epoxy resin having the skeleton represented by formula (1) can be easily produced even though it is a compound that can be obtained from biomass.
  • R 1 and R 3 may be derived from a monohydroxy compound, and R 2 may be derived from a dihydroxy compound; It is preferable that the monohydroxy compound and the dihydroxy compound are derived from biomass.
  • biomass-derived epoxy resins it is possible to obtain epoxy resins with even higher biomass content.
  • biomass-derived methanol, ethanol, and butanol are known as monohydroxy compounds
  • biomass-derived ethylene glycol, 1,3-propanediol, and 1,4-butanediol are known as dihydroxy compounds. etc. are known, and by using these, the biorate of epoxy resin can be further improved.
  • the cured product of the present invention (hereinafter also referred to as "epoxy cured product") is obtained by curing the above-mentioned epoxy resin.
  • the epoxy cured product is generally cured with a curing agent, and therefore is preferably a cured product of a curable composition containing an epoxy resin and a curing agent.
  • the curing agent that can be used in the epoxy cured product is not particularly limited as long as it can cure the epoxy resin, but compounds that react with the epoxy resin to form a three-dimensional network structure (network polymer) are preferred.
  • Specific curing agents include amine-based curing agents, acid anhydride-based curing agents, polyamide resins that are condensates of dimer or trimer acids and polyamines, Lewis acids such as boron trifluoride-amine complexes, phenol or its like. Examples include derivatives. Further, as the curing agent, a mercapto curing agent can also be used.
  • Examples of the amine curing agent include polyamines such as aliphatic polyamines and aromatic polyamines.
  • the aliphatic polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tetraethylenepentamine, dimethylaminopropylamine, bishexamylenetriamine, cyclohexylaminopropylamine, aminoethylethanolamine, and monohydroxyethyl Diethylenetriamine, bishydroxyethyldiethylenetriamine, N-(2-hydroxypropyl)ethylenediamine, hexamethylenediamine, diethylene glycol bis(3-aminopropyl)ether, diethylaminopropylamine, 3,9-bis(3-aminopropyl)-2,4 , 8,10-tetrasoxaspiro[5,5]undecane, menthanediamine, isophoronediamine, 4,4'-methylenebis(cyclohex
  • Aromatic polyamines are amines having an aromatic ring, and specifically include various xylylene diamines such as phenylene diamine, diaminodiphenylmethane, diaminoanisole, toluene diamine, metaxylylene diamine, and diaminodiphenylsulfone.
  • the amine curing agent may be an imidazole curing agent, an amidoamine curing agent, or the like.
  • imidazole curing agents include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 1,2-diethylimidazole.
  • acid anhydride curing agents examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, chlorendic anhydride, dodecynyl succinic anhydride, and methyltetrahydro
  • acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, chlorendic anhydride, dodecynyl succinic anhydride, and methyltetrahydro
  • examples include phthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride represented by 4-methylhexahydro
  • phenol derivatives include bisphenols and their derivatives such as bisphenol F and bisphenol A, trifunctional phenols and their derivatives such as tri(hydroxyphenyl)methane and tri(hydroxyphenyl)ethane, phenols such as phenol novolak, and formaldehyde.
  • examples include compounds obtained by reacting with.
  • Examples of mercapto curing agents include compounds with two mercapto groups in the molecule such as 1,4-bis(3-mercaptobutyryloxy)butane, and compounds with mercapto groups such as pentaerythritol tetrakis (3-mercaptobutyrate). Compounds having three or more can also be used.
  • the curing agents may be used alone or in combination of two or more.
  • the polyamines preferably have a total of two or more primary amino groups and secondary amino groups in one molecule, and preferably have at least one primary amino group, and more preferably have a primary amino group. Have two or more.
  • the total number of primary amino groups and secondary amino groups in one molecule of polyamines is not particularly limited, but is, for example, 8 or less, preferably 5 or less, more preferably 3 or less.
  • the blending amount of the curing agent is, for example, 1 to 100 parts by weight, preferably 2 to 50 parts by weight, based on 100 parts by weight of the epoxy resin. If it is above these lower limits, it can be properly cured. For example, when a three-dimensional network structure is formed, the structure becomes strong and mechanical properties and thermal properties tend to be good. In addition, by setting the amount to be below these upper limits, the amount of the curing agent can be prevented from increasing more than necessary, and mechanical properties and thermal properties tend to be good.
  • the blending amount of the curing agent should be adjusted according to the epoxy equivalent of the epoxy resin and, if an amine curing agent is used, the amount of active hydrogen in the amine curing agent (i.e., the hydrogen atom bonded to the nitrogen atom in the amino group). You can adjust it as appropriate.
  • the ratio of the number of active hydrogens to the number of epoxy groups may be adjusted to 1 or close to 1, specifically 0.5 to 2, preferably 0.75 to 1.5, more preferably It is 0.9 to 1.1.
  • the glass transition temperature (Tg) of the epoxy cured product measured with a differential scanning calorimeter is preferably 150° C. or higher. When the temperature is 150° C. or higher, thermal performance can be improved, and the heat resistance of the cured epoxy product can be improved. Further, the glass transition temperature (Tg) of the epoxy cured product is more preferably 160°C or higher, and still more preferably 170°C or higher. The glass transition temperature (Tg) of the epoxy cured product is not particularly limited, but is, for example, 300° C. or lower.
  • the glass transition temperature (Tg) of the epoxy cured product measured with a dynamic viscoelasticity device is preferably 150°C or higher, more preferably 160°C or higher, and even more preferably 170°C or higher. , for example, 300°C or less.
  • the epoxy cured product is not particularly limited, it can be produced by mixing an epoxy resin and a curing agent to obtain a curable composition, and heating as necessary.
  • the heating temperature is not particularly limited, but is, for example, room temperature (23°C) to 300°C, preferably 40°C to 250°C, and heating within the above temperature range is for example 10 minutes to 13 hours, preferably 1 to 6 hours. good.
  • the heating temperature may be increased stepwise as curing progresses.
  • the curable composition containing an epoxy resin and a curing agent may be diluted by adding a solvent or the like, or may contain other components as appropriate. In the case of diluting with a solvent, the solvent may be removed by appropriately drying the solvent by the above-mentioned heating.
  • the curable composition may contain a curing accelerator in addition to the epoxy resin and curing agent of the present invention.
  • a curing accelerator is a component that accelerates curing by a curing agent.
  • the curing agents dicyandiamide and the like have a high curing temperature when used alone, so a curing accelerator can be used to increase the curing activity of dicyandiamide and the like.
  • the curing accelerator for dicyandiamide include urea-based, imidazole-based, tertiary amine-based, caprolactam, and the like.
  • urea-based and imidazole-based are preferred, including 2,4-diamino-6-(2-methylimidazolyl-(1))-ethyl-s-triazine, 3-(3,4-dichlorophenyl)-1,1 -dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea) are more preferred.
  • the content of the curing accelerator is, for example, about 0.1 to 10 parts by mass based on 100 parts by mass of the epoxy resin.
  • the epoxy resin and epoxy cured product of the present invention can be used in various fields, including, but not limited to, electrical fields, transportation fields, civil engineering fields, architecture fields, mechanical fields, medical fields, etc. be.
  • the epoxy resin and epoxy cured product of the present invention can be used in various forms such as various molded products, adhesives, paints, fillers, films, powders, composite materials, and foams. More specifically, adhesives for dissimilar materials, rubber-resin adhesives, well bonding applications, bonding between substrates and semiconductor elements such as die attach, flexible substrate adhesives such as bonding films, and various construction and civil engineering applications.
  • adhesives such as adhesives, anti-fog paints, electrodeposition paints, anti-corrosion paints, floor coatings, other paints for architecture and civil engineering, sealing for covered electric wires, etc. It can be used for various purposes such as fiber reinforcement materials, fiber sizing agents, prepregs, electrical insulation materials and protective materials for electronic components, photosensitive resins, lens applications, and dental materials, but is not limited to these applications.
  • the epoxy resin-containing composition containing the epoxy resin of the present invention can contain various components depending on the intended use.
  • such components include resins other than the epoxy resin of the present invention, latex, fillers, pigments, silane coupling agents, surfactants, ultraviolet absorbers, and antioxidants. , stabilizers, plasticizers, leveling agents, antifoaming agents, antistatic agents, flame retardants, lubricants, dispersants and the like.
  • epoxy resin-containing compositions used for various purposes
  • compositions containing components derived from the epoxy resin of the present invention will be explained in more detail. However, each of the following compositions may contain components other than those specifically explained below, as necessary.
  • the epoxy resin-containing composition when used as an adhesive, may contain an epoxy resin and a curing agent. From this point of view, for example, polymer fine particles may be contained.
  • the adhesive is preferably used for dissimilar material adhesive applications in fields such as automobiles, and for well bond applications.
  • the dissimilar materials used in dissimilar adhesive applications include two types selected from various materials such as various steel materials, aluminum, aluminum alloys, fiber reinforced plastic (FRP) plates such as carbon fiber and glass fiber, and carbon fiber reinforced plastic (CFRP). Examples include combinations.
  • the epoxy resin-containing composition used for the adhesive application may contain an epoxy resin other than the epoxy resin of the present invention.
  • the polymer fine particles are preferably polymer fine particles having a core-shell structure.
  • a polymer particle having a core-shell structure refers to a polymer particle in which the molecular structure is different between the central part (core part) and the outer peripheral part (shell part).
  • the components constituting the core part of the polymer fine particles having a core-shell structure include butadiene rubber (BR), acrylic rubber (ACM), silicone rubber (Si), butyl rubber (IIR), nitrile rubber (NBR), and styrene-butadiene rubber. (SBR), isoprene rubber (IR), ethylene propylene rubber (EPR), and the like. Among them, butadiene rubber is preferred.
  • the component constituting the shell part of the polymer fine particles having a core-shell structure is graft-polymerized to the above-mentioned core part and covalently bonded to the polymer constituting the core component.
  • the components constituting the shell portion include acrylic ester monomers, methacrylic ester monomers, and aromatic vinyl monomers.
  • the content of the polymer fine particles is, for example, 1 to 100 parts by weight, preferably 2 to 80 parts by weight, and more preferably 4 to 60 parts by weight, based on 100 parts by weight of the epoxy resin contained in the curable composition.
  • Polymer fine particles having a core-shell structure may be used alone, or two or more types may be used in combination.
  • the epoxy resin-containing composition preferably contains dicyandiamide, although the curing agents listed above are used as appropriate.
  • the content of the curing agent is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 25 parts by weight, and even more preferably 1 to 20 parts by weight, based on 100 parts by weight of the epoxy resin.
  • the epoxy resin containing composition contains blocked urethane.
  • Blocked urethane is an elastomer type compound containing a urethane group and/or a urea group, and has an isocyanate group at the end of various blocks in which all or part of the terminal isocyanate group has an active hydrogen group.
  • Compounds capped with agents are contemplated. Particularly preferred is a compound in which all of the terminal isocyanate groups are capped with a blocking agent.
  • Specific examples of blocked urethanes include compounds described in International Publication No. 2016/163491.
  • the content of blocked urethane in the epoxy resin-containing composition is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, and even more preferably 5 to 30 parts by weight, based on 100 parts by weight of the epoxy resin.
  • the epoxy resin-containing composition may also be used as a rubber-resin adhesive in tires and the like.
  • An example of the rubber-resin adhesive includes, in addition to the epoxy resin of the present invention, a curable composition containing synthetic rubber latex.
  • Synthetic rubber latexes include, but are not particularly limited to, those containing unsaturated dienes, such as styrene-butadiene copolymer rubber latex, vinylpyridine-styrene-butadiene copolymer rubber latex, and carboxyl group-modified styrene.
  • -Butadiene copolymer rubber latex, nitrile rubber latex, chloroprene rubber latex, etc. can be mentioned.
  • the content of the synthetic rubber latex is not particularly limited, but is, for example, 25 to 80% by mass, preferably 35% by mass, based on solid content. ⁇ 75% by weight, more preferably 55-75% by weight.
  • the curable composition containing the synthetic rubber latex preferably further contains a water-soluble carbodiimide.
  • Water-soluble carbodiimide refers to a carbodiimide that is soluble in water, and includes carbodiimides that are water-based and partially water-soluble.
  • Water-soluble carbodiimide can be used as a dehydration condensation agent capable of forming an ester bond or an amide bond between a COOH group and an OH group or an amino group of a compound contained in an aqueous solution.
  • 1-ethyl-3-(3-(dimethylaminopropyl)carbodiimide (WSC) activates carboxyl groups, and its active intermediates can react with amino and hydroxyl groups to form amides and esters.
  • WSC 1-ethyl-3-(3-(dimethylaminopropyl)carbodiimide
  • the water-soluble carbodiimide can coat the surface of synthetic rubber latex containing an unsaturated diene while crosslinking, and can be combined with the epoxy resin of the present invention to bond the resin of the adherend to the rubber.
  • Ru The water-soluble carbodiimide is preferably a water-soluble salt such as a hydrochloride or a sulfate.
  • the water-soluble carbodiimide includes 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC); 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide-meth-p -Water-soluble salts of 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide such as toluene sulfate; 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmol Examples include triazine condensing agents such as phorinium chloride (DMT-MM), and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) is preferably used.
  • EDC 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride
  • DMT-MM 1-ethyl-3-(
  • the content of water-soluble carbodiimide is not particularly limited, but is preferably 0.1 to 15% by mass on a solid content basis. It is more preferably 0.3 to 10% by weight, even more preferably 0.5 to 7% by weight, even more preferably 0.5 to 5% by weight.
  • the epoxy resin of the present invention used in the rubber-resin adhesive may have two or more epoxy groups in one molecule, but preferably contains four or more epoxy groups in one molecule. It's good to do that.
  • the content of the epoxy resin is not particularly limited, but is preferably 0.1 to 40% by mass on a solid content basis, and It is preferably 0.4 to 40% by weight, particularly preferably 1.0 to 30% by weight.
  • the epoxy resin-containing composition for the rubber-resin adhesive is not particularly limited, but each component is preferably dispersed or dissolved in water and used as a dispersion.
  • the epoxy resin-containing composition may include silver particles, the epoxy resin of the present invention, and a curing agent, and the composition is used after being diluted with a solvent. Good.
  • the epoxy resin-containing composition may contain epoxy resins other than the epoxy resin of the present invention. Further, as the curing agent, phenol derivatives and dicyandiamide are preferable, and these may be used in combination.
  • the content of silver particles is, for example, 70 to 98% by mass, preferably 75 to 95% by mass, based on solid content. Further, the content of the epoxy resin is, for example, 1 to 20% by mass, preferably 2 to 15% by mass, based on solid content. Further, the content of the curing agent is, for example, 0.1 to 1.5% by mass, preferably 0.2 to 1.0% by mass.
  • the epoxy resin-containing composition for flexible substrates is preferably a curable resin composition containing the epoxy resin of the present invention and a curing agent, and may also contain epoxy resins other than the epoxy resin of the present invention, or epoxy resins other than the epoxy resin of the present invention. It may contain a resin, and such resins include polyester polymers such as polyester polyurethane resins.
  • the polyester polyurethane resin is preferably a resin obtained by reacting at least a polyester polyol, a polyisocyanate, and a chain extender such as a diol compound other than the polyester polyol as raw materials.
  • a resin having a carboxy group or a carboxylic acid anhydride structure may be contained.
  • the curing agent those mentioned above may be used as appropriate, but imidazole derivatives such as imidazole silane compounds may also be used in addition to those mentioned above.
  • the above-described epoxy resin-containing composition for flexible substrates may contain an organic filler, a metal filler, an inorganic filler other than the metal filler, and the like.
  • the content of the epoxy resin is preferably 1 to 60% by mass, and preferably 2 to 40% by mass, based on the total amount of components other than the filler. %, and even more preferably 3 to 20% by mass.
  • the epoxy resin of the present invention may be used for paint purposes, or may be used as a binder resin for paints.
  • a coating composition containing the epoxy resin of the present invention and silica particles.
  • the present coating composition may contain a silane coupling agent and the like as appropriate.
  • the coating composition is preferably used as a dispersion by dispersing or dissolving each component in a liquid medium such as water.
  • the binder resin may include an epoxy resin other than the epoxy resin of the present invention or a resin other than the epoxy resin.
  • the silica particles water-dispersed silica is preferred, and colloidal silica or the like is preferably used.
  • the liquid medium include water and organic solvents, preferably water or a mixed solvent of water and an organic solvent.
  • the organic solvent may be any organic solvent as long as it can disperse silica.
  • ethylene glycol monobutyl ether may be used.
  • the content of the epoxy resin may be 0.1 to 1000 parts by mass, 0.5 to 500 parts by mass, and 1 to 100 parts by mass, based on 100 parts by mass of silica particles. It may be up to 100 parts by mass.
  • an epoxy resin when used in electrodeposition coating applications, an epoxy resin may be reacted with an amine and used as an aminated epoxy resin.
  • amines include primary amines such as butylamine, octylamine, and monoethanolamine; secondary amines such as diethylamine, dibutylamine, methylbutylamine, diethanolamine, and N-methylethanolamine; and complex amines such as diethylenetriamine.
  • the reaction of the above-mentioned primary amine can be controlled by forming a ketimine group using a ketone compound and forming a so-called block.
  • the coating composition for electrodeposition coating may contain, for example, an aminated epoxy resin and a curing agent such as a blocked polyisocyanate curing agent, and may further contain a pigment dispersion paste if necessary.
  • the pigment dispersion paste includes a pigment dispersion resin and a pigment.
  • the coating composition for electrodeposition coating may be used as an emulsion or the like.
  • the coating composition may be a cured composition containing the epoxy resin of the present invention and a curing agent.
  • a coating composition may contain an epoxy resin other than the epoxy resin of the present invention, a pigment or a pigment dispersant, and a silane coupling agent or the like to improve adhesion. May contain. Further, it may generally be used after being diluted with an organic solvent.
  • a coating composition containing an epoxy resin and a curing agent is preferably used, for example, as an anticorrosive coating composition, and particularly preferably used for anticorrosion of ships.
  • the content of the epoxy resin is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, based on solid content.
  • the epoxy resin of the present invention may be used in architecture and civil engineering applications, for example, as a floor coating agent.
  • the epoxy resin-containing composition used as a floor coating agent preferably contains the epoxy resin of the present invention and a curing agent, and further preferably contains an inorganic filler.
  • known inorganic fillers used as flooring agents such as carbon nanotubes, silica, silica sand, barite, calcium carbonate, and talc may be used.
  • pigments used as colorants may also be appropriately blended.
  • the epoxy resin may contain epoxy resins other than those of the present invention.
  • the content of the inorganic filler is, for example, about 1 to 1000 parts by mass, preferably 10 to 200 parts by mass, more preferably 20 to 200 parts by mass, based on 100 parts by mass of the epoxy resin. It is 100 parts by mass.
  • the epoxy resin-containing composition may be used in construction and civil engineering applications other than as a floor coating, and may also be used as a tank paint, a pipe interior paint, an exterior paint, and the like. It may also be used as an adhesive in architecture and civil engineering applications, for example, for bonding various structures.
  • the epoxy resin of the present invention when used as a sealing material, preferably for sealing a covered electric wire, it may be used, for example, as a curable composition containing an epoxy resin and a curing agent.
  • the curing agent used in the sealant application the above-mentioned curing agents can be used as appropriate, but amine-based curing agents and mercapto-based curing agents can be preferably used.
  • the curable composition used as a sealant contains a silane coupling agent.
  • the epoxy resin of the present invention When the epoxy resin of the present invention is used as a fiber sizing agent, it may be used in combination with a polyester resin having a sulfonic acid group.
  • a polyester resin having a sulfonic acid group an aromatic polyester resin, an aliphatic polyester resin, etc. can be used, but it is preferable to use an aromatic polyester resin.
  • the aromatic polyester resin preferably has a structural unit derived from an aromatic dicarboxylic acid such as isophthalic acid or terephthalic acid.
  • the epoxy resin-containing composition for the fiber sizing agent preferably contains a surfactant in addition to the above-mentioned epoxy resin and polyester resin having a sulfonic acid group. Surfactants are preferred.
  • Aromatic nonionic surfactants include polyoxyalkylene alkylphenyl ether, polyoxyalkylene styrenated phenyl ether, polyoxyalkylene benzylphenyl ether, polyoxyalkylene cumyl phenyl ether, polyoxyalkylene naphthylphenyl ether, polyoxyalkylene Examples include styrenated phenyl ethers (alkylphenyl ethers), and among these, polyoxyalkylene styrenated phenyl ethers such as polyoxyethylene styrenated phenyl ethers are preferred.
  • the epoxy resin-containing composition for fiber sizing agent may contain epoxy resins other than the epoxy resin of the present invention.
  • the epoxy resin-containing composition for a fiber sizing agent is preferably used as an aqueous composition, for example, as an aqueous dispersant.
  • the content of the epoxy resin is, for example, 75 to 95% by mass, and preferably 80 to 95% by mass, based on the solid content.
  • the epoxy resin of the present invention may be used for prepreg applications, and is preferably used as a matrix resin to be impregnated into fiber materials such as reinforcing fibers used for prepreg applications.
  • the epoxy resin-containing composition may be a curable composition and may contain the epoxy resin of the present invention and a curing agent.
  • the epoxy resin of the present invention may be used alone as a resin component, but it may also be used in combination with other resin components, and epoxy resins other than the epoxy resin of the present invention, polyfunctional A (meth)acrylate compound, a cyanate ester resin containing two or more cyanato groups, etc. may be contained.
  • the epoxy resin-containing composition contains a thermoplastic resin.
  • the epoxy resin-containing composition used for prepreg applications may contain a flame retardant.
  • the flame retardant include phosphorus-containing compounds such as phosphoric acid esters, nitrogen-containing compounds such as red phosphorus, melamine, melamine cyanurate, and melamine isocyanurate, metal hydroxides, metal oxides, and the like.
  • the content of epoxy resin is preferably about 20 to 99% by mass, more preferably about 50 to 80% by mass.
  • the content of the curing agent is preferably 1 to 25% by mass, more preferably 2 to 20% by mass.
  • the epoxy resin of the present invention may be used in electronic substrates and the like, and specifically, it may be used as a protective material and an electrically insulating material for forming an electrically insulating layer.
  • a curable resin composition containing a filler in addition to the epoxy resin of the present invention and a curing agent is preferable.
  • the filler is preferably insulating.
  • Such fillers include silica, alumina, aluminum nitride, boron nitride, silicon carbide, silicon nitride, and the like.
  • fillers other than the above-mentioned inorganic fillers may be used, or organic fillers may be used.
  • the filler content is, for example, 50 to 90% by mass, preferably 65 to 85% by mass, based on solid content.
  • Curable resin compositions used for electrical insulation materials and protective materials may contain resins other than the epoxy resin of the present invention, for example, may contain rubbery polymer compounds such as conjugated diene rubber. Good too.
  • the content of the rubbery polymer compound is, for example, 30 to 70% by mass, preferably 40 to 60% by mass, based on the solid content of all components other than the filler.
  • it may contain an epoxy resin other than the epoxy resin of the present invention, and may contain a thermosetting resin other than the epoxy resin, such as a phenoxy resin. It may also contain a silane coupling agent.
  • the content of epoxy resin is, for example, 20 to 70% by mass, preferably 25 to 40% by mass, based on the solid content of the total amount of components other than fillers. .
  • the epoxy resin-containing composition When used as an electrical insulation material or protective material for electronic boards, the epoxy resin-containing composition may be used as a photosensitive resin composition, and in such a case, in addition to the epoxy resin, It may be a composition containing a photosensitive resin such as a carboxyl group-containing photosensitive resin, a photopolymerization initiator, a reactive diluent, a photosensitive monomer, a filler, and the like. Furthermore, when used as a photosensitive resin composition, it may be used for purposes other than the above-mentioned protective material for electronic substrates and electrical insulating material.
  • a photosensitive resin such as a carboxyl group-containing photosensitive resin, a photopolymerization initiator, a reactive diluent, a photosensitive monomer, a filler, and the like.
  • the epoxy resin of the present invention may be used in combination with a photoacid generator such as iodonium salts, sulfonium salts, and pyridinium salts.
  • the photoacid generator is an agent that generates acid upon irradiation with light, and the epoxy resin is preferably polymerized by the acid generated by decomposition of the photoacid generator.
  • applications include, but are not limited to, dental applications, and more specifically, filling and restoring materials used for repairing damaged teeth. , lining materials for denture bases, hybrid ceramics for dental crown restorations, etc. Further, it may be used for lens applications as described below.
  • the epoxy resin of the present invention may be used in combination with resin components such as epoxy resins other than the epoxy resin of the present invention and oxtacene compounds.
  • resin components such as epoxy resins other than the epoxy resin of the present invention and oxtacene compounds.
  • other epoxy resins, oxtacene compounds, etc. may be contained.
  • other epoxy resins include diglycidyl ether compounds having a bisphenol skeleton, bifunctional alicyclic epoxy compounds having no bisphenol skeleton, and trifunctional or higher functional epoxy compounds having an isocyanurate ring structure.
  • the epoxy resin-containing composition is preferably a photosensitive resin composition, and may contain, for example, the above-mentioned photoacid generator.
  • the uses and specific formulations for each use explained above are only examples, and may be used for purposes other than those explained above, and the formulation of each composition for each use may be different from the above-mentioned formulation. Anything other than that is fine.
  • Glass transition temperature (Tg) Using a differential scanning calorimeter (product name: "DSC-60”) manufactured by Shimadzu Corporation, measurements were performed under argon atmosphere at a heating rate of 10°C/min, and the midpoint of the baseline displacement was determined as the glass transition temperature. did. At this time, the temperature was raised to 250°C at a rate of 10°C/min, the temperature was lowered to 30°C, and the glass transition temperature was measured when the temperature was raised again. Using a dynamic viscoelasticity device (trade name "Rheogel-E4000”) manufactured by UBM Co., Ltd., it was measured under a nitrogen atmosphere at a temperature increase of 3°C/min, and the peak top temperature of tan ⁇ was taken as the glass transition temperature. .
  • DSC-60 differential scanning calorimeter
  • Synthesis example 1 [Synthesis of paracoumaric acid dimer] Paracoumaric acid (manufactured by Tokyo Kasei Co., Ltd.) was suspended in hexane, and the suspended solution was irradiated with UV light using an incandescent mercury lamp. The double bond at the beta position of paracoumaric acid was cleaved by UV irradiation, and the molecules recombined with each other, resulting in dimerization. After removing hexane from the reaction solution, it was resuspended in ethanol and filtered. The powder remaining on the filtration membrane was obtained as paracoumaric acid dimer. In addition, when the powder remaining on the filter membrane was subjected to 1 H-NMR measurement, it was confirmed that it was paracoumaric acid dimer (4,4'-dihydroxytruxylic acid) shown by formula (2-1). did it.
  • Example 1 5 g of the paracoumaric acid dimer obtained in Synthesis Example 1 was suspended in 50 ml of methanol and 0.3 ml of concentrated sulfuric acid, and reacted at 80° C. for 6 hours. After the reaction was completed, methanol was removed and the mixture was dried. The dried methyl ester was dissolved in 50 ml of ethyl acetate, and then washed twice with 5% by mass NaHCO 3 solution. It was further washed twice with saturated brine, and the ethyl acetate layer was collected.
  • Example 2 4.64 g of the epoxy resin obtained in Example 1 and 0.85 g of isophorone diamine were mixed. Thereafter, a cured product was produced by heating at 100°C for 1 hour, at 160°C for 1 hour, and then at 200°C for 1 hour. When the obtained cured product was finely crushed and its Tg was measured using a differential scanning calorimeter (DSC), the Tg was 165° C., indicating good heat resistance.
  • DSC differential scanning calorimeter
  • Example 3 [Synthesis of epoxy resin] 5 g of the paracoumaric acid dimer obtained in Synthesis Example 1, 56.4 g of epichlorohydrin (10 equivalents to the paracoumaric acid dimer), and 1 g of tetrabutylammonium bromide were reacted at 100° C. for 5 hours. After the reaction was completed, 2.5 ml of a 40% by mass aqueous sodium hydroxide solution was added dropwise to the solution while cooling it with ice, and then the reaction was allowed to proceed in ice-cold water for 1 hour.
  • Example 4 5.52 g of the epoxy resin obtained in Example 3 and 1.70 g of isophoronediamine were mixed. Thereafter, a cured product was produced by heating at 100°C for 1 hour, at 160°C for 1 hour, and then at 200°C for 1 hour. When the obtained cured product was finely crushed and the Tg was measured using a differential scanning calorimeter (DSC), no clear Tg could be shown. Therefore, measurement was performed using a dynamic viscoelasticity method (DMA), and the Tg could be read as 251° C. from the peak top temperature of tan ⁇ . It showed good heat resistance.
  • DMA dynamic viscoelasticity method
  • Comparative example 1 A petroleum-derived bisphenol A epoxy resin (trade name "jER828", manufactured by Mitsubishi Chemical Corporation) was mixed with isophorone diamine as a curing agent so that the ratio of epoxy group to NH group was 1:1. Curing was performed under the same conditions to produce a cured product. The obtained cured product was cut into pieces and the Tg was measured using a differential scanning calorimeter (DSC), and the result was that the Tg was 152°C.
  • DSC differential scanning calorimeter

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Compounds (AREA)

Abstract

La présente invention concerne une résine époxy qui a un squelette représenté par la formule (1). Dans la formule (1), chacun de R4 et R5 représente indépendamment un atome d'hydrogène, un groupe alcoxy ou -OG ; * peut être un site de liaison destiné à être lié à une autre structure ; n représente un nombre entier de 0 à 100 ; et G représente un groupe glycidyle.
PCT/JP2023/012033 2022-03-24 2023-03-24 Résine époxy, corps durci de celle-ci et procédé de production de résine époxy WO2023182522A1 (fr)

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JP2013113937A (ja) * 2011-11-25 2013-06-10 Jsr Corp 液晶配向剤、液晶配向膜、液晶配向膜の形成方法及び液晶表示素子
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US9878039B1 (en) * 2016-09-01 2018-01-30 International Business Machines Corporation Microcapsule having a microcapsule shell material that is rupturable via a retro-dimerization reaction
WO2018119157A1 (fr) * 2016-12-20 2018-06-28 Arizona Board Of Regents On Behalf Of Arizona State University Polymères greffés par mécanophore pour former un réseau thermodurci sensible à la contrainte
WO2019026795A1 (fr) * 2017-07-29 2019-02-07 国立大学法人北陸先端科学技術大学院大学 Polyamide ou polyimide hydrophile
US20200055807A1 (en) * 2017-05-08 2020-02-20 Asymchem Laboratories (Tianjin) Co., Ltd Method for alcoholysis of amide
JP2021028371A (ja) * 2019-08-09 2021-02-25 積水化学工業株式会社 重合物、及びエポキシ樹脂
CN114326306A (zh) * 2022-01-06 2022-04-12 武汉柔显科技股份有限公司 感光树脂组合物、感光树脂组合物薄膜以及图案化的固化物
CN114874412A (zh) * 2022-06-14 2022-08-09 中国科学院宁波材料技术与工程研究所 深紫外光促降解环氧材料、复合涂层及其制备方法与应用

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013073519A1 (fr) * 2011-11-17 2013-05-23 国立大学法人北陸先端科学技術大学院大学 Matériau polymère brut et matériau polymère
JP2013113937A (ja) * 2011-11-25 2013-06-10 Jsr Corp 液晶配向剤、液晶配向膜、液晶配向膜の形成方法及び液晶表示素子
US9878039B1 (en) * 2016-09-01 2018-01-30 International Business Machines Corporation Microcapsule having a microcapsule shell material that is rupturable via a retro-dimerization reaction
WO2018119157A1 (fr) * 2016-12-20 2018-06-28 Arizona Board Of Regents On Behalf Of Arizona State University Polymères greffés par mécanophore pour former un réseau thermodurci sensible à la contrainte
CN107417594A (zh) * 2017-05-08 2017-12-01 凯莱英医药集团（天津）股份有限公司 一种酰胺醇解的方法
US20200055807A1 (en) * 2017-05-08 2020-02-20 Asymchem Laboratories (Tianjin) Co., Ltd Method for alcoholysis of amide
WO2019026795A1 (fr) * 2017-07-29 2019-02-07 国立大学法人北陸先端科学技術大学院大学 Polyamide ou polyimide hydrophile
JP2021028371A (ja) * 2019-08-09 2021-02-25 積水化学工業株式会社 重合物、及びエポキシ樹脂
CN114326306A (zh) * 2022-01-06 2022-04-12 武汉柔显科技股份有限公司 感光树脂组合物、感光树脂组合物薄膜以及图案化的固化物
CN114874412A (zh) * 2022-06-14 2022-08-09 中国科学院宁波材料技术与工程研究所 深紫外光促降解环氧材料、复合涂层及其制备方法与应用

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