WO2022201985A1 - 変性エポキシ樹脂、その製造方法、硬化性樹脂組成物、その硬化物、塗料及び接着剤 - Google Patents

変性エポキシ樹脂、その製造方法、硬化性樹脂組成物、その硬化物、塗料及び接着剤 Download PDF

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WO2022201985A1
WO2022201985A1 PCT/JP2022/006176 JP2022006176W WO2022201985A1 WO 2022201985 A1 WO2022201985 A1 WO 2022201985A1 JP 2022006176 W JP2022006176 W JP 2022006176W WO 2022201985 A1 WO2022201985 A1 WO 2022201985A1
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Prior art keywords
epoxy resin
acid
formula
modified epoxy
group
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PCT/JP2022/006176
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English (en)
French (fr)
Japanese (ja)
Inventor
大樹 杉山
隼人 小笠原
航 深山
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三菱ケミカル株式会社
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Priority to JP2023508781A priority Critical patent/JPWO2022201985A1/ja
Publication of WO2022201985A1 publication Critical patent/WO2022201985A1/ja

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    • 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
    • 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

Definitions

  • the present invention relates to a modified epoxy resin, a curable resin composition containing the same, a cured product, and a paint or adhesive containing the cured product.
  • Epoxy resins are used in many applications, mainly in the fields of paints, civil engineering, and electricity, due to their excellent electrical properties, adhesiveness, heat resistance, and the like. Epoxy resins used in these applications are generally used as adhesives or paints by curing with a curing agent. In recent years, in applications such as paints, electrical and electronic materials, adhesives, CFRP, etc., various advanced functions are progressing, and the cured products containing conventionally used epoxy resins are hard and brittle. It is becoming difficult to meet the performance required in applications. In order to improve this hard and brittle property, conventionally, flexible epoxy resins have been studied.
  • a modified epoxy resin obtained by reacting an acid-terminated polyester with a bifunctional epoxy resin is known. and then reacting the adduct with an acid-terminated polyester having a ring to obtain a flexible modified epoxy resin.
  • a modified epoxy equivalent having an epoxy equivalent in the range of 450 to 800 g/equivalent is obtained by reacting an acid-terminated polyester obtained from an aliphatic divalent carboxylic acid and an aliphatic dihydric alcohol with a bifunctional epoxy resin.
  • Epoxy resins are disclosed, and in Patent Document 3, a block copolymer composed of 5 to 95% by weight of a polyester having carboxyl groups at both ends and 5 to 95% by weight of an epoxy resin is mainly used as a raw material for a heat laminating adhesive for cans.
  • a modified epoxy resin is described as a component, and a modified epoxy resin obtained by reacting an acid-terminated polyester obtained from an aliphatic dicarboxylic acid and an aliphatic dihydric alcohol with a bifunctional aromatic epoxy resin is disclosed.
  • the modified epoxy resin described in Patent Document 1 cannot sufficiently control the purity of the acid terminal when producing the raw material acid-terminated polyester because it uses a diol component with a high boiling point.
  • the flexibility of the modified epoxy resin obtained was insufficient.
  • Patent Document 2 since a low-molecular-weight acid-terminated polyester is used, the ratio of the skeleton derived from the bifunctional epoxy resin component contained in the modified epoxy resin is increased, resulting in insufficient flexibility.
  • the high-molecular-weight resin described in Patent Document 3 has a high skeleton ratio derived from a bifunctional epoxy resin contained in the high-molecular-weight resin, and has insufficient flexibility.
  • the present invention provides a modified epoxy resin that has excellent flexibility and adhesiveness, has good reactivity with a curing agent, and can exhibit properties even when blended with other epoxy resins, including this modified epoxy resin.
  • An object of the present invention is to provide a curable resin composition and a cured product.
  • n is the average number of repetitions and is a positive number of 1 to 10.
  • X is a divalent group represented by the following formula (2)
  • Y is the following formula (3 ) is a divalent group represented by (In formula (2) above, R 1 is a hydrocarbon group having 2 to 40 carbon atoms and may have a heteroatom. p is a repeating number and is an integer of 0 to 10.)
  • R 2 is a hydrocarbon group having 2 to 40 carbon atoms, may have a heteroatom, and the proportion of the aliphatic hydrocarbon group in all of R 2 is 50 mol% or more.
  • R 3 is a hydrocarbon group having 2 to 30 carbon atoms and may have a heteroatom, q is a repeating number and is an integer of 1 to 50.)
  • [2] The modified epoxy resin according to [1], wherein the proportion of aliphatic hydrocarbon groups having 3 or less carbon atoms in the entirety of R 3 in formula (3) is 50 mol % or more.
  • [3] The modified epoxy resin according to [1] or [2], wherein R 1 contains a divalent group represented by the following formula (4) and/or the following formula (5).
  • R 4 is a single bond, or -CH 2 -, -C(CH 3 ) 2 -, -CH(CH 3 )-, -S-, -SO 2 -, -O- , and —CO—
  • R 5 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group; may be different.
  • R 6 is selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms, each of which may be the same or different, and part of R 6 is , may form a ring condensed to this benzene ring.
  • [4] The modified epoxy resin according to any one of [1] to [3], wherein R 1 is a divalent group represented by the following formula (6).
  • R 7 in the above formula (6) is a hydrocarbon group having 1 to 10 carbon atoms. r is the number of repetitions and is an integer of 0 to 20.
  • Mw/Mn molecular weight distribution
  • a curable resin composition comprising the modified epoxy resin according to any one of [1] to [5] and a curing agent.
  • a paint comprising the cured product of [8].
  • An adhesive comprising the cured product of [8].
  • a modified epoxy resin that is excellent in flexibility and adhesiveness, has good reactivity with a curing agent, and can exhibit properties even when blended with other epoxy resins, and the modified epoxy resin.
  • a curable resin composition and a cured product thereof can be provided.
  • the modified epoxy resin, curable resin composition and cured product of the present invention can be applied and developed in fields such as electric/electronic materials, FRP (fiber reinforced resin), adhesives and paints.
  • 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 term “bifunctional” and “divalent” of the compound means that it is substantially bifunctional, and trifunctional if it does not induce gelation during production of the modified epoxy resin, i.e., 5% by weight or less. It may contain the above compounds.
  • a modified epoxy resin (hereinafter sometimes simply referred to as a modified epoxy resin), which is one embodiment of the present invention, is represented by the formula (1), wherein a structural unit (X) derived from an epoxy resin and a structure derived from an acid-terminated polyester are A modified epoxy resin containing a unit (Y), having a weight average molecular weight of 3000 to 50000 and an epoxy equivalent of 500 to 10000 g / eq, and a structural unit derived from the acid-terminated polyester in formula (1) The proportion of (Y) is 50 to 90% by weight.
  • n is the average number of repetitions and is a positive number of 1-10.
  • X is a divalent group represented by the following formula (2)
  • Y is a divalent group represented by the following formula (3).
  • R 1 is a hydrocarbon group having 2 to 40 carbon atoms, preferably 2 to 38 carbon atoms, more preferably 2 to 35 carbon atoms, and may have a heteroatom.
  • the hydrocarbon group includes a hydrocarbon group containing an alicyclic skeleton, an aromatic hydrocarbon group, and a chain hydrocarbon group.
  • Hydrocarbon groups containing an alicyclic skeleton include cycloalkylene groups, alkylenebiscycloalkylene groups, alkyl-substituted cycloalkylene groups, alkylenebis(alkyl-substituted cycloalkylene) groups, and the like.
  • the aromatic hydrocarbon group may be any hydrocarbon group containing an aromatic ring, such as an alkylenebisphenylene group, a phenylene group, a bisphenylene group, an oxybisphenylene group, a sulfonylbisphenylene group, a carbonylbisphenylene group, and Alkyl-substituted groups and the like can be mentioned.
  • chain hydrocarbon group examples include an alkylene group and an alkylene group containing an oxygen atom. Among them, aromatic hydrocarbon groups and chain hydrocarbon groups are more preferable.
  • p is the number of repetitions and is an integer from 0 to 10;
  • R 2 is a hydrocarbon group having 2 to 40 carbon atoms, may have a heteroatom, and the proportion of aliphatic hydrocarbon groups in all of R 2 is 50 mol% or more.
  • R 3 is a hydrocarbon group having 2 to 30 carbon atoms and may have a heteroatom.
  • q is the number of repetitions and is an integer of 1-50.
  • the hydrocarbon group for R 2 is not particularly limited, but includes, for example, linear or branched aliphatic hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups, aromatic hydrocarbon groups, Straight-chain aliphatic hydrocarbon groups are preferred.
  • the number of carbon atoms in the hydrocarbon group for R 2 is preferably 3-35, more preferably 3-25, even more preferably 5-20, and particularly preferably 6-15.
  • the proportion of the aliphatic hydrocarbon groups present in all R 2 is 50 mol % or more, preferably 60 mol % or more, and more preferably 80 mol % or more. As this value increases, the flexibility tends to improve when the modified epoxy resin of the present invention is cured together with the cured product.
  • the hydrocarbon group for R 3 is not particularly limited, but includes, for example, a linear or branched aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an aromatic hydrocarbon group, Straight-chain aliphatic hydrocarbon groups are preferred.
  • the proportion of aliphatic hydrocarbon groups having 3 or less carbon atoms in all of R 3 is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 80 mol% or more, and particularly preferably 95 mol% or more. As this value increases, the flexibility tends to improve when the modified epoxy resin of the present invention is cured together with the cured product.
  • the modified epoxy resin of this embodiment has excellent adhesiveness, flexibility, and good reactivity with the curing agent. This effect is due to the presence of an ester bond in the molecule, the adjustment of the ratio of the structural unit Y in the modified epoxy resin to a specific amount, and the structural unit (X) and the structural unit ( It is expressed by adjusting Y) to a specific structure.
  • the epoxy equivalent of the modified epoxy resin is 500 to 10000 g/eq, preferably 800 g/eq or more, more preferably 1000 g/eq or more, still more preferably 1300 g/eq or more, and particularly preferably 1400 g/eq or more.
  • the larger the epoxy equivalent the better the flexibility, but if the epoxy equivalent is less than 500 g/eq, the distance between the cross-linking points of the cured product becomes short, and the three-dimensional network structure becomes excessively dense. It is not preferable because there is a possibility that it will become hard and brittle.
  • it is preferably 6000 g/eq or less, more preferably 5000 g/eq or less, and even more preferably 4000 g/eq or less.
  • the smaller the epoxy equivalent the better the adhesiveness, but if it exceeds 10,000 g/eq, the distance between the cross-linking points becomes long and a dense three-dimensional network structure cannot be formed, which may reduce the adhesive strength. I don't like it.
  • the weight average molecular weight (Mw) of the modified epoxy resin is 3000 to 50000, preferably 4000 or more, more preferably 5500 or more, and even more preferably 7000 or more. On the other hand, it is more preferably 40,000 or less, more preferably 25,000 or less, and particularly preferably 20,000 or less. If the weight-average molecular weight exceeds 50,000, the distance between cross-linking points becomes long and a dense three-dimensional network structure cannot be formed, which tends to reduce the adhesive strength, which is not preferable.
  • the upper limit is preferably 20.0 or less, more preferably 15.0 or less, even more preferably 10.0 or less.
  • 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 below.
  • the modified epoxy resin exhibits excellent effects when the proportion of the acid-terminated polyester-derived structural unit (Y) in the above formula (1) is within a specific range.
  • the ratio of structural units (Y) in the modified epoxy resin is represented by the following formula.
  • Proportion (% by weight) of structural unit (Y) (weight of structural unit (Y)) x 100)/weight of modified epoxy resin
  • the proportion of the structural unit (Y) is 50 to 90% by weight, preferably 88% by weight or less, more preferably 85% by weight or less, and even more preferably 83% by weight or less. If the ratio of the structural unit (Y) exceeds 90% by weight, the ratio of the epoxy compound (A) to the acid-terminated polyester (B) is small when producing the modified epoxy resin, so there is a risk that the reaction will not proceed uniformly. There is On the other hand, the proportion of the structural unit (Y) is preferably 55% by weight, more preferably 60% by weight, and even more preferably 70% by weight or more.
  • the ratio of the structural unit (Y) is less than 50% by weight, the properties derived from the flexible polyester skeleton exhibited by the modified epoxy resin are impaired, and the properties of the epoxy compound (A) tend to be greatly reflected. Elongation tends to deteriorate.
  • the modified epoxy resin has the structure of formula (1) above, where n is the average number of repetitions and is a positive number of 1 to 10, preferably a positive number of 1 to 8, more preferably It is a positive number from 1 to 5.
  • X is a structural unit derived from a bifunctional epoxy compound, specifically a divalent group represented by formula (2).
  • R 1 is a hydrocarbon group having 2 to 40 carbon atoms and may have a heteroatom.
  • p is the number of repetitions and is an integer of 0 to 10, preferably 1 to 8, more preferably 1 to 5.
  • R 1 preferably contains a divalent group represented by the following formula (4) and/or the following formula (5).
  • R 4 is a single bond, or —CH 2 —, —C(CH 3 ) 2 —, —CH(CH 3 )—, —S—, —SO 2 —, —O—, and It is a divalent group selected from the group consisting of groups represented by -CO-.
  • R 5 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, each of which may be the same or different.
  • R 6 is selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms, each of which may be the same or different, and part of R 6 is bonded to each other to A ring condensed to the benzene ring may be formed.
  • R 1 includes formula (4) and/or formula (5)
  • the total content of R 1 is preferably 50% by weight or more, more preferably 65% by weight or more, still more preferably 75% by weight or more, and particularly preferably is 85% by weight or more.
  • R 1 is also preferably a divalent group represented by formula (6).
  • R 7 is a hydrocarbon group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms.
  • the hydrocarbon group is preferably an alkylene group, a cycloalkylene group or an aromatic hydrocarbon group, more preferably an alkylene group.
  • the alkylene group is preferably an ethylene group, a propylene group, a trimethylene group, a butanediyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group or an octanediyl group, more preferably an ethylene group, a propylene group, a butanediyl group, a pentanediyl group or a hexanediyl group.
  • An ethylene group and a propylene group are particularly preferred.
  • r is a repetition number and is an integer from 0 to 20;
  • the modified epoxy resin can also be produced by reacting the epoxy compound (A) represented by formula (7) with the acid-terminated polyester (B) represented by formula (8).
  • R 1 and p have the same meanings as in formula (2) above.
  • R 2 , R 3 and q have the same meanings as in formula (3) above.
  • Epoxy compound (A) The epoxy compound (A) represented by formula (7) is a compound having two epoxy groups in the molecule.
  • Examples of bifunctional epoxy compounds having two epoxy groups include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, bisphenol Z diglycidyl ether, bisphenol S diglycidyl ether, and bisphenol AD diglycidyl ether.
  • the epoxy compound (A) is not particularly limited, but from the viewpoint of being able to control adhesion, bisphenol-based diglycidyl ethers, benzenediol-based diglycidyl ethers, biphenol-based diglycidyl ethers, polyalkylene polyol-based diglycidyl ethers, Alkylene glycol diglycidyl ethers are preferably used, and polyalkylene polyol-based diglycidyl ethers and alkylene glycol diglycidyl ethers are particularly preferably used.
  • the epoxy equivalent of the epoxy compound (A) is not particularly limited, it is preferably 100 g/eq to 1200 g/eq. From the viewpoints of handling, improvement of flexibility and adhesiveness, it is more preferably 110 g/eq to 1000 g/eq, still more preferably 120 g/eq to 800 g/eq.
  • the properties of the epoxy compound (A) are not particularly limited, and may be solid, liquid, or semi-solid, preferably liquid or semi-solid.
  • the epoxy compounds (A) listed above can be used alone or in combination of multiple types.
  • a preferred combination is a combination selected from bisphenol-based diglycidyl ethers, benzenediol-based diglycidyl ethers, biphenol-based diglycidyl ethers, polyalkylenepolyol-based diglycidyl ethers, and alkylene glycol diglycidyl ethers.
  • the acid-terminated polyester (B) represented by formula (8) is a carboxylic acid-terminated polyester resin produced by polycondensation of a dihydric carboxylic acid and a dihydric alcohol.
  • R 2 in the above formula (3) corresponds to a repeating structural unit derived from a divalent carboxylic acid described later in the acid-terminated polyester (B)
  • R 3 is 2 in the acid-terminated polyester (B). It corresponds to a repeating unit derived from a functional alcohol, and in the above formula (3), R 2 and R 3 may also be referred to as compound units for compounds from which the respective repeating units are derived.
  • the divalent carboxylic acid is not particularly limited, it includes the following. Isomers of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid (specifically 1,4-, 1,5-, 1,6-, 1,7-, 2,5-, 2,6-, 2,7 -, 2,8-), succinic acid, sebacic acid, isodecylsuccinic acid, dodecenylsuccinic acid, maleic acid, adipic acid, furandicarboxylic 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-ethyl-3-methylglutaric acid, 3,3-t
  • the divalent carboxylic acid it is preferable to use an aliphatic divalent carboxylic acid from the viewpoint of increasing flexibility.
  • the amount of the aliphatic dicarboxylic acid used is preferably 50 mol% or more, more preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and 90 mol% or more of the total divalent carboxylic acid component. It is particularly preferred for this reason.
  • the dihydric alcohol is not particularly limited, but includes the following. Ethylene glycol, polyethylene glycol, 1,2-propylene glycol, 1,3-propanediol, polypropylene glycol, 1,4-butanediol, polytetramethylene glycol, 1,5-pentanediol, polypentamethylene glycol, neopentyl glycol , 1,6-hexanediol, polyhexamethylene glycol, 1,7-heptanediol, polyheptamethylene glycol, 1,8-octanediol, 1,10-decanediol, 2,2-dimethyl-1,3-propane Diols consisting only of a chain structure such as diols, diols having a cyclic structure such as 1,4-cyclohexanedimethanol and isosorbide, bisphenols such as bisphenol A ethylene oxide adducts, bisphenol A propylene oxide
  • the dihydric alcohol it is preferable to use a dihydric alcohol having 3 or less carbon atoms, and it is more preferable to use ethylene glycol and 1,2-propylene glycol. Both ethylene glycol and 1,2-propylene glycol have a boiling point of 200° C. or less, and can be reacted while sufficiently distilling off unnecessary dihydric alcohol components during the reaction under reduced pressure in the production process of acid-terminated polyester.
  • the acid terminal purity of the polyester can be increased.
  • the acid terminal purity of the acid-terminated polyester is low, that is, when it is hydroxyl-terminated, it cannot participate in the copolymerization reaction with the epoxy resin, and the terminal epoxy group purity of the resulting modified epoxy resin is lowered. As a result, the three-dimensional network structure as designed cannot be constructed during curing, and flexibility and adhesiveness tend to decrease.
  • the amount of the dihydric alcohol having 3 or less carbon atoms used is preferably 50 mol% or more, more preferably 55 mol% or more, more preferably 60 mol% or more, more preferably 70 mol% or more, and further preferably 80 mol% or more of the total dihydric alcohol component.
  • 90 mol % or more is particularly preferable for the reason described above.
  • 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 divalent Remove the alcohol component. After that, the polycondensation reaction is continued. 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. I do.
  • Catalysts used for esterification reaction, transesterification reaction and polycondensation reaction include titanium-based catalysts, calcium acetate, calcium acetate hydrate, dibutyltin oxide, tin acetate, tin disulfide, tin oxide, 2-ethylhexanetin and the like.
  • titanium-based catalysts are preferred because of their good reactivity.
  • titanium-based catalysts examples 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 include, for example, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetrapentoxytitanium, tetraoctoxytitanium and the like.
  • titanium carboxylate compounds include titanium formate, titanium acetate, titanium propionate, titanium octanoate, titanium oxalate, titanium succinate, titanium maleate, titanium adipate, titanium sebacate, titanium hexanetricarboxylate, and isooctanetricarboxylic acid.
  • titanium-based catalysts tetrabutoxy titanium is preferred. Titanium-based catalysts may be used alone or in combination of two or more.
  • the reaction temperature for the esterification reaction, transesterification reaction, or 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 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. If the amount of the catalyst used is less than 10 ppm or more than 10000 ppm, the time adjustment for polycondensation cannot cope with this, resulting in a decrease in 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 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), and polystyrene equivalent values are used. A specific measuring method is as described in the section of Examples below.
  • the properties of the acid-terminated polyester (B) at room temperature are not particularly limited, such as a vitreous solid, a crystalline solid, or a liquid, but a crystalline solid or liquid is preferable from the viewpoint of lowering the viscosity of the modified epoxy resin and increasing miscibility.
  • the hydroxyl value of the acid-terminated polyester (B) is not particularly limited. It is particularly preferable 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 30 mgKOH/g or less. is particularly preferable from the viewpoint of improving adhesiveness and flexibility.
  • 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, and particularly preferably 30 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. By adjusting the content within the above range, the purity of the terminal epoxy group of the modified epoxy resin can be improved, and the adhesiveness and flexibility can be improved.
  • the acid-terminated polyester (B) may be used singly or in combination with a plurality of divalent carboxylic acids or dihydric alcohols having different types and physical properties.
  • the acid-terminated polyester (B) contains an aliphatic skeleton, this structural unit contained in the modified epoxy resin behaves as a soft segment. Therefore, by using an epoxy compound (A) having an aromatic skeleton that behaves as a hard segment, it is possible to control the physical properties of the modified epoxy resin as a whole. On the other hand, it is possible to further improve the flexibility of the modified epoxy resin by using the epoxy compound (A) having a polyalkylene polyol-based or alkylene glycol-based skeleton that behaves as a soft segment. By appropriately blending such a modified epoxy resin with other epoxy compounds, it is possible to exhibit excellent cured physical properties.
  • [Modified epoxy resin] [Batch ratio] The charge ratio of the epoxy compound (A) and the acid-terminated polyester (B) at the time of manufacturing the modified epoxy resin is calculated from the theoretical epoxy equivalent of the modified epoxy resin to be obtained, and the lower limit of the theoretical epoxy equivalent is It should be 500 g/eq or more, preferably 800 g/eq or more, more preferably 1000 g/eq or more, more preferably 1300 g/eq or more, still more preferably 1400 g/eq or more. The reason why it is preferable is as described in the section on the modified epoxy resin.
  • the upper limit of the theoretical epoxy equivalent must be 5000 g/eq or less, preferably 4500 g/eq or less, more preferably 4000 g/eq or less.
  • the reason why it is preferable is as described in the section on the modified epoxy resin.
  • the modified epoxy resin is produced by reacting the epoxy compound (A) represented by the formula (7) and the acid-terminated polyester (B) represented by the formula (8) in the presence of a catalyst at a suitable feed ratio. can get.
  • a catalyst (E) may be used in the reaction step for producing the modified epoxy resin.
  • the catalyst (E) 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 (E) 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 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-o
  • 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, benzyltributylammonium chloride, phenyltrimethylammonium chloride, etc. be done.
  • 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.
  • the catalysts (E) listed above may be used alone or in combination of two or more.
  • a tertiary amine having a boiling point higher than the reaction temperature it is preferable to use a tertiary amine having a boiling point higher than the reaction temperature, in order to allow the polymerization reaction to proceed smoothly.
  • 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.
  • the amount of the catalyst used exceeds 10000 ppm by weight, the catalyst remaining in the modified epoxy resin induces anionic polymerization of epoxy groups, resulting in a marked decrease in storage stability.
  • reaction solvent (F) A reaction solvent (F) may be used in the reaction step for producing the modified epoxy resin.
  • 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-methylpyrrolidone 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, and diethylene glycol.
  • reaction solvents (F) listed above may be used alone or in combination of two or more.
  • the reaction solvent (F) can be further added to continue the reaction.
  • 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 generally 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 highly pure 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.
  • reaction time is equal to or less than the above upper limit, it is preferable from the viewpoint of improving production efficiency, and when it is equal to or more than the above lower limit, it is preferable from the point of being able to reduce unreacted components.
  • the modified epoxy resin may be mixed with a diluent solvent (G) after completion of the reaction to adjust the solid content concentration.
  • a diluent solvent G
  • any solvent can be used as long as it dissolves the epoxy resin, but it is usually an organic solvent.
  • the organic solvent the same ones as those mentioned above as the reaction solvent (F) can be used.
  • solvent and “solvent” are used to refer to those used during the reaction as “solvent” and those used after completion of the reaction as “solvent”. Different species may be used.
  • a curable resin composition which is one embodiment of the present invention, contains at least the above-described modified epoxy resin and a curing agent.
  • a curing agent e.g., ethylene glycol dimethacrylate copolymer, ethylene glycol dimethacrylate copolymer, ethylene glycol dimethacrylate copolymer, ethylene glycol dimethacrylate copolymer, ethylene glycol dimethacrylate copolymer, terethacrylate, terethacrylate, terethacrylate, terethacrylate, acrylate, acrylate, acrylate, acrylate, tere-diol dimethacrylate, acrylate, acrylate, terpolymer graft copolymer, graft copolymer, graft copolymer, graft copolymer, graft copolymer, graft copolymer, graft copolymer, graft copolymer, graft cop
  • a curing agent is a substance that contributes to cross-linking and/or chain extension reactions between epoxy groups of an epoxy resin.
  • a substance is usually called a "curing accelerator"
  • it is regarded as a curing agent if it is a substance that contributes to the cross-linking reaction and/or chain extension reaction between the epoxy groups of the epoxy resin. do.
  • the content of the curing agent in the curable resin composition is preferably 0.1 to 1000 parts by weight, more preferably 100 parts by weight or less, and still more preferably 80 parts by weight with respect to 100 parts by weight of the modified epoxy resin. or less, particularly preferably 60 parts by weight or less.
  • the content of the curing agent is preferably 0.1 to 1000 parts by weight with respect to 100 parts by weight of the total epoxy component as a solid content, It is more preferably 100 parts by weight or less, still more preferably 80 parts by weight or less, and particularly preferably 60 parts by weight or less.
  • a more preferred amount of curing agent is as described below, depending on the type of curing agent.
  • solid content means components excluding 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 and other epoxy compounds described later.
  • Curing agents include polyfunctional phenols, polyisocyanate compounds, amine compounds, acid anhydride compounds and acid-terminated polyester resins, imidazole compounds, amide compounds, cationic polymerization initiators, and organic phosphines. It is preferable to use at least one of
  • polyfunctional phenols include bisphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol AD, bisphenol Z, tetrabromobisphenol A, 4,4'-biphenol, 3,3',5, Biphenols such as 5'-tetramethyl-4,4'-biphenol; catechol, resorcinol, hydroquinone, dihydroxynaphthalenes; and hydrogen atoms bonded to aromatic rings of these compounds are halogen groups, alkyl groups, aryl groups, ethers and those substituted with non-interfering substituents such as organic substituents containing heteroatoms such as group, ester group, sulfur, phosphorus, silicon and the like. Furthermore, these phenols, phenol, cresol, polycondensation products of monofunctional phenols such as alkylphenols and aldehydes, novolacs and resols, etc., can also be used.
  • polyisocyanate compounds include tolylene diisocyanate, methylcyclohexane diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dimer acid diisocyanate, trimethylhexamethylene diisocyanate, Examples include polyisocyanate compounds such as lysine triisocyanate.
  • a compound having at least two active hydrogen atoms such as an amino group, a hydroxyl group, a carboxyl group and water, or 3 to 5 amounts of the above polyisocyanate compound.
  • the body and the like can be mentioned.
  • amine compounds include aliphatic primary, secondary and tertiary amines, aromatic primary, secondary and tertiary amines, cyclic amines, guanidines, urea derivatives and the like.
  • Ethylenetetramine, diaminodiphenylmethane, diaminodiphenyl ether, metaxylenediamine, dicyandiamide, 1,8-diazabicyclo(5,4,0)-7-undecene, 1,5-diazabicyclo(4,3,0)-5-nonene, dimethyl Urea, guanyl urea and the like can be mentioned.
  • 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).
  • imidazole compounds include 1-isobutyl-2-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, benzimidazole and the like. be done. Although the imidazole compound also functions as a curing accelerator, which will be described later, it is classified as a curing agent in the present invention.
  • amide compounds include dicyandiamide and derivatives thereof, 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 and the like anionic components such as SbF 6 -, BF 4 -, AsF 6 -, PF 6 -, CF 3 SO 32 -, B(C 6 F 5 ) 4 - and iodine, sulfur, nitrogen, phosphorus, etc.
  • a compound consisting of an aromatic cation component containing atoms and the like can be mentioned.
  • Diaryliodonium salts and triarylsulfonium salts are particularly preferred.
  • organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine.
  • Phosphonium salts include tetraphenylphosphonium/tetraphenylborate, tetraphenylphosphonium/ethyltriphenylborate, tetra Examples include butylphosphonium/tetrabutylborate and the like, and tetraphenylboron salts include 2-ethyl-4-methylimidazole/tetraphenylborate and N-methylmorpholine/tetraphenylborate.
  • the functional groups in the curing agent for all epoxy groups in the curable resin composition (hydroxyl groups of the polyfunctional phenol , the amino group of the amine-based compound or the acid anhydride group of the acid anhydride-based compound) is preferably used so that the equivalent ratio is 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 in the range of 1:0.01 to 1:1.5 in terms of equivalent ratio. preferable.
  • 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 compound When an amide compound is used, it is preferably used in the range of 0.1 to 20% by weight with respect to the total amount of all epoxy components and the amide compound as solid content in the curable resin composition.
  • a cationic polymerization initiator 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.
  • organic phosphines When organic phosphines are used, they are preferably used in a range of 0.1 to 20% by weight based on the total amount of all epoxy components and organic phosphines as solid content in the curable resin composition.
  • curing agents for example, mercaptan compounds, organic acid dihydrazides, halogenated boron amine complexes, and the like can also be used as curing agents. These curing agents may be used alone or in combination of two or more.
  • Epoxy compounds other than the above modified epoxy resin can be used in the curable resin composition.
  • Other 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 Tetrabromobisphenol A type epoxy resin
  • glycidyl ether type epoxy resin such as other polyfunctional phenol type epoxy resin
  • epoxy resin obtained by hydrogenating the aromatic ring of the above aromatic epoxy resin glycidyl ester type epoxy resin
  • glycidyl amine type epoxy Epoxy compounds such as resins, linear aliphatic epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins can be mentioned.
  • the other epoxy compounds listed above may be used alone or in combination of two or more.
  • the proportion of the other epoxy compound in the total epoxy component as a solid content in the epoxy resin-containing composition is preferably 1 weight. % or more, more preferably 5 wt % or more, and preferably 99 wt % or less, more preferably 95 wt % 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, the effect of improving the flexibility of the modified epoxy resin can be obtained.
  • the curable resin composition may be mixed with and diluted with a solvent in order to appropriately adjust the viscosity of the epoxy resin-containing 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 mode of use, but the same type or different types may be used independently.
  • the solvent that the modified epoxy resin may contain, one or more of the organic solvents exemplified as the reaction solvent (F) used in the production of the modified epoxy resin can be used.
  • the curable resin composition 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, Examples include inorganic fillers and organic fillers.
  • the other components listed above can be used in appropriate combination depending on the desired physical properties of the epoxy resin-containing composition. The fact that the above compound is blended in the curable resin composition can be confirmed by SEC-MALS, elemental analysis, and functional group analysis after separation and purification of the epoxy resin composition.
  • a cured product can be obtained by curing the curable resin composition.
  • the term "curing" as used herein means intentionally curing the epoxy resin with heat and/or light, and the degree of curing may be controlled according to desired physical properties and applications.
  • the curing method for curing the curable resin composition to obtain a cured product varies depending on the ingredients and amounts in the curable resin composition and the shape of the compound, but is usually 50 to 200 ° C. for 5 seconds. Heating conditions of ⁇ 180 minutes can be mentioned. This heating should be carried out in two stages: 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. is preferable from the viewpoint of reducing poor curing.
  • the curing reaction of the curable resin composition may be allowed to proceed by heating or the like to such an extent that the shape can be maintained.
  • the curable resin composition contains a solvent, most of the solvent is removed by heating, depressurization, air drying, etc., but 5% by weight or less of the solvent may remain in the semi-cured product. .
  • the presence of the modified epoxy resin in the cured product can be confirmed by identifying the modified epoxy resin from the cured product by infrared spectroscopy of the cured product.
  • the present invention relates to a modified epoxy resin excellent in flexibility and adhesiveness, a curable resin composition containing this modified epoxy resin, and a cured product.
  • the above-mentioned modified epoxy, curable resin composition, and cured product are excellent in electrical properties, adhesiveness, flexibility, heat resistance, etc., and are mainly used in many applications in the fields of coatings, adhesives, civil engineering, and electrical fields. It can be used particularly preferably in the field of paints and adhesive applications.
  • Epoxy compound (A) The epoxy resins, acid-terminated polyesters, and evaluation methods used in the following examples and comparative examples are as follows.
  • A-1 to A-7 were used as the epoxy compound (A).
  • A-1 1,6-hexanediol diglycidyl ether (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 116 g/eq, liquid)
  • A-2 Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation jER (registered trademark) 828US, epoxy equivalent: 186 g / eq, liquid)
  • A-3 Bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation jER (registered trademark) 806H, epoxy equivalent: 169 g / eq, liquid)
  • A-4 Polyoxypropylene glycol diglycidyl ether (manufactured by Sanyo Chemical Co., Ltd.
  • A-5 Resorcinol-type epoxy resin (Denacol EX-201 manufactured by Nagase ChemteX Corporation, epoxy equivalent: 113 g/eq, liquid)
  • A-6 Ultra-flexible epoxy resin (YX7110 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 1000 g / eq, semi-solid)
  • A-7 Dimer acid type epoxy resin (manufactured by Mitsubishi Chemical Corporation jER (registered trademark) 871, epoxy equivalent: 415 g / eq, liquid)
  • Acid-terminated polyester (B)] B-1 to B-5 shown in Table 1 were used as the acid-terminated polyester (B). All of them are obtained by reacting dihydric carboxylic acids and dihydric alcohols shown in Table-1.
  • production methods, acid values, carboxylic acid equivalents, hydroxyl values, glass transition temperatures, acid terminal purities, weight average molecular weights and number average molecular weights of B-1 to B-5 are shown in order.
  • B-1 to B-5 Synthesis of B-1 to B-5 was carried out as follows. First, 1000 ppm of tetrabutoxytitanium with respect to the total weight of the dihydric carboxylic acid component and the dihydric alcohol component shown in Table 1 was put into a reaction vessel equipped with a distillation column. Next, while stirring, the temperature was started to rise, and the temperature in the reaction system was heated to 265°C, and this temperature was maintained. After the esterification reaction is completed and no more water is distilled out from the reaction system, the pressure in the reaction system is reduced while maintaining the temperature in the reaction system at 265° C. to distill off the dihydric alcohol component from the reaction system. Condensation reaction was carried out while letting out.
  • the viscosity of the reaction system increases with the reaction, and when the torque of the stirring blade reaches a predetermined torque, the stirring is stopped, the reaction system is returned to normal pressure, and pressurized with nitrogen to take out the reactant, and B-1 to B-5 was produced.
  • 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 in a side-armed Erlenmeyer flask (A (g)), 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 dissolve completely. did.
  • ⁇ Measurement of hydroxyl value> The hydroxyl value of the acid-terminated polyester (B) was measured by the following procedure.
  • Solution 1 About 5 g of acid-terminated polyester (B) was precisely weighed into a side-armed Erlenmeyer flask (A (g)), and 50 mL of THF was added to dissolve completely.
  • Solution 2 30 mL of dimethylaminopyridine THF solution prepared by dissolving 5 g of N,N-dimethylaminopyridine in 500 mL of THF was added to "Solution 1".
  • Tg glass transition temperature
  • Acid terminal purity number average molecular weight/carboxylic acid equivalent (g/eq)
  • Acid terminal purity number average molecular weight/carboxylic acid equivalent (g/eq)
  • the weight average molecular weight and number average molecular weight of the acid-terminated polyester (B) were measured by gel permeation chromatography (GPC).
  • the apparatus and measurement conditions used for GPC measurement are as follows.
  • 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 THF (1 mL/min, 40°C)
  • Sample 0.04% tetrahydrofuran solution (100 ⁇ injection)
  • Calibration curve standard polystyrene (manufactured by Tosoh)
  • 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 THF (0.5 mL/min, 40°C)
  • Sample 1% tetrahydrofuran solution (10 ⁇ L injection)
  • Calibration curve standard polystyrene (manufactured by Tosoh)
  • Glass transition temperature (Tg) The glass transition point (Tg) in the examples and comparative examples was measured using a differential scanning calorimeter "DSC7020" manufactured by SII Nanotechnology Co., Ltd. by heating from -50 to 200°C at a rate of 10°C/min. rice field. It was obtained as the temperature at the intersection of the base line on the low temperature side of the chart measured at a heating rate of 10°C/min and the tangent line of the endothermic curve in the vicinity of the glass transition temperature.
  • DSC7020 differential scanning calorimeter
  • miscibility Two items of miscibility and reactivity with the curing agent were evaluated for handleability. The miscibility was evaluated as follows to determine whether or not each component was easily mixed uniformly at the time of blending, and was used as an index. If the miscibility rating was C or lower, no further evaluation was performed. ⁇ Evaluation Criteria ⁇ A: Easy to mix. B1: The formulation is highly viscous and requires heating, but can be easily mixed. B2: The formulation is crystalline and requires warming, but is easily miscible. C: It is difficult to mix uniformly because the viscosity of the formulation is remarkably high.
  • the reactivity with the curing agent was obtained by preheating the composition at 80° C. for 1 hour and then heating it at 130° C. for 1.5 hours to cure the cured product.
  • the evaluation of reactivity with the curing agent was x, subsequent evaluation was not performed.
  • ⁇ Glass transition temperature (Tg)> A portion of the tensile test piece was used and measured in the same manner as in the section [Glass transition temperature (Tg) and melting point].
  • the extrapolated glass transition start temperature (Tig) is the intersection of a straight line extending the base line on the low temperature side to the high temperature side and a tangent line drawn at a point where the gradient of the stepwise change portion of the glass transition curve is maximized. was the temperature of 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.
  • ⁇ Tensile test> After preheating the formulation at 80° C. for 1 hour, it was cured by heating at 130° C. for 1.5 hours to prepare a cured plate having a thickness of 3 mm. This cured product was processed into a dumbbell shape to obtain a test piece. The tensile strain at break of the obtained test piece was measured according to JIS K7161 using a precision universal testing machine "INSTRON 5582 type" manufactured by Instron. The value of the tensile breaking strain was evaluated as follows and used as an index. ⁇ Evaluation Criteria ⁇ S: 80% or more. A: 40% or more and less than 80%. B: 7% or more and less than 40%. C: 5% or more and less than 7%. D: Less than 5%.
  • the coating liquid is applied to two substrates, the coated surfaces are bonded together and fixed, preheated at 80 ° C. for 1 hour, and then cured by heating at 130 ° C. for 1.5 hours to obtain a laminate. rice field.
  • the hardened material protruding from the side surface of the laminate was scraped off, and the gripping margins of the two steel plates were bent outward at a right angle by 90° to obtain a T-shaped test piece.
  • the peel adhesive strength of the obtained test piece was measured according to JIS K6854.
  • the value of the peel adhesive strength was evaluated as follows and used as an index. ⁇ Evaluation Criteria ⁇ S: 100 N/25 mm or more. A: 15 N/25 mm or more and less than 100 N/25 mm. B: 10 N/25 mm or more and less than 15 N/25 mm. C: less than 10 N/25 mm.
  • a modified epoxy resin containing a structural unit (X) derived from an epoxy resin and a structural unit (Y) derived from an acid-terminated polyester represented by formula (1) It has a weight average molecular weight of 3000 to 50000 and an epoxy equivalent of 500 to 10000 g / eq. It has excellent reactivity with curing agents, and can exhibit its properties even when blended with other epoxy resins.

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51131599A (en) * 1975-04-28 1976-11-16 Ciba Geigy Ag Process for preparing epoxide resin of crystalline crossslinked elastomer and epoxide resin prepared by same process
JPH1087789A (ja) * 1996-07-26 1998-04-07 Vianova Resins Gmbh 缶塗装及びコイル塗装のための弾性の自己架橋性バインダー、及びそれの製造方法及び使用法
JP2017008155A (ja) * 2015-06-18 2017-01-12 Dic株式会社 ポリエステル変性エポキシ樹脂及び接着剤

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51131599A (en) * 1975-04-28 1976-11-16 Ciba Geigy Ag Process for preparing epoxide resin of crystalline crossslinked elastomer and epoxide resin prepared by same process
JPH1087789A (ja) * 1996-07-26 1998-04-07 Vianova Resins Gmbh 缶塗装及びコイル塗装のための弾性の自己架橋性バインダー、及びそれの製造方法及び使用法
JP2017008155A (ja) * 2015-06-18 2017-01-12 Dic株式会社 ポリエステル変性エポキシ樹脂及び接着剤

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