WO2018181649A1 - 変性樹脂及びそれを含む硬化性樹脂組成物 - Google Patents

変性樹脂及びそれを含む硬化性樹脂組成物 Download PDF

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Publication number
WO2018181649A1
WO2018181649A1 PCT/JP2018/013093 JP2018013093W WO2018181649A1 WO 2018181649 A1 WO2018181649 A1 WO 2018181649A1 JP 2018013093 W JP2018013093 W JP 2018013093W WO 2018181649 A1 WO2018181649 A1 WO 2018181649A1
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group
formula
group represented
represented
modified
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PCT/JP2018/013093
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English (en)
French (fr)
Japanese (ja)
Inventor
大晃 臼井
健介 宮崎
白石　大輔
竜一 吉川
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協立化学産業株式会社
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Priority to KR1020197028437A priority Critical patent/KR102220144B1/ko
Priority to CN201880014530.8A priority patent/CN110366571B/zh
Publication of WO2018181649A1 publication Critical patent/WO2018181649A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • 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
    • 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
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells

Definitions

  • the present invention relates to a modified resin and a curable resin composition containing the same.
  • the dropping method is a method in which a panel can be formed by directly dropping and bonding liquid crystal into a closed loop of a sealing agent under vacuum and releasing the vacuum.
  • This dripping method has many merits such as a reduction in the amount of liquid crystal used and a time required for injecting the liquid crystal into the panel, and has become the mainstream method for manufacturing a liquid crystal panel using a large substrate.
  • a sealant is applied using, for example, a dispenser, liquid crystal is dropped and bonded, a gap is formed, alignment is performed, and the sealant is cured by energy ray curing and / or heat curing. It is done by.
  • Patent Document 1 proposes improving the alignment characteristics of liquid crystal by partially modifying a bifunctional phenol novolac type epoxy resin with a (meth) acrylic acid derivative as a raw material for a sealing agent.
  • Patent Document 2 discloses that, as a raw material for a sealing agent, a hydroxyl group of an ethylene glycol ring-opened product of an epoxy resin obtained by reacting a bifunctional bisphenol A type epoxy resin and ethylene glycol is glycidyloxylated. And a (meth) acrylate resin obtained by partially modifying the epoxy resin with a (meth) acrylic acid derivative.
  • An object of the present invention is to provide a modified resin and a curable resin composition containing the same that exhibit high adhesive strength when substrates are bonded to each other.
  • the present invention has the following configuration.
  • the molecule has one or more groups selected from the group consisting of a group represented by the following formula (1-1) and a group represented by the following formula (1-2), and Having one or more groups selected from the group consisting of a group represented by the formula (2-1), a group represented by the following formula (2-2), and a group represented by the following formula (2-3)
  • a modified resin, A curable resin composition comprising a thermosetting agent and / or a polymerization initiator.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom or a methyl group
  • R 21 is an alkyl group, an alkenyl group, an alkynyl group or an aryl group
  • R 22 and R 23 are each independently an alkyl group, alkenyl group, alkynyl group or aryl group, or R 22 and R 23 together form a ring structure
  • X 1 is an oxygen atom or a sulfur atom
  • R 24 is an alkyl group, an alkenyl group, an alkynyl group or an aryl group
  • R 21 , R 22 and R 23 are not a vinyl group or a 1-methylvinyl group.
  • a modified resin represented by the following formula (3) Ar 1 (—O—A 1 ) n1 (3)
  • Ar 1 is an n1 valent group having a total number of carbon atoms and heteroatoms of 5 or more, and including one or more aromatic rings or heteroaromatic rings, n1 is 1 or more
  • a 1 is independently a hydrogen atom, a group represented by the following formula (1-1), a group represented by the following formula (1-2), a group represented by the following formula (2-1), the following A group represented by the formula (2-2), a group represented by the following formula (2-3), a group represented by the formula (4-1), or a group represented by the formula (4-2)
  • a group represented by the formula (4-1) having a group represented by the formula (1-1) or a group represented by the formula (1-2)
  • a group represented by formula (4-2) having a group represented by formula and / or a group represented by formula (1-2); a group represented by formula (1-1); and formula (1-2)
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom or a methyl group
  • R 21 is an alkyl group, an alkenyl group, an alkynyl group or an aryl group
  • R 22 and R 23 are each independently an alkyl group, alkenyl group, alkynyl group or aryl group, or R 22 and R 23 together form a ring structure
  • X 1 is an oxygen atom or a sulfur atom
  • R 24 is an alkyl group, an alkenyl group, an alkynyl group or an aryl group
  • B 1 is independently an alkylene group
  • m 1 is 1 or more
  • D 1 is an arylene group, an alkylene-arylene-alkylene group, an alkylene-arylene group, an arylene-alkylene-arylene group or
  • an epoxy resin (excluding the modified resin of [1]), a modified epoxy resin in which a part or all of the epoxy group of the epoxy resin is modified with (meth) acrylic anhydride, an epoxy resin epoxy Including one or more resins selected from the group consisting of modified epoxy resins wherein all of the groups are modified with a modifying compound;
  • the modifying compound is selected from the group consisting of carboxylic acid (excluding (meth) acrylic acid), carboxylic anhydride (excluding (meth) acrylic anhydride), alcohol and thiol.
  • a step of reacting an epoxy resin, a modified compound as an essential component, and (meth) acrylic anhydride as an optional component, wherein the modified compound is a carboxylic acid provided that (meth) Production of a modified resin according to [2], which is one or more compounds selected from the group consisting of carboxylic acid anhydrides (excluding (meth) acrylic anhydrides), alcohols and thiols, excluding acrylic acid).
  • a modified resin and a curable resin composition containing the same which exhibit high adhesive strength when the substrates are bonded together.
  • the “glycidyl group” means a 2,3-epoxypropyl group.
  • the “methyl glycidyl group” means a 2,3-epoxy-2-methylpropyl group.
  • the “epoxy group” includes at least one of a glycidyl group and a methylglycidyl group.
  • (meth) acryloyl group means an acryloyl group (CH 2 ⁇ CH 2 —C ( ⁇ O) —) and a methacryloyl group (CH 2 ⁇ CH (CH 3 ) —C ( ⁇ O) —). At least one of the above.
  • “Optionally substituted” means “substituted or unsubstituted”.
  • a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
  • the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. .
  • an “alkyl group” is a monovalent group that is linear or branched.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 4 carbon atoms.
  • Alkyl groups are methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n- Examples include heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like.
  • alkylene group alone or in combination with other terms is a divalent group which is linear or branched.
  • the number of carbon atoms of the alkylene group is preferably 1-20, and particularly preferably 1-8.
  • the alkylene group includes a methylene group, an ethylene group, an ethylidene group (ethane-1,1-diyl group), a trimethylene group, a propylene group (propane-1,2-diyl group), and a propylidene group (propane-1,1-diyl group).
  • Isopropylidene group (propane-2,2-diyl group), tetramethylene group, butylidene group (butane-1,1-diyl group), isopropylidene group (2-methylpropane-1,1-diyl group), penta
  • examples include a methylene group, 2-methylpentane-1,5-diyl group, hexamethylene group, 2-ethylhexane-1,6-diyl group, heptamethylene group, octamethylene group and the like.
  • an “alkenyl group” is a monovalent group which is linear or branched.
  • the number of unsaturated bonds of the alkenyl group is preferably 1 to 5, and particularly preferably 1 or 2.
  • the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 3 to 20 carbon atoms, still more preferably 3 to 15 carbon atoms, and particularly preferably 3 to 10 carbon atoms.
  • the alkenyl group may have 2 to 20 carbon atoms, 2 to 15 carbon atoms, or 2 to 10 carbon atoms. Good.
  • Alkenyl groups are vinyl, 1-methylvinyl, 1-propenyl, 2-propenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 2-butenyl, and 3-butenyl.
  • an “alkynyl group” is a monovalent group that is linear or branched.
  • the number of carbon atoms in the alkynyl group is preferably 2-20, and particularly preferably 2-15.
  • Alkynyl group includes ethynyl group, propargyl group, 2-butynyl group, 3-butynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, Examples include 5-hexynyl group.
  • the alkyl group, alkylene group, alkenyl group and alkynyl group may be substituted with a substituent.
  • the substituent is not particularly limited, and examples thereof include a halogen atom and an amino group.
  • the “aryl group” alone or in combination with other terms is a monovalent group having a monocyclic or polycyclic aromatic ring.
  • the aryl group preferably has 6 to 20 carbon atoms.
  • Examples of the aryl group include a phenyl group, a biphenylyl group, a naphthyl group, a terphenylyl group, an anthracenyl group, a fluorenyl group, and the like, and a phenyl group is preferable.
  • the “arylene group” alone or in combination with other terms is a divalent group having a monocyclic or polycyclic aromatic ring.
  • the number of carbon atoms in the arylene group is preferably 6-20.
  • Examples of the arylene group include a phenylene group, a naphthylene group, an anthranylene group, and a phenanthranylene group, and a phenylene group and a naphthylene group are preferable.
  • the aryl group and arylene group may be substituted with a substituent.
  • the substituent is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkyl mercapto group, a cycloalkyl group, and a halogen atom.
  • the alkyl group preferably has 1 to 4 carbon atoms.
  • the alkyl moiety in the alkoxy group is preferably an alkyl group having 1 to 4 carbon atoms.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, and a tert-butoxy group.
  • the alkyl moiety in the alkylcarbonyl group and the alkylmercapto group is preferably an alkyl group having 1 to 4 carbon atoms.
  • Examples of the alkylcarbonyl group include an acetyl group, a propanoyl group, a 2-methylpropanoyl group, and a butanoyl group.
  • alkyl mercapto group examples include methyl mercapto group, ethyl mercapto group, propyl mercapto group, i-propyl mercapto group, butyl mercapto group, i-butyl mercapto group, sec-butyl mercapto group, tert-butyl mercapto group and the like.
  • the cycloalkyl group is a monocyclic or polycyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, and includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, A cyclododecyl group, an adamantyl group, etc. are mentioned.
  • the curable resin composition has one or more groups selected from the group consisting of a group represented by the following formula (1-1) and a group represented by the following formula (1-2) in the molecule. And one or more selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), and a group represented by the following formula (2-3) A modified resin having a group of: a thermosetting agent and / or a polymerization initiator.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom or a methyl group
  • R 21 is an alkyl group, an alkenyl group, an alkynyl group or an aryl group
  • R 22 and R 23 are each independently an alkyl group, alkenyl group, alkynyl group or aryl group, or R 22 and R 23 together form a ring structure
  • X 1 is an oxygen atom or a sulfur atom
  • R 24 is an alkyl group, an alkenyl group, an alkynyl group or an aryl group
  • R 21 , R 22 and R 23 are not a vinyl group or a 1-methylvinyl group.
  • the modified resin has one or more groups selected from the group consisting of a group represented by the formula (1-1) and a group represented by the formula (1-2) in the molecule, and the formula ( 2-1), one or more groups selected from the group consisting of a group represented by formula (2-2) and a group represented by formula (2-3) (hereinafter referred to as “ Also referred to as “first modified resin”).
  • the first modified resin has one or more groups selected from the group consisting of the group represented by the formula (1-1) and the group represented by the formula (1-2), the epoxy resin and / or It has properties as a (meth) acrylic anhydride modified resin of epoxy resin.
  • the first modified resin includes a group represented by the formula (2-1), By having one or more groups selected from the group consisting of the group represented by the formula (2-2) and the group represented by the formula (2-3), in addition to the properties of the epoxy resin and the like described above, One or more selected from the group consisting of modified compounds (that is, carboxylic acid (excluding (meth) acrylic acid), carboxylic acid anhydride (excluding (meth) acrylic anhydride), alcohol and thiol. It may also have additional properties imparted by
  • a group represented by formula (1-1), a group represented by formula (1-2), a group represented by formula (2-1), a group represented by formula (2-2), and a formula ( The group represented by 2-3) is a monovalent group, and “*” in these groups means a bonding position.
  • a group represented by formula (4-1), a group represented by formula (4-2), a group represented by formula (4-3), and a group represented by formula (4-4), which will be described later Is the same.
  • R 22 and R 23 which together form a ring structure are a C ( ⁇ O) OC * CH 2 OC ( ⁇ O) group to which R 22 and R 23 are bonded. It means to form a ring structure together.
  • C * is a carbon atom to which R 6 is bonded.
  • -R 22 R 23 - is not particularly limited, but is an alkylene group; an alkenylene group; an alkynylene group; an arylene group; a cycloalkylene group; an alkylene group, an alkenylene group interrupted by an arylene group or a cycloalkylene group, or Alkynylene group etc. are mentioned.
  • examples of the alkenylene group and the alkynylene group include groups obtained by removing one hydrogen atom from an alkenyl group and an alkynyl group.
  • Portions other than the group represented by the formula and the group represented by formula (2-3) are optional, and can be, for example, an aromatic or aliphatic group.
  • Examples of the first modified resin include a modified resin represented by the following formula (3) (hereinafter also referred to as “second modified resin”).
  • Ar 1 (—O—A 1 ) n1 (3) Ar 1 is an n1 valent group having a total number of carbon atoms and heteroatoms of 5 or more, and including one or more aromatic rings or heteroaromatic rings, n1 is 1 or more, A 1 is independently a hydrogen atom, a group represented by the following formula (1-1), a group represented by the following formula (1-2), a group represented by the following formula (2-1), the following A group represented by the formula (2-2), a group represented by the following formula (2-3), a group represented by the following formula (4-1), or a group represented by the following formula (4-2).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom or a methyl group
  • R 21 is an alkyl group, an alkenyl group, an alkynyl group or an aryl group
  • R 22 and R 23 are each independently an alkyl group, alkenyl group, alkynyl group or aryl group, or R 22 and R 23 together form a ring structure
  • X 1 is an oxygen atom or a sulfur atom
  • R 24 is an alkyl group, an alkenyl group, an alkynyl group or an aryl group
  • B 1 is independently an alkylene group
  • m 1 is 1 or more
  • D 1 is an arylene group, an alkylene-arylene-alkylene group, an alkylene-arylene group, an arylene-alkylene-arylene group or
  • n1 is preferably 1 to 8, and particularly preferably 1 to 4.
  • Ar 1 has 4 to 40 carbon atoms, 0 to 5 oxygen atoms, 0 to 5 nitrogen atoms, and 0 to 5 sulfur atoms. And the number of ring structures contained in Ar 1 is preferably 1 to 5.
  • the ring structure (aromatic ring and / or heteroaromatic ring) contained in Ar 1 may be a single type or a plurality of types of two or more types, and the ring structure may be a monocyclic structure or a condensed ring. It may be a structure. A plurality of these ring structures may be bonded to each other through a direct bond or a linking group.
  • Ar 1 is selected from the group consisting of one or more ring structures (aromatic ring and / or heteroaromatic ring) as an essential group and a linking group 1, a linking group 2 and a substituent as an optional group It is preferable that it is group which consists only of 1 type or more.
  • the connecting group 1 connects a plurality of ring structures
  • the connecting group 2 connects Ar 1 and (—O—A 1 ) in the formula (3).
  • linking groups 1 and 2 examples include an alkylene group, an alkylidene group, an alkyleneoxy group, an ether group, an ester group, a keto group, a sulfide group, and a sulfonyl group.
  • the ring structure included in the oxygen atom and the Ar 1 that binds to Ar 1 the ring structure may be bonded via a linking group 2, but contained in Ar 1 is, Ar It is preferably directly bonded to an oxygen atom bonded to 1 .
  • the linking group 2 an alkylene group, an alkylidene group, an alkyleneoxy group, or a keto group is more preferable.
  • An alkylene group, which is an example of the linking group 1 or 2 more preferably has 1 to 4 carbon atoms, and an alkylidene group more preferably has 2 to 4 carbon atoms.
  • These ring structures may each independently have a substituent.
  • substituents include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkyl mercapto group, a cycloalkyl group, and a halogen atom.
  • Examples of the ring structure contained in Ar 1 include benzene ring, naphthalene ring, fluorene ring, anthracene ring, furan ring, pyrrole ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, thiazine ring, and these And those having the above substituents bonded to the ring.
  • Ar 1 when n1 is 1 include a phenyl group, a biphenylyl group, a naphthyl group, a terphenylyl group, an anthracenyl group, a fluorenyl group, and the like.
  • Ar 1 when n1 is 2 include arylene groups having 6 to 20 carbon atoms, arylene groups having 6 to 20 carbon atoms, alkylene groups having 1 to 6 carbon atoms, and arylene groups having 6 to 20 carbon atoms.
  • R 51 is an alkylene group having 1 to 8 carbon atoms
  • m3 is 0 or an integer of 1 to 6, and includes a phenylene-isopropylidene-phenylene group (a group obtained by removing two hydroxyl groups from bisphenol A), a phenylene-methylene-phenylene group (two hydroxyl groups derived from bisphenol F). Group), phenylene-ethylidene-phenylene group (group in which two hydroxyl groups are removed from bisphenol AD), etc. Group is preferred.
  • a phenol novolak represented by the following formula may also be mentioned.
  • R 61 is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • m4 is 0 or 1 or more
  • R 62 is independently a bonding position or a hydroxyl group, The number of bonding positions in R 62 matches the valence of Ar 1 .
  • n1 when n1 is 5 or more, a group in which 4 or more hydrogen atoms bonded to the aromatic carbon atom of the specific example of Ar 1 when n1 is 1 is removed, or n1 is 2 3 above except groups and the hydrogen atoms bonded to aromatic carbon atoms of the examples of Ar 1 in the case where, bonded to aromatic carbon atoms of the aromatic group examples of Ar 1 when n1 is 3 And a group in which one or more hydrogen atoms bonded to the aromatic carbon atom of the specific example of Ar 1 when n1 is 4 are removed.
  • m1 is preferably an integer of 1 to 6.
  • m2 when m2 is 1 or more, it is preferably an integer of 1 to 6.
  • D 1 include a specific example of Ar 1 when n 1 is 2.
  • R 21 is an alkenyl group, it preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, from the viewpoint of further increasing the adhesive strength, and includes a 1-propenyl group, a 2-propenyl group, 1 -Methyl-1-propenyl, 2-methyl-1-propenyl, 3-butenyl, 1,3-dipentenyl and 9-decenyl are particularly preferred.
  • R 21 is an alkyl group, it preferably has 1 to 18 carbon atoms, more preferably 1 to 4, and particularly preferably a methyl group, a propyl group, and an isopropyl group.
  • R 22 and R 23 are alkenyl groups, they preferably have 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 1-propenyl groups.
  • R 22 and R 23 are alkyl groups, the number of carbon atoms is preferably 1 to 18, more preferably 1 to 4, and particularly preferably a methyl group, a propyl group, and an isopropyl group.
  • R 22 and R 23 are aryl groups, a phenyl group is preferred.
  • R 24 is an alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 4, and particularly preferably a methyl group and a butyl group.
  • the first modified resin is preferably a second modified resin.
  • the modified resin is preferably contained in an amount of 5 to 95 parts by weight, more preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight based on 100 parts by weight of the curable resin composition. More preferably, parts by weight are included.
  • the method for producing the modified resin is not particularly limited as long as the first modified resin is obtained.
  • the method for producing a modified resin includes, for example, a step of reacting an epoxy resin, a modified compound as an essential component, and (meth) acrylic anhydride as an optional component, wherein the modified compound is a carboxylic acid. (However, (meth) acrylic acid is excluded), Carboxylic anhydride (however, (meth) acrylic anhydride is excluded), The manufacturing method which is 1 or more types of compounds selected from the group which consists of alcohol and thiol. Is mentioned.
  • the method for producing the modified resin is preferably a method for producing the second modified resin.
  • a method for producing a modified resin will be described by taking as an example a production method including a step of reacting an epoxy resin, a modified compound as an essential component, and (meth) acrylic anhydride as an optional component.
  • the epoxy resin is not particularly limited as long as it is a resin having two or more epoxy groups in one molecule.
  • the manufacturing method of modified resin is the manufacturing method of 2nd modified resin
  • the epoxy resin represented by following formula (5) is mentioned, for example.
  • Formula: Ar 2 (—O—A 2 ) n2 (5) [Where, Ar 2 is synonymous with Ar 1 , n2 is synonymous with n1, A 2 is independently a hydrogen atom; a group represented by the following formula (1-1); a group represented by the following formula (4-3); or a group represented by the following formula (4-4): In Although, However, it has 2 or more epoxy groups in the molecule.
  • the epoxy resin represented by the formula (5) has two or more epoxy groups in one molecule, and this epoxy group is an epoxy group possessed by the group represented by the formula (1-1). Therefore, when n2 is 1, A 2 is a group represented by the formula (4-4), and C 5 and C 6 are groups represented by the formula (1-1).
  • the formula Ar 2 any structure of the epoxy resin represented by (5) (e.g., an aromatic or aliphatic group) With, or as a manufacturing process of the first modified resin.
  • Such a resin having two or more epoxy groups in one molecule is not particularly limited, and is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy.
  • diglycidyl etherified products of difunctional phenols diglycidyl etherified products of difunctional alcohols and their halides, hydrogenated products, and the like can also be used.
  • the epoxy resin is commercially available or can be prepared according to a known method.
  • the epoxy resin having a group represented by the formula (4-3) can be obtained by, for example, the method described in JP-A-8-333356 or a method similar thereto.
  • the epoxy resin having a group represented by the formula (4-4) can be obtained by, for example, the method described in JP2012-077720A and JP2013-241488A or a method similar thereto. it can.
  • the modifying compound is one or more compounds selected from the group consisting of carboxylic acid (excluding (meth) acrylic acid), carboxylic anhydride (excluding (meth) acrylic anhydride), alcohol and thiol. It is.
  • a modification compound may be used individually by 1 type, respectively, or may be used in combination of 2 or more type.
  • Carboxylic acid (where (meth) excluding acrylic acid) as the formula: R 41 -COOH wherein, R 41 has the same meaning as R 21. ]
  • the compound represented by this is mentioned.
  • carboxylic acid excluding (meth) acrylic acid
  • a modified resin having a group represented by the formula (2-1) can be obtained.
  • R 5 is a hydrogen atom when the epoxy group of the epoxy resin represented by formula (5) is a glycidyl group, and the epoxy group of the epoxy resin represented by formula (5) is methyl glycidyl. When it is a group, it is a methyl group.
  • Carboxylic anhydride (excluding (meth) acrylic anhydride) has the formula R 42 —C ( ⁇ O) —O—C ( ⁇ O) —R 43 [wherein R 42 and R 43 Is synonymous with R 22 and R 23 . ]
  • the compound represented by this is mentioned.
  • a carboxylic acid anhydride excluding (meth) acrylic anhydride
  • a modified resin having a group represented by the formula (2-2) can be obtained.
  • R 22 and R 23 which together form a ring structure are a reaction between an epoxy group in an epoxy resin and a dicarboxylic anhydride such as succinic anhydride, maleic anhydride, phthalic anhydride, etc. It is formed by.
  • R 6 is the same as R 5 .
  • the alcohol and thiol are represented by the formula: R 44 —X 2 —H [wherein R 44 has the same meaning as R 24 and X 2 has the same meaning as X 1 . ]
  • the compound represented by this is mentioned.
  • a modified resin having a group represented by the formula (2-3) can be obtained.
  • R 7 is the same as R 5 .
  • the (meth) acrylic anhydride is one or more selected from the group consisting of acrylic anhydride and methacrylic anhydride.
  • a modified resin having a group represented by the formula (1-2) is obtained by reacting an epoxy group in the epoxy resin with (meth) acrylic anhydride.
  • R 2 and R 3 are hydrogen atoms when the (meth) acrylic anhydride is acrylic anhydride, and methyl when the (meth) acrylic anhydride is methacrylic anhydride. It is a group.
  • R 4 is the same as R 5 .
  • the modified resin obtained when there is an epoxy group that has not reacted with (meth) acrylic anhydride and the modifying compound, the modified resin has a group represented by the formula (1-1).
  • R 1 is the same as R 5 .
  • reaction conditions for obtaining the modified resin known conditions used by the reaction of the epoxy resin, the modified compound as an essential component, and (meth) acrylic anhydride as an optional component can be appropriately applied.
  • the reaction can be carried out in the presence or absence of a basic catalyst and / or an acid catalyst.
  • a basic catalyst and an acid catalyst the well-known basic catalyst and acid catalyst used by reaction with an epoxy resin, the modified compound as an essential component, and the (meth) acrylic anhydride as an arbitrary component are mentioned.
  • Basic catalysts include alkali metal hydroxides (sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (sodium carbonate, potassium carbonate, etc.), alkali metal alkoxides (sodium methoxide, etc.), trivalent organic compounds. Phosphorus compounds and / or amine compounds are preferred.
  • a polymer-supported basic catalyst in which a basic catalyst is supported on a polymer can also be used.
  • trivalent organic phosphorus compound examples include alkylphosphines such as triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine and salts thereof, triphenylphosphine, tri-m-tolylphosphine, tris- (2 , 6-Dimethoxyphenyl) phosphine, arylphosphines such as bis [2- (diphenylphosphino) phenyl] ether and salts thereof, phosphorous acid such as triphenylphosphite, triethylphosphite, tris (nonylphenyl) phosphite Examples include triesters and salts thereof.
  • alkylphosphines such as triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine and salts thereof
  • triphenylphosphine tri-m-tolyl
  • amine compounds include secondary amines such as diethanolamine, tertiary amines such as triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol, trisdiethylaminomethylphenol, 1,5,7-triazabicyclo [4.
  • dec-5-ene TBD
  • 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene Me-TBD
  • 1,8-diazabicyclo DBU
  • 6-dibutylamino-1,8-diazabicyclo [5.4.0] undec-7-ene 1,5-diazabicyclo [4.3.0]
  • Examples include strongly basic amines such as non-5-ene (DBN) and 1,1,3,3-tetramethylguanidine and salts thereof. Of these, 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) is preferable.
  • the salt of the amine compound include benzyltrimethylammonium chloride and benzyltriethylammonium chloride.
  • the acid catalyst examples include sulfuric acid, sulfonic acid such as trifluoromethanesulfonic acid, graphite oxide, and antimony fluoride. Moreover, you may use a cation exchanger (For example, amber list is mentioned as a commercial item) as an acid catalyst.
  • the acid catalyst can be used for the reaction of the epoxy resin with one or more compounds selected from the group consisting of alcohols and thiols.
  • the reaction can be performed in the presence or absence of a solvent.
  • a solvent inert to the reaction such as hydrocarbon, ether or ketone can be used.
  • the resin also functions as a solvent. is not.
  • the reaction temperature can be appropriately set by those skilled in the art depending on the catalyst and the raw material compound used.
  • the catalyst is a basic catalyst, (meth) acrylic acid anhydride, and carboxylic acid (however, excluding (meth) acrylic acid) and carboxylic acid anhydride (however, (meth) acrylic acid anhydride) as the modifying compound
  • the reaction temperature is preferably 60 to 120 ° C., more preferably 80 to 120 ° C., still more preferably 90 to 120 ° C., particularly preferably 100 ° C to 120 ° C.
  • the reaction temperature is preferably 0 to 100 ° C., more preferably 10 to 90 ° C., and particularly preferably 25 to 80 ° C.
  • the reaction amount of the modified compound with respect to 1 equivalent of epoxy group of the epoxy resin is more than 0 equivalent% and less than 100 equivalent%, and the reaction amount of (meth) acrylic anhydride with respect to 1 equivalent of epoxy group is 0 equivalent%.
  • the total reaction amount of the modifying compound and the (meth) acrylic anhydride with respect to 1 equivalent of epoxy group is more than 0 equivalent% and less than 100 equivalent%, preferably 5 to 95 equivalent%. More preferably, it is 10 to 90 equivalent%, and particularly preferably 20 to 80 equivalent%.
  • the reaction between the epoxy group, the (meth) acrylic anhydride, and the modified compound proceeds quantitatively, and therefore the modification rate of the obtained modified resin can be estimated from the epoxy equivalent.
  • the modified compound as an essential component and the (meth) acrylic anhydride as an optional component may be simultaneously reacted with an epoxy resin to obtain a modified resin.
  • the epoxy resin and the modifying compound are reacted to obtain an epoxy resin partially modified with the modifying compound, and the epoxy resin partially modified with the modifying compound is reacted with (meth) acrylic anhydride to modify the epoxy resin.
  • a resin may be obtained.
  • An epoxy resin partially modified with (meth) acrylic anhydride is obtained by reacting an epoxy resin with (meth) acrylic anhydride, and partially modified with (meth) acrylic anhydride.
  • the modified epoxy resin may be reacted with a modifying compound to obtain a modified resin.
  • the modified resin obtained by the method for producing a modified resin may be obtained as a resin mixture containing a resin having the same skeleton.
  • the skeleton in the second modified resin refers to the Ar 1 portion.
  • the skeleton in the first modified resin is a group represented by the formula (1-1), a group represented by the formula (1-2), a group represented by the formula (2-1), a formula It refers to a moiety other than the group represented by (2-2) and the group represented by formula (2-3).
  • thermosetting agent and / or polymerization initiator A thermosetting agent and / or a polymerization initiator can be suitably selected according to the component contained in curable resin composition.
  • a thermosetting agent a curable resin composition can be made into a thermosetting resin composition.
  • a polymerization initiator the curable resin composition can be made into a radical polymerization curable, anionic polymerization curable and / or cationic polymerization curable resin composition.
  • the blending amount of the thermosetting agent is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the curable resin composition. More preferably.
  • the blending amount of the polymerization initiator is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, with respect to 100 parts by weight of the curable resin composition. More preferably, parts by weight are included.
  • thermosetting agent is not particularly limited, and examples thereof include amine thermosetting agents such as organic acid dihydrazide compounds, amine adducts, imidazoles and derivatives thereof, dicyandiamide, aromatic amines, epoxy-modified polyamines, and polyaminoureas.
  • amine thermosetting agents such as organic acid dihydrazide compounds, amine adducts, imidazoles and derivatives thereof, dicyandiamide, aromatic amines, epoxy-modified polyamines, and polyaminoureas.
  • thermosetting agents 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin), ADH (adipic acid dihydrazide), UDH (7,11-octadecadien-1,18-dicarbohydrazide) and LDH (octadecane-1, Organic acid dihydrazides such as 18-dicarboxylic acid dihydrazide); polyamine compounds sold as ADEKA HARDNER EH5030S etc. from ADEKA Corporation; Ajinomoto Fine Techno Co., Ltd., Amicure PN-23, Amicure PN-30, Amicure Y-24, preferably an amine adduct commercially available as Amicure MY-H, and the like. These thermosetting agents may be used alone or in combination.
  • polymerization initiator examples include a radical polymerization initiator, an anionic polymerization initiator and / or a cationic polymerization initiator.
  • the polymerization initiator is a component that becomes a radical generation source when radically polymerizing a curable component contained in the curable resin composition, an anion generation source when anionic polymerization is performed, and a cation generation source when cationic polymerization is performed.
  • radical polymerization initiators benzoins, acetophenones, benzophenones, thioxanthones, ⁇ -acyloxime esters, phenylglyoxylates, benzyls, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, Examples include benzoin ethers, anthraquinones, and organic peroxides.
  • the radical polymerization initiator preferably has a low solubility in the liquid crystal and a reactive group that itself does not gasify the decomposition product when irradiated with light.
  • radical polymerization initiator a compound obtained by reacting a compound having at least two epoxy groups with dimethylaminobenzoic acid described in WO2012 / 0777720, and at least two epoxy groups
  • a polymerization initiator which is a mixture of a compound obtained by reacting the compound having a compound with hydroxythioxanthone is preferable.
  • anionic polymerization initiator examples include imidazoles, amines, phosphines, organometallic salts, metal chlorides, and organic peroxides.
  • Cationic polymerization initiators include onium salts, iron allene complexes, titanocene complexes, arylsilanol aluminum complexes, Lewis acid compounds, Bronsted acid compounds, benzylsulfonium salts, thiophenium salts, thiolanium salts, benzylammonium, pyridinium salts, hydrazinium salts, Examples thereof include carboxylic acid esters, sulfonic acid esters, amine imides, sulfone compounds, sulfonic acid esters, sulfonimides, disulfonyldiazomethanes, and amines.
  • the polymerization initiator is commercially available or can be prepared according to a known method. Each of the radical polymerization initiator, the anionic polymerization initiator and the cationic polymerization initiator may be used alone or in combination of two or more. The polymerization initiator can be appropriately used according to desired curing conditions (energy ray curing and / or heat curing).
  • the curable resin composition can include one or more additional components selected from the group consisting of a further resin (excluding the first modified resin), a photosensitizer, a filler, and a coupling agent. .
  • the additional resin is not particularly limited as long as it is a resin other than the first modified resin, and is a conventional resin having an unsaturated group and / or an epoxy group used as a main component of a liquid crystal sealant, and an unsaturated group and an epoxy. Resins that do not have any of the groups are mentioned.
  • the “unsaturated group” means an ethylenically unsaturated group and / or an acetylenically unsaturated group.
  • resin having an unsaturated group examples include (meth) acrylate compounds, aliphatic acrylamide compounds, alicyclic acrylamide compounds, acrylamide compounds containing aromatics, N-substituted acrylamide compounds, diene polymers (eg, polybutadiene polymers, poly Isoprene polymer).
  • the functionality of the (meth) acrylate compound can be monofunctional, bifunctional or trifunctional or higher polyfunctional.
  • Monofunctional (meth) acrylate compounds include hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate , Dicyclopentanyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) Acrylate, tert-butyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, paracumylphenoxyethylene glycol (meth) Acrylate, and one or more compounds selected
  • Bifunctional (meth) acrylate compounds include tricyclodecane dimethanol di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, and EO-modified.
  • EO means ethylene oxide
  • PO means propylene oxide.
  • Trifunctional or higher polyfunctional (meth) acrylate compounds include EO-modified glycerol tri (meth) acrylate (trifunctional), PO-modified glycerol tri (meth) acrylate (trifunctional), pentaerythritol tri (meth) acrylate ( One or more compounds selected from trifunctional), dipentaerythritol hexa (meth) acrylate (hexafunctional) and pentaerythritol tetra (meth) acrylate (tetrafunctional) are preferred.
  • epoxy resin As the resin having an unsaturated group, all of the epoxy groups of the epoxy resin are modified with (meth) acrylic acid, and all of the epoxy groups of the epoxy resin are modified with a modifying compound having an unsaturated group.
  • An epoxy resin is mentioned.
  • the resin having an epoxy group is not particularly limited as long as it has one or more epoxy groups.
  • Examples of the resin having one epoxy group include aromatic epoxy resins and aliphatic epoxy resins.
  • Examples of the resin having two or more epoxy groups include those described above as the epoxy resin.
  • Resin having unsaturated group and epoxy group examples include a partial (meth) acrylate-modified epoxy resin in which a part of the epoxy group of the epoxy resin is modified with a (meth) acrylic acid compound.
  • Resin having neither unsaturated group nor epoxy group As a resin having neither an unsaturated group nor an epoxy group, all of the epoxy groups of the epoxy resin are modified with a modified compound having no unsaturated group, a hydroxyl group-containing compound and an isocyanate group-containing compound. The urethane resin etc. which are formed are mentioned.
  • Further resins include epoxy resins (excluding epoxy resins having a (meth) acryloyl group), modified epoxy resins in which part or all of the epoxy groups of the epoxy resin are modified with (meth) acrylic anhydride, epoxy One or more resins selected from the group consisting of modified epoxy resins in which all of the epoxy groups of the resin are modified with a modifying compound, wherein the modifying compound is a carboxylic acid (except (meth) acrylic acid)
  • a resin that is one or more compounds selected from the group consisting of carboxylic anhydrides (excluding (meth) acrylic anhydride), alcohols and thiols is preferred.
  • the epoxy resin (excluding an epoxy resin having a (meth) acryloyl group) may be a raw material epoxy resin for obtaining a modified resin.
  • denatured with the (meth) acrylic anhydride is a component which can be obtained as components other than modified resin with the manufacturing method of modified resin.
  • the modified epoxy resin which is one or more compounds selected from the group consisting of alcohol and thiol (excluding acrylic anhydride), is a component that can be obtained as a component other than the modified resin by the method for producing the modified resin.
  • the curable resin composition may further contain a photosensitizer in order to increase sensitivity to light during photocuring.
  • a photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes from the viewpoint of curability.
  • Specific examples of the photosensitizer include an acridone derivative such as N-methylacridone and N-butylacridone; in addition, ⁇ , ⁇ -diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compound and the like.
  • Some of the polymerization initiators function as photosensitizers.
  • a photosensitizer may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the purpose of the filler is to improve the adhesive reliability of the curable resin composition by controlling the viscosity of the curable resin composition, improving the strength of the cured product obtained by curing the curable resin composition, or suppressing linear expansion.
  • a filler is not specifically limited, An inorganic filler and an organic filler are mentioned.
  • Inorganic fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and nitriding Silicon may be mentioned.
  • Examples of the organic filler include polymethyl methacrylate, polystyrene, a copolymer obtained by copolymerizing the monomer and other monomers, polyester fine particles, polyurethane fine particles, rubber fine particles, and a copolymer having a high glass transition temperature.
  • Examples thereof include core-shell type particles composed of a shell containing a polymer and a copolymer core having a low glass transition temperature.
  • a commercial item can be used for a filler.
  • Examples of commercially available silicon dioxide particles include the Seahoster KE series (such as KE-C50).
  • Examples of the core-shell type particles include the Zefiac series (F-351 and the like, manufactured by Aika Industry Co., Ltd.) and the like.
  • a filler may be used individually by 1 type, respectively, or may be used in combination of 2 or more type.
  • the silane coupling agent is added for the purpose of further increasing the adhesive strength.
  • the silane coupling agent is not particularly limited, and examples thereof include ⁇ -aminopropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane.
  • a silane coupling agent may be used independently and may be used in combination of 2 or more type.
  • the curable resin composition is preferably a sealant, and more preferably a sealant used for a display element, a light amount adjusting element, a focus variable element, a light modulation element, and the like.
  • the curable resin composition is a liquid crystal display (or liquid crystal display element) including a module-type display, a three-dimensional display, a head-mounted display, a projection-type display, etc .; a dimming filter, a dimming shutter, an anti-glare mirror, a spatial light quantity
  • Light modulation liquid crystal elements such as modulators
  • variable focus liquid crystal elements such as liquid crystal lenses
  • light modulation liquid crystals such as optical deflectors, optical demultiplexers, phase control, polarization control, holograms, diffraction gratings, wavelength filters, and frequency filters
  • it is a liquid crystal sealant used in the element; and a liquid crystal dropping method sealant is particularly preferable.
  • the curable resin composition can be cured by applying heat by irradiation with energy rays such as ultraviolet rays, or by applying heat before, after or simultaneously with irradiation of energy rays such as ultraviolet rays.
  • Comparative modified resin 1 (partially methacrylated bisphenol A type epoxy resin) Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 340.0 g, methacrylic acid (Tokyo Chemical Industry Co., Ltd.) 86.1 g, and triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) 500 mg are mixed and mixed. Stir at 6 ° C. for 6 hours. 418.0g of comparative (meth) acrylate resin 1 of the pale yellow transparent viscous substance was obtained.
  • Modified resin 3 Mix bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0g, 3-butenoic acid (Tokyo Chemical Industry Co., Ltd.) 21.5g, and triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) 132mg And stirred at 100 ° C. for 6 hours. 102.0 g of modified resin 3 having a transparent viscous substance was obtained.
  • EXA-850CRP manufactured by DIC Corporation
  • 3-butenoic acid Tokyo Chemical Industry Co., Ltd.
  • triphenylphosphine Tokyo Chemical Industry Co., Ltd.
  • Modified resin 8 Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, acetic acid (manufactured by Kanto Chemical Co., Ltd.) 15.0 g, and triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 132 mg were mixed at 100 ° C. Stir for 7 hours. 89.0 g of modified resin 8 having a transparent viscous substance was obtained.
  • EXA-850CRP manufactured by DIC Corporation
  • acetic acid manufactured by Kanto Chemical Co., Ltd.
  • triphenylphosphine manufactured by Tokyo Chemical Industry Co., Ltd.
  • Modified Resin 11 85.0 g of bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 39.6 g of butyric anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 132 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed. The mixture was stirred at 100 ° C. for 72 hours. 122.0 g of modified resin 11 having a transparent viscous substance was obtained.
  • EXA-850CRP bisphenol A type epoxy resin
  • butyric anhydride manufactured by Tokyo Chemical Industry Co., Ltd.
  • triphenylphosphine manufactured by Tokyo Chemical Industry Co., Ltd.
  • Modified Resin 12 85.0 g of bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 38.7 g of crotonic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 132 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed. And stirred at 100 ° C. for 30 hours. 120.0 g of a modified resin 12 having a transparent viscous substance was obtained.
  • EXA-850CRP bisphenol A type epoxy resin
  • crotonic anhydride manufactured by Tokyo Chemical Industry Co., Ltd.
  • triphenylphosphine manufactured by Tokyo Chemical Industry Co., Ltd.
  • Modified resin 13 Mix bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0g, benzoic anhydride (Tokyo Chemical Industry Co., Ltd.) 56.6g, and triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) 132mg And stirred at 100 ° C. for 6 hours. 138.0g of modified resin 13 of a transparent viscous material was obtained.
  • EXA-850CRP bisphenol A type epoxy resin
  • benzoic anhydride Tokyo Chemical Industry Co., Ltd.
  • triphenylphosphine Tokyo Chemical Industry Co., Ltd.
  • Modified Resin 15 425 g of 1-butanol (manufactured by Kanto Chemical Co., Ltd.) and 2.7 g of sodium methoxide (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 70 ° C. for 3 hours. The reaction mixture was cooled to 50 ° C., 85.0 g of bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) was added and stirred for 110 minutes, 50.0 g of 3% hydrochloric acid was added, and 1-butanol was reduced in pressure. After evaporation, 300 mL of ethyl acetate was added and washed with 300 mL of water four times.
  • EXA-850CRP bisphenol A type epoxy resin
  • Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is filtered off by filtration or the like, and the solvent of the obtained organic phase is distilled off under reduced pressure to remove a transparent viscous modified resin 15 by 106. 0.0 g was obtained.
  • Epoxy resin A (Reference Synthesis Example 1-1) Synthesis of EXA-850CRP ethylene glycol ring-opened product 500.0 g of ethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 45% tin borofluoride aqueous solution (manufactured by Morita Chemical Co., Ltd.) ) 1.0 g was placed in an eggplant flask. 340.0 g of bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) was gradually added over 1 hour while stirring at 80 ° C., and stirred at 80 ° C. for 1 hour from the end of addition.
  • reaction mixture was cooled to room temperature, 1 L of chloroform was added, and the mixture was washed 6 times with 1 L of water.
  • the solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 410.0 g of a colorless transparent viscous EXA-850CRP-ethylene glycol ring-opened product.
  • Modified resin 17 45.7 g of epoxy resin A, 8.6 g of 3-butenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 53 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 ° C. for 16 hours. 50.0 g of a modified resin 17 having a transparent viscous substance was obtained.
  • Modified resin 20 228.0 g of epoxy resin A, 77.1 g of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 39.5 g of isobutyric anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 262 mg was mixed and stirred at 100 ° C. for 8 hours. 338.0 g of yellowish transparent viscous modified resin 20 was obtained.
  • Modified resin 21 228.0 g of epoxy resin A, 77.1 g of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 22.0 g of isobutyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 262 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) Mix and stir at 100 ° C. for 7 hours. 324.0g of modified resin 21 of a yellow transparent viscous substance was obtained.
  • Modified Resin 22 228.0 g of epoxy resin A, 57.8 g of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 59.3 g of isobutyric anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 262 mg was mixed and stirred at 100 ° C. for 8 hours. 342.0g of modified resin 22 of yellow transparent viscous material was obtained.
  • Modified Resin 24 228.0 g of epoxy resin A, 25.7 g of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 26.4 g of isobutyl acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 262 mg was mixed and stirred at 100 ° C. for 5 hours. 277.0 g of a yellow transparent viscous modified resin 24 was obtained.
  • Modified Resin 25 228.0 g of epoxy resin A, 17.1 g of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 35.1 g of isobutyric anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 262 mg was mixed and stirred at 100 ° C. for 5 hours. 276.0g of modified resin 25 of yellow transparent viscous material was obtained.
  • Comparative modified resin 2 228.0 g of epoxy resin A, 43.0 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 262 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 ° C. for 7 hours. 265.0g of comparative modified resin 2 of a yellow transparent viscous substance was obtained.
  • Comparative modified resin 3 228.0 g of epoxy resin A, 115.6 g of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 262 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 ° C. for 8 hours. 339.0g of comparative modified resin 3 of a yellow transparent viscous substance was obtained.
  • Comparative modified resin 4 228.0 g of epoxy resin A, 51.3 g of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 262 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 ° C. for 5 hours. 272.0g of comparative modified resin 4 of a yellow transparent viscous substance was obtained.
  • photopolymerization initiator used in Examples and Comparative Examples was produced as follows.
  • (Production of photopolymerization initiator 1) 26.8 g of PEG400 diglycidyl ether (Denacol EX-830, manufactured by Nagase ChemteX Corporation), 16.5 g of 4-dimethylaminobenzoic acid, 3.7 g of benzyltrimethylammonium chloride, and 25.0 g of methyl isobutyl ketone (MIBK) was placed in a flask and stirred at 110 ° C. for 24 hours.
  • MIBK methyl isobutyl ketone
  • the reaction mixture was cooled to room temperature, dissolved in 50.0 g of chloroform, and washed 6 times with 100 mL of water.
  • the solvent of the organic phase was distilled off under reduced pressure to obtain 35.3 g of photopolymerization initiator 1.
  • Photopolymerization initiator 2 26.8 g of PEG400 diglycidyl ether (Denacol EX-830, manufactured by Nagase ChemteX Corporation), 22.8 g of 2-hydroxy-9H-thioxanthen-9-one, 3.7 g of benzyltrimethylammonium chloride, and 40.0 g of MIBK was placed in a flask and stirred at 110 ° C. for 72 hours.
  • the reaction mixture was cooled to room temperature, dissolved in 50.0 g of chloroform, and washed 6 times with 100 mL of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 36.2 g of photopolymerization initiator 2.
  • Examples 1 to 55 and Comparative Examples 1 to 4 Each of the modified resins and comparative modified resins produced in the synthesis examples and comparative synthesis examples, photopolymerization initiators 1 and 2, fillers; core-shell type particles (Zefiac F-351, manufactured by Aika Industry Co., Ltd.), fillers; silicon dioxide particles (Seahoster KE-C50, manufactured by Nippon Shokubai Co., Ltd.), silane coupling agent; 3-glycidoxypropylmethyldiethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), curing agent; polyamine compound (EH- 5030S, manufactured by ADEKA Corporation, active hydrogen equivalent of 105 g / eq), mixed at the blending amounts (parts by weight) shown in Tables 1 to 9 below, followed by a three-roll mill (C-4 3/4 ⁇ 10, The curable resin compositions of Examples and Comparative Examples were sufficiently kneaded by Inoue Seisakusho Co.
  • Epoxy equivalent (WPE) measurement It measured on the conditions of JISK7236: 2001.
  • the unit of epoxy equivalent in the table is g / eq.
  • Viscosity measurement It measured at 25 degreeC using the E-type viscosity meter (RE105U, the Toki Sangyo Co., Ltd. make).
  • Adhesive strength measurement A polyimide-based alignment liquid (Sunever SE-7492, manufactured by Nissan Chemical Industries, Ltd.) was dropped onto an ITO substrate (403005XG-10SQ1500A, manufactured by Geomatic Co., Ltd.) that had been washed with pure water and dried using an air dispenser. (0.4 MPa, 5.0 seconds), and then, it was uniformly applied under the condition of reaching 5000 rpm in 10 seconds with a spin coater and then keeping for 20 seconds. After uniformly coating, pre-baking (1 minute) on an 85 ° C. hot plate and post-baking (60 minutes) in an oven at 230 ° C., a substrate with a polyimide alignment film was prepared.
  • Curable resin composition after bonding the curable resin composition to the positions of 15 mm ⁇ 3 mm, 15 mm ⁇ 21 mm on an ITO substrate with a 6 ⁇ m spacer dispersed, a substrate with a polyimide alignment film (30 mm ⁇ 30 mm ⁇ 0.5 mmt) Spot coating was performed so that the diameter of the object was in the range of 1.5 to 2.5 mm ⁇ . Thereafter, the same type of substrates (23 mm ⁇ 23 mm ⁇ 0.5 mmt) are bonded together, and ultraviolet rays are irradiated with an integrated light amount of 3000 mJ / cm 2 (irradiation apparatus: UVX-01224S1, manufactured by USHIO INC.) To be cured and heated at 120 ° C.
  • Tables 1 to 9 The results of the epoxy equivalent and viscosity measurement are shown in Tables 1 to 9 together with the blending compositions of the curable resin compositions of Examples 1 to 55 and Comparative Examples 1 to 4.
  • Tables 10 to 17 show the results of adhesive strength measurement performed on some of the examples and comparative examples.

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