WO2018181647A1 - （メタ）アクリレート樹脂及びそれを含む硬化性樹脂組成物 - Google Patents

（メタ）アクリレート樹脂及びそれを含む硬化性樹脂組成物 Download PDF

Info

Publication number
WO2018181647A1
WO2018181647A1 PCT/JP2018/013091 JP2018013091W WO2018181647A1 WO 2018181647 A1 WO2018181647 A1 WO 2018181647A1 JP 2018013091 W JP2018013091 W JP 2018013091W WO 2018181647 A1 WO2018181647 A1 WO 2018181647A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
meth
formula
represented
group represented
Prior art date
Application number
PCT/JP2018/013091
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
大晃 臼井
健介 宮崎
白石　大輔
Original Assignee
協立化学産業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 協立化学産業株式会社 filed Critical 協立化学産業株式会社
Priority to KR1020197028436A priority Critical patent/KR102267158B1/ko
Priority to CN201880014468.2A priority patent/CN110366570B/zh
Publication of WO2018181647A1 publication Critical patent/WO2018181647A1/ja

Links

Classifications

    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • 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
    • C08G59/18—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 (meth) acrylate 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 (meth) acrylate resin and a curable resin composition containing the same that exhibit high adhesive strength when the substrates are bonded to each other.
  • the present invention has the following configuration.
  • the molecule has one or more groups represented by the following formula (1), a group represented by the following formula (2-1), and a group represented by the following formula (2-2).
  • a (meth) acrylate resin having one or more groups selected from the group consisting of a group represented by the following formula (2-3):
  • a curable resin composition comprising a thermosetting agent and / or a polymerization initiator.
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom or a methyl group
  • R 21 is an alkenyl group or an alkynyl 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.
  • Ar 1 (—O—A 1 ) n1 (5)
  • 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), a group represented by the following formula (2-1), a group represented by the following formula (2-2), the following formula ( 2-3), a group represented by the following formula (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 and R 7 are each independently a hydrogen atom or a methyl group
  • R 21 is an alkenyl group or an alkynyl 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 a group: —B 2 — (O—B 2 —
  • [6] The curable resin composition according to [1], [2], [4] or [5], which is a liquid crystal sealant.
  • [7] including a step of reacting an epoxy resin, a modifying compound, and (meth) acrylic acid, wherein the modifying compound is an unsaturated aliphatic carboxylic acid (excluding (meth) acrylic acid), carboxylic acid
  • a (meth) acrylate resin and a curable resin composition containing the same that exhibit high adhesive strength when substrates are bonded to each other.
  • 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 represented by the following formula (1) in the molecule, and a group represented by the following formula (2-1):
  • a (meth) acrylate resin having at least one group selected from the group consisting of a group represented by the following formula (2-3) and a thermosetting agent and / or a polymerization initiator: contains.
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom or a methyl group
  • R 21 is an alkenyl group or an alkynyl 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 (meth) acrylate resin has one or more groups represented by the formula (1) in the molecule, and a group represented by the formula (2-1), represented by the formula (2-2). And one or more groups selected from the group consisting of groups represented by formula (2-3) (hereinafter also referred to as “first (meth) acrylate resin”).
  • the first (meth) acrylate resin includes a group represented by the formula (2-1), a group represented by the formula (2-2), and a formula (2 -3) having one or more groups selected from the group consisting of groups represented by, in addition to the properties as a (meth) acrylate resin, modified compounds (ie unsaturated aliphatic carboxylic acids (however, Further properties imparted by (excluding (meth) acrylic acid), carboxylic anhydrides (excluding (meth) acrylic anhydride), one or more compounds selected from the group consisting of alcohols and thiols) Can have.
  • modified compounds ie unsaturated aliphatic carboxylic acids (however, Further properties imparted by (excluding (meth) acrylic acid), carboxylic anhydrides (excluding (meth) acrylic anhydride), one or more compounds selected from the group consisting of alcohols and thiols) Can have.
  • the group represented by Formula (1), the group represented by Formula (2-1), the group represented by Formula (2-2), and the group represented by Formula (2-3) are monovalent Group, and “*” in these groups means a bonding position.
  • 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 4 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.
  • the first (meth) acrylate resin may further have a group represented by the following formula (3). [Wherein, R 6 represents a hydrogen atom or a methyl group. ]
  • the first (meth) acrylate resin has a group represented by the formula (3)
  • the first (meth) acrylate resin also has characteristics as an epoxy resin.
  • a group represented by the formula (1) a group represented by the formula (2-1), a group represented by the formula (2-2), a formula (2-3)
  • the portion other than the group represented by formula (3) and the group represented by formula (3) is arbitrary, and can be, for example, an aromatic or aliphatic group.
  • Examples of the first (meth) acrylate resin include a (meth) acrylate resin represented by the following formula (5) (hereinafter also referred to as “second (meth) acrylate resin”).
  • Ar 1 (—O—A 1 ) n1 (5) 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), a group represented by the following formula (2-1), a group represented by the following formula (2-2), the following formula ( 2-3), a group represented by the following formula (3), a group represented by the following formula (4-1) or a group represented by the following formula (4-2), However, the group represented by formula (4-1) having a group represented by formula (1) in the molecule; represented by formula (4-2) having a group represented by formula (1) A group; and one or more groups selected from the group consisting of groups represented by
  • 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 alkenyl group or an alkynyl 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 a group: —B 2 — (O—B 2 —
  • n1 is preferably 1 to 8, 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 (5).
  • 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 .
  • 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. or arylene -O- (R 51 -O) 6 to 20 carbon atoms m3 - in arylene group having 6 to 20 carbon atoms [wherein, R 51 is an alkylene group having 1 to 8 carbon atoms, m3 is 0 or an integer of 1 to 6.
  • a phenylene-isopropylidene-phenylene group (a group obtained by removing two hydroxyl groups from bisphenol A), a phenylene-methylene-phenylene group (a group obtained by removing two hydroxyl groups from bisphenol F), a phenylene-ethylidene-phenylene group A group obtained by removing two hydroxyl groups from bisphenols such as (a group obtained by removing two hydroxyl groups from bisphenol AD) 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 and 9-decenyl are particularly preferred.
  • 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 butyl group.
  • R 24 is an alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably a methyl group. When R 24 is an aryl group, a phenyl group is particularly preferable.
  • the first (meth) acrylate resin is preferably a second (meth) acrylate resin.
  • the (meth) acrylate resin is preferably contained in an amount of 5 to 95 parts by weight, more preferably 10 to 90 parts by weight, based on 100 parts by weight of the curable resin composition. More preferably, 20 to 80 parts by weight are contained.
  • the method for producing the (meth) acrylate resin is not particularly limited as long as the first (meth) acrylate resin is obtained.
  • the method for producing a (meth) acrylate resin is, for example, a production method including a step of reacting an epoxy resin, a modified compound, and (meth) acrylic acid, wherein the modified compound is an unsaturated aliphatic carboxylic acid.
  • Production method which is one or more compounds selected from the group consisting of acids (excluding (meth) acrylic acid), carboxylic anhydrides (excluding (meth) acrylic anhydride), alcohols and thiols Is mentioned.
  • the method for producing a (meth) acrylate resin includes a step of forming a group represented by the formula (1) by reacting a compound having a hydroxyl group with glycidyl (meth) acrylate, for example. Is mentioned.
  • the method for producing a (meth) acrylate resin is preferably a method for producing a second (meth) acrylate resin.
  • a method for producing a (meth) acrylate resin will be described with reference to an example of a production method including a step of reacting an epoxy resin, a modifying compound, and (meth) acrylic acid.
  • 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 (meth) acrylate resin is a manufacturing method of 2nd (meth) acrylate resin
  • the epoxy resin represented by following formula (6) is mentioned, for example.
  • Formula: Ar 2 (—O—A 2 ) n2 (6) [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 (3); a group represented by the following formula (4-3); or a group represented by the following formula (4-4). But, however, it has 2 or more epoxy groups in the molecule.
  • R 6 is as defined above; B 3 is synonymous with B 1 ; m 5 is synonymous with m 1; R 8 is synonymous with R 7 ; D 2 is D 1 and C 4 , C 5 and C 6 are each independently a hydrogen atom or a group represented by the formula (3). ]
  • the epoxy resin represented by the formula (6) 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 (3). Therefore, if n2 is 1, A 2 is a group represented by the formula (4-4), a group C 5 and C 6 are represented by the formula (3).
  • 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 selected from the group consisting of unsaturated aliphatic carboxylic acids (excluding (meth) acrylic acid), carboxylic anhydrides (excluding (meth) acrylic anhydride), alcohols and thiols.
  • unsaturated aliphatic carboxylic acids excluding (meth) acrylic acid
  • carboxylic anhydrides excluding (meth) acrylic anhydride
  • alcohols and thiols One or more compounds.
  • a modification compound may be used individually by 1 type, respectively, or may be used in combination of 2 or more type.
  • Unsaturated aliphatic carboxylic acids (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.
  • an unsaturated aliphatic carboxylic acid (excluding (meth) acrylic acid)
  • a (meth) acrylate resin having a group represented by the formula (2-1) can be obtained.
  • R 3 is a hydrogen atom when the epoxy group of the epoxy resin represented by formula (6) is a glycidyl group, and the epoxy group of the epoxy resin represented by formula (6) 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 anhydride excluding (meth) acrylic anhydride
  • a (meth) acrylate 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 4 is the same as R 3 .
  • 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 (meth) acrylate resin having a group represented by the formula (2-3) can be obtained.
  • R 5 is the same as R 3 .
  • (Meth) acrylic acid is one or more selected from the group consisting of acrylic acid and methacrylic acid.
  • a (meth) acrylate resin having a group represented by the formula (1) is obtained.
  • R 1 is a hydrogen atom when the (meth) acrylic acid is acrylic acid, and a methyl group when the (meth) acrylic acid is methacrylic acid.
  • R 2 is the same as R 3 .
  • the (meth) acrylate resin obtained when an epoxy group that has not reacted with (meth) acrylic acid and the modifying compound is present, the (meth) acrylate resin has a group represented by the formula (3).
  • R 6 is the same as R 3 .
  • reaction conditions for obtaining a (meth) acrylate resin known conditions used by the reaction of an epoxy resin, a modifying compound, and (meth) acrylic acid 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 and a modified compound 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, and carboxylic acid (excluding (meth) acrylic acid) and carboxylic acid anhydride (excluding (meth) acrylic acid anhydride) as the modifying compound )
  • the reaction temperature is preferably 60 to 120 ° C., more preferably 80 to 120 ° C., further 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 (meth) acrylic acid with respect to 1 equivalent of epoxy group in the epoxy resin is more than 0 equivalent percent and less than 100 equivalent percent, and the reaction amount of the modifying compound with respect to 1 equivalent of epoxy group is more than 0 equivalent percent to 100.
  • the total reaction amount of (meth) acrylic acid and the modifying compound with respect to 1 equivalent of epoxy group is less than equivalent%, more than 0 equivalent% and not more than 100 equivalent%, preferably 10 to 90 equivalent%, more preferably Is 20 to 80 equivalent%, particularly preferably 30 to 70 equivalent%.
  • the reaction between the epoxy group, (meth) acrylic acid and the modifying compound proceeds quantitatively, and therefore the modification rate of the obtained (meth) acrylate resin is estimated from the epoxy equivalent. You can also.
  • (Meth) acrylic acid and the modifying compound may be reacted with an epoxy resin at the same time to obtain a (meth) acrylate resin. Moreover, the epoxy resin and the modified compound are reacted to obtain an epoxy resin partially modified with the modified compound, and the epoxy resin partially modified with the modified compound and (meth) acrylic acid are reacted to obtain (meth) An acrylate resin may be obtained, and an epoxy resin partially modified with (meth) acrylic acid is obtained by reacting an epoxy resin with (meth) acrylic acid, and the epoxy resin partially modified with (meth) acrylic acid is modified. A (meth) acrylate resin may be obtained by reacting with a compound.
  • (meth) acrylate resin obtained by the manufacturing method of (meth) acrylate resin may be obtained as a resin mixture containing resin which has the same frame
  • the skeleton in the second (meth) acrylate resin refers to a portion of Ar 1 .
  • the skeleton in the first (meth) acrylate resin includes a group represented by the formula (1), a group represented by the formula (2-1), a group represented by the formula (2-2), and It means a part other than the group represented by the 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 25 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 includes one or more additional components selected from the group consisting of a further resin (excluding the first (meth) acrylate resin), a photosensitizer, a filler, and a coupling agent. be able to.
  • the additional resin is not particularly limited as long as it is a resin other than the first (meth) acrylate 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 unsaturated. And resins having neither a group nor an epoxy group.
  • 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.
  • the resin having one epoxy group include aromatic epoxy resins and aliphatic epoxy resins.
  • the resin having two or more epoxy groups include those described above as the epoxy resin.
  • denatured with the modification compound is mentioned.
  • Resin having unsaturated group and epoxy group a resin having an unsaturated group and an epoxy group
  • a partially modified epoxy resin in which a part of the epoxy group of the epoxy resin is modified with a compound having an unsaturated group for example, a portion modified with a (meth) acrylic acid compound) (Meth) acrylate-modified epoxy resin).
  • 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 an epoxy resin (except for an epoxy resin having a (meth) acryloyl group), a modified epoxy resin in which part or all of the epoxy group of the epoxy resin is modified with (meth) acrylic acid, and an epoxy A modified epoxy resin in which part or all of the epoxy group of the resin is modified with a modifying compound, wherein the modifying compound is an unsaturated aliphatic carboxylic acid (except for (meth) acrylic acid), carboxylic acid A resin that is one or more compounds selected from the group consisting of anhydrides (excluding (meth) acrylic anhydride), alcohols, and thiols is preferred.
  • the epoxy resin (excluding an epoxy resin having a (meth) acryloyl group) can be a raw material epoxy resin for obtaining a (meth) acrylate resin.
  • a modified epoxy resin in which part or all of the epoxy group of the epoxy resin is modified with (meth) acrylic acid is a component that can be obtained as a component other than the (meth) acrylate resin by the production method of the (meth) acrylate resin It is.
  • Modified epoxy resin which is one or more compounds selected from the group consisting of products (excluding (meth) acrylic anhydride), alcohols and thiols, depending on the method for producing (meth) acrylate resin, It is a component that can be obtained as a component other than the 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 (meth) acrylate 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.
  • (Meth) acrylate resin 8 170.0 g of bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 32.3 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.7 g of crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and triphenyl 262 mg of phosphine (Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 5 hours. 205.2g of (meth) acrylate resin 8 of a yellow transparent viscous substance was obtained.
  • EXA-850CRP bisphenol A type epoxy resin
  • methacrylic acid manufactured by Tokyo Chemical Industry Co., Ltd.
  • crotonic acid manufactured by Tokyo Chemical Industry Co., Ltd.
  • triphenyl 262 mg of phosphine Tokyo Chemical Industry Co., Ltd.
  • (Meth) acrylate resin 10 Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 16.1 g, 10-undecenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 11.5 g, and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 5 hours. 107.1g of (meth) acrylate resin 10 of yellow transparent viscous substance was obtained.
  • EXA-850CRP Bisphenol A type epoxy resin
  • methacrylic acid manufactured by Tokyo Chemical Industry Co., Ltd.
  • 10-undecenoic acid manufactured by Tokyo Chemical Industry Co., Ltd.
  • triphenylphosphine manufactured by Tokyo Chemical Industry Co., Ltd.
  • (Meth) acrylate resin 12 Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (Tokyo Chemical Industry Co., Ltd.) 5.4 g, 3-butenoic acid (Tokyo Chemical Industry Co., Ltd.) 16.1 g, and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 5 hours. 101.7g of (meth) acrylate resin 12 of yellow transparent viscous substance was obtained.
  • EXA-850CRP manufactured by DIC Corporation
  • (Meth) acrylate resin 14 Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (Tokyo Chemical Industry Co., Ltd.) 16.1 g, crotonic acid (Tokyo Chemical Industry Co., Ltd.) 10.7 g, and triphenyl 130 mg of phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 7 hours. 108.5g of (meth) acrylate resin 14 of a yellow transparent viscous substance was obtained.
  • EXA-850CRP manufactured by DIC Corporation
  • (Meth) acrylate resin 15 Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 21.5 g, crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.7 g, and triphenyl 130 mg of phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 7 hours. 112.0g of (meth) acrylate resin 15 of the yellow transparent viscous substance was obtained.
  • EXA-850CRP manufactured by DIC Corporation
  • (Meth) acrylate resin 16 Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (Tokyo Chemical Industry Co., Ltd.) 14.3 g, crotonic acid (Tokyo Chemical Industry Co., Ltd.) 14.3 g, and triphenyl 130 mg of phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 7 hours. 111.2g of (meth) acrylate resin 16 of the yellow transparent viscous substance was obtained.
  • EXA-850CRP manufactured by DIC Corporation
  • (Meth) acrylate resin 20 Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, phenol (Tokyo Chemical Industry Co., Ltd.) 11.8 g and triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) 130 mg were mixed at 100 ° C. Stir for 15 hours. 18.8 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 ° C. for 7 hours. 102.2g of (meth) acrylate resin 20 of a yellow transparent viscous substance was obtained.
  • EXA-850CRP Bisphenol A type epoxy resin
  • phenol Tokyo Chemical Industry Co., Ltd.
  • triphenylphosphine Tokyo Chemical Industry Co., Ltd. 130 mg were mixed at 100 ° C. Stir for 15 hours. 18.8 g of meth
  • (Meth) acrylate resin 21 Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.7 g, acetic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 12.7 g, and tri 130 mg of phenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 6 hours. 102.3g of (meth) acrylate resin 21 of yellow transparent viscous substance was obtained.
  • EXA-850CRP manufactured by DIC Corporation
  • (Meth) acrylate resin 22 Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.7 g, butyric anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 19.8 g, and tri 130 mg of phenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 6 hours. 108.3g of (meth) acrylate resin 22 of a yellow transparent viscous substance was obtained.
  • EXA-850CRP manufactured by DIC Corporation
  • (Meth) acrylate resin 23 Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.7 g, crotonic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 19.3 g, and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 6 hours. 99.5g of (meth) acrylate resin 23 of the yellow transparent viscous substance was obtained.
  • EXA-850CRP manufactured by DIC Corporation
  • 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.
  • Comparative (meth) acrylate 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. Comparison (meth) acrylate resin 2 of yellow transparent viscous material 265.0g was obtained.
  • (Meth) acrylate resin 24 114.0 g of epoxy resin A, 10.8 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.8 g of crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed. Stir at 100 ° C. for 7 hours. 128.0g of (meth) acrylate resin 24 of a yellow transparent viscous substance was obtained.
  • (Meth) acrylate resin 25 114.0 g of epoxy resin A, 10.8 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.8 g of 3-butenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) Mix and stir at 100 ° C. for 7 hours. 124.0g of (meth) acrylate resin 25 of a yellow transparent viscous substance was obtained.
  • (Meth) acrylate resin 26 114.0 g of epoxy resin A, 10.8 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 23.0 g of 10-undecenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) Mix and stir at 100 ° C. for 7 hours. 136.0g of (meth) acrylate resin 26 of the 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.
  • 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 4 The results of the epoxy equivalent and viscosity measurement are shown in Tables 1 to 4 together with the blending compositions of the curable resin compositions of Examples 1 to 26 and Comparative Examples 1 and 2.
  • Tables 5 to 8 show the results of adhesion strength measurements performed on some of the examples and comparative examples.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Epoxy Resins (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Liquid Crystal (AREA)
PCT/JP2018/013091 2017-03-31 2018-03-29 （メタ）アクリレート樹脂及びそれを含む硬化性樹脂組成物 WO2018181647A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020197028436A KR102267158B1 (ko) 2017-03-31 2018-03-29 (메트)아크릴레이트 수지 및 그것을 포함하는 경화성 수지 조성물
CN201880014468.2A CN110366570B (zh) 2017-03-31 2018-03-29 (甲基)丙烯酸酯树脂和包含该(甲基)丙烯酸酯树脂的固化性树脂组合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017070657A JP6601633B2 (ja) 2017-03-31 2017-03-31 （メタ）アクリレート樹脂及びそれを含む硬化性樹脂組成物
JP2017-070657 2017-03-31

Publications (1)

Publication Number Publication Date
WO2018181647A1 true WO2018181647A1 (ja) 2018-10-04

Family

ID=63677936

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/013091 WO2018181647A1 (ja) 2017-03-31 2018-03-29 （メタ）アクリレート樹脂及びそれを含む硬化性樹脂組成物

Country Status (5)

Country Link
JP (1) JP6601633B2 (enrdf_load_stackoverflow)
KR (1) KR102267158B1 (enrdf_load_stackoverflow)
CN (1) CN110366570B (enrdf_load_stackoverflow)
TW (1) TWI719297B (enrdf_load_stackoverflow)
WO (1) WO2018181647A1 (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115286968A (zh) * 2022-08-30 2022-11-04 铁科金化检测中心有限公司 一种预防纵连无砟高速铁路混凝土温度应力病害的反射隔热涂料及其制备方法和应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6601634B2 (ja) * 2017-03-31 2019-11-06 協立化学産業株式会社 変性樹脂及びそれを含む硬化性樹脂組成物
CN110563896A (zh) * 2019-09-12 2019-12-13 烟台艾格路电子科技有限公司 一种自由基和阳离子双重聚合uv光固化树脂及其制备方法
JP7680027B2 (ja) * 2021-10-20 2025-05-20 協立化学産業株式会社 変性樹脂を含む液晶シール剤及びその製造方法
KR102486314B1 (ko) * 2022-04-25 2023-01-10 주식회사 한솔케미칼 무용제형 열경화성 양자점 수지 조성물, 이로부터 제조된 양자점 수지 복합체, 이를 적용한 led 패키지 및 디스플레이 장치

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4855280A (enrdf_load_stackoverflow) * 1971-11-11 1973-08-03
JPS5116107A (ja) * 1974-07-31 1976-02-09 Mitsubishi Rayon Co Insatsuinkyojushisoseibutsu
JP2004143119A (ja) * 2002-10-28 2004-05-20 Shinnakamura Kagaku Kogyo Kk ウンデセン基を有する化合物、重合物、および組成物
JP2005187746A (ja) * 2003-12-26 2005-07-14 Toyo Ink Mfg Co Ltd 感光性組成物及び該感光性組成物を用いてなる積層体
JP2012188533A (ja) * 2011-03-10 2012-10-04 Hitachi Chemical Co Ltd 揺変性液状絶縁ワニス並びにそれを用いた電気機器絶縁物及び電動モーター
JP2013130873A (ja) * 2006-09-07 2013-07-04 Mitsui Chemicals Inc 液晶シール剤、およびそれを用いた液晶表示パネルの製造方法、ならびに液晶表示パネル
JP2016117887A (ja) * 2014-03-31 2016-06-30 協立化学産業株式会社 硬化後柔軟性に優れる硬化性樹脂、（メタ）アクリル化硬化性樹脂、及び液晶シール剤組成物

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5172321B2 (ja) 2006-12-26 2013-03-27 三井化学株式会社 液晶シール剤
KR101134635B1 (ko) * 2009-10-12 2012-04-09 금호석유화학 주식회사 액정 표시 소자용 실란트 조성물
JP5979972B2 (ja) 2012-05-17 2016-08-31 協立化学産業株式会社 エステル化エポキシ樹脂、その製造方法、及びそれを含む硬化性組成物
JP6601634B2 (ja) * 2017-03-31 2019-11-06 協立化学産業株式会社 変性樹脂及びそれを含む硬化性樹脂組成物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4855280A (enrdf_load_stackoverflow) * 1971-11-11 1973-08-03
JPS5116107A (ja) * 1974-07-31 1976-02-09 Mitsubishi Rayon Co Insatsuinkyojushisoseibutsu
JP2004143119A (ja) * 2002-10-28 2004-05-20 Shinnakamura Kagaku Kogyo Kk ウンデセン基を有する化合物、重合物、および組成物
JP2005187746A (ja) * 2003-12-26 2005-07-14 Toyo Ink Mfg Co Ltd 感光性組成物及び該感光性組成物を用いてなる積層体
JP2013130873A (ja) * 2006-09-07 2013-07-04 Mitsui Chemicals Inc 液晶シール剤、およびそれを用いた液晶表示パネルの製造方法、ならびに液晶表示パネル
JP2012188533A (ja) * 2011-03-10 2012-10-04 Hitachi Chemical Co Ltd 揺変性液状絶縁ワニス並びにそれを用いた電気機器絶縁物及び電動モーター
JP2016117887A (ja) * 2014-03-31 2016-06-30 協立化学産業株式会社 硬化後柔軟性に優れる硬化性樹脂、（メタ）アクリル化硬化性樹脂、及び液晶シール剤組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115286968A (zh) * 2022-08-30 2022-11-04 铁科金化检测中心有限公司 一种预防纵连无砟高速铁路混凝土温度应力病害的反射隔热涂料及其制备方法和应用

Also Published As

Publication number Publication date
KR102267158B1 (ko) 2021-06-22
TW201900711A (zh) 2019-01-01
TWI719297B (zh) 2021-02-21
JP6601633B2 (ja) 2019-11-06
JP2018172483A (ja) 2018-11-08
CN110366570A (zh) 2019-10-22
CN110366570B (zh) 2020-09-15
KR20190130581A (ko) 2019-11-22

Similar Documents

Publication Publication Date Title
JP6601633B2 (ja) （メタ）アクリレート樹脂及びそれを含む硬化性樹脂組成物
JP6248221B2 (ja) 硬化後柔軟性に優れる硬化性樹脂、（メタ）アクリル化硬化性樹脂、及び液晶シール剤組成物
CN113544183B (zh) 固化性树脂组合物
JP6601634B2 (ja) 変性樹脂及びそれを含む硬化性樹脂組成物
US20180134839A1 (en) Monomeric and oligomeric resins for one drop fill sealant application
JP6310852B2 (ja) グリシジルエーテル系化合物、液晶シール剤及びグリシジルエーテル系化合物の製造方法
JP5773782B2 (ja) 新規（メタ）アクリル樹脂及びそれを用いた樹脂組成物
JP2017125033A (ja) 光重合開始剤に適した化合物
JP7680027B2 (ja) 変性樹脂を含む液晶シール剤及びその製造方法
JP6643949B2 (ja) 新規（メタ）アクリル化合物及びそれを用いた樹脂組成物
KR102211198B1 (ko) 경화성 조성물, 액정용 씰제, 액정 패널, 및 액정 패널의 제조 방법
JP2017203830A (ja) 液晶シール剤及びそれを用いた液晶表示セル
JP6618186B2 (ja) 樹脂組成物および電子部品用接着剤
JP2017134124A5 (ja) 光硬化性樹脂組成物、表示素子シール剤、液晶表示素子シール剤、液晶表示パネル及び液晶表示パネルの製造方法
CN115003709B (zh) 化合物、化合物的制造方法及固化性组合物
JP2017203067A (ja) 樹脂組成物および電子部品用接着剤
TWI894142B (zh) 硬化性樹脂組合物
JP2024033212A (ja) 保管安定性に優れる硬化性樹脂、及びその製造方法
JP2018063274A (ja) 液晶シール剤及びそれを用いた液晶表示セル

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18776908

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20197028436

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18776908

Country of ref document: EP

Kind code of ref document: A1