WO2022014552A1 - Composition, cured product, and method for producing cured product - Google Patents

Composition, cured product, and method for producing cured product Download PDF

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Publication number
WO2022014552A1
WO2022014552A1 PCT/JP2021/026214 JP2021026214W WO2022014552A1 WO 2022014552 A1 WO2022014552 A1 WO 2022014552A1 JP 2021026214 W JP2021026214 W JP 2021026214W WO 2022014552 A1 WO2022014552 A1 WO 2022014552A1
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group
mass
parts
composition
adhesive strength
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PCT/JP2021/026214
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French (fr)
Japanese (ja)
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拓也 松本
泰延 大野
智幸 岩島
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株式会社Adeka
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/18Macromolecules 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
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22Di-epoxy compounds
    • C08G59/24Di-epoxy compounds carbocyclic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the present disclosure relates to a composition, a cured product thereof, and a method for producing the cured product.
  • Patent Document 1 discloses a thermosetting composition containing an epoxy compound and a filler.
  • Patent Document 2 discloses a photocurable composition containing an epoxy resin and a filler.
  • thermosetting composition as in Patent Document 1 Due to the recent progress in miniaturization of electronic parts and optical parts, when a thermosetting composition as in Patent Document 1 is used as an adhesive, the members around the bonded portion are removed by heat treatment during heat curing. There is a problem that heat deterioration may occur.
  • a photocurable composition as in Patent Document 2 is used as an adhesive, the defect of thermal deterioration can be reduced, but the deep curability is low and it may be difficult to form a thick adhesive portion. ..
  • the present disclosure has been made in view of the above problems, and an object of the present disclosure is to provide a composition having excellent dimensional stability, adhesive strength and deep curability.
  • the present inventor has made diligent studies, and by combining a specific cyclic ether component, a hydroxyl group-containing component, a predetermined amount of a filler and a photoacid generator, an excellent balance between dimensional stability, adhesive strength and deep curability is excellent. It has been found that the composition can be obtained.
  • the present disclosure is a composition containing a cyclic ether component, a hydroxyl group-containing component, a filler, and a photoacid generator, wherein the cyclic ether component contains an alicyclic epoxy compound and the above fat.
  • the content of the cyclic epoxy compound is 80 parts by mass or more in 100 parts by mass of the cyclic ether component
  • the content of the filler is 100 parts by mass in total of the cyclic ether component and the hydroxyl group-containing component. , 40 parts by mass or more are provided.
  • the above composition has an excellent balance of dimensional stability, adhesive strength and deep curability.
  • the average particle size of the filler is 1 ⁇ m or more and 100 ⁇ m or less. This is because the above composition has excellent coatability.
  • the filler contains particles coated with a surface treatment layer.
  • the above composition has an excellent balance of dimensional stability, adhesive strength, deep curability, and dispersibility.
  • the hydroxyl group-containing component contains a compound having 3 or more hydroxyl groups. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the hydroxyl group-containing component contains an aliphatic alcohol compound. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the content of the hydroxyl group-containing component is preferably 5 parts by mass or more and 50 parts by mass or less in a total of 100 parts by mass of the cyclic ether component and the hydroxyl group-containing component. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in deep curability.
  • the alicyclic epoxy compound contains a compound having two or more cycloalkene oxide structures. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the above composition is an adhesive. This is because the above composition can more effectively exert the effect of having an excellent balance of dimensional stability, adhesive strength and deep curability.
  • the present disclosure provides a cured product of the above composition.
  • the present disclosure provides a method for producing a cured product, which comprises a light irradiation step of irradiating the above-mentioned composition with light.
  • the present disclosure can provide a composition excellent in dimensional stability, adhesive strength and deep curability.
  • FIG. 1 (a) is a schematic view of an evaluation sample viewed from a plan view on the glass substrate side
  • FIG. 1 (b) is a sectional view taken along line AA of FIG. 1 (a).
  • the present disclosure relates to a composition, a cured product using the composition, and a method for producing the cured product.
  • composition of the present disclosure is a composition containing a cyclic ether component, a hydroxyl group-containing component, a filler, and a photoacid generator, and the cyclic ether component contains an alicyclic epoxy compound and is described above.
  • the content of the alicyclic epoxy compound is 80 parts by mass or more in 100 parts by mass of the cyclic ether component
  • the content of the filler is 100 parts by mass in total of the cyclic ether component and the hydroxyl group-containing component. It is characterized by having 40 parts by mass or more.
  • the balance between dimensional stability, adhesive strength and deep curability is excellent.
  • the reason why such an effect can be obtained by combining each of the above-mentioned components is not clear, but it is presumed as follows.
  • the curing reaction can be sufficiently advanced not only on the surface of the coating film but also in the deep part, and the above composition can exhibit excellent deep curing property.
  • the above composition forms a cured product in which the cyclic ether component and the hydroxyl group-containing component are sufficiently cured, and forms a cured product having a uniform cured state on the surface side and the deep side. It becomes possible to do such things.
  • the cured product has excellent dimensional stability and adhesive strength. Therefore, by combining each specific component, the above composition has an excellent balance of dimensional stability, adhesive strength and deep curability.
  • the viscosity becomes high and the dispersibility and coatability deteriorate.
  • a predetermined amount of the filler by combining a predetermined amount of filler with a specific cyclic ether component, a hydroxyl group-containing component and a photoacid generator, an increase in viscosity can be suppressed, and the above composition is excellent in dispersibility and coatability. It will be. Further, since the composition can exhibit the excellent deep curability as described above, the composition can be stably cured even when the heat treatment is not performed after the exposure or the heating temperature in the heat treatment is low. Demonstrates excellent dimensional stability, adhesive strength and deep curability. Therefore, the composition has less deterioration and deformation of the adherend, and has excellent positional accuracy.
  • composition of the present disclosure comprises a specific cyclic ether component, a hydroxyl group-containing component, a predetermined amount of a filler and a photoacid generator.
  • the cyclic ether component refers to a component that is one or more of a compound having a cyclic ether group (hereinafter, may be referred to as a cyclic ether compound).
  • the cyclic ether group may be any one having at least one ether bond in the ring structure, and examples thereof include an epoxy group and an oxetanyl group. That is, examples of the cyclic ether compound include an epoxy compound having an epoxy group and an oxetane compound having an oxetane group.
  • the epoxy compound includes all compounds having an epoxy group, and a compound containing both an epoxy group and an oxetane group corresponds to an epoxy compound.
  • the compound having a cyclic ether group and a hydroxyl group shall be included in the cyclic ether compound and shall not correspond to the hydroxyl group-containing component. Further, the compound having a cyclic ether group and an ethylenically unsaturated group shall be included in the cyclic ether compound. Examples of the ethylenically unsaturated group include an acryloyl group, a methacryloyl group, and a vinyl group. Further, a compound having an alkoxysilyl group together with a cyclic ether group is usually classified as a silane coupling agent, and does not correspond to the above cyclic ether compound.
  • compounds having an alkoxysilyl group together with an epoxy group such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane are usually used.
  • It is classified as a silane coupling agent and does not correspond to an epoxy compound.
  • those having a cyclic ether group are classified as fillers and do not correspond to the cyclic ether component.
  • a silane coupling agent having an epoxy group may be bonded to the surface of the particles, and a surface treatment layer having an epoxy group formed on the surface of the particles may be used.
  • Such a filler having an epoxy group on the surface of the particles does not fall under the epoxy compound as the cyclic ether component in the present disclosure.
  • the photoacid generator those having a cyclic ether group are also classified as photoacid generators and do not correspond to the cyclic ether component.
  • the cyclic ether component contains a predetermined amount of an alicyclic epoxy compound as an epoxy compound.
  • the alicyclic epoxy compound is a compound having a cycloalkene oxide structure and no aromatic ring.
  • the cycloalkene oxide structure is obtained by epoxidizing a cyclohexene ring-containing compound or a cyclopentene ring-containing compound with an oxidizing agent.
  • the aliphatic ring and the epoxy ring are one of the ring structures. It is a structure that shares a part.
  • the alicyclic epoxy compound may be any compound having an epoxy group having a cycloalkene oxide structure.
  • those having a cycloalkene oxide structure and an aliphatic ring and an epoxy group that does not share a part of the ring structure are also alicyclic epoxies. It corresponds to a compound.
  • the alicyclic epoxy compound has only a cycloalkene oxide structure as an epoxy group. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the number of cycloalkene oxide structures contained in the alicyclic epoxy compound may be 1 or more, but 2 or more, that is, the alicyclic epoxy compound is a compound having 2 or more cycloalkene oxide structures. It is preferably 2 or more, 4 or less, particularly preferably 2 or 3, and particularly preferably 2.
  • the above composition is excellent in the balance of dimensional stability, adhesive strength and deep curability, and in particular, excellent in adhesive strength and deep curability. Because it becomes.
  • Examples of the cycloalkene oxide structure contained in the alicyclic epoxy compound include a cyclopentene oxide structure (5-membered ring) and a cyclohexene oxide structure (6-membered ring) depending on the number of carbon atoms constituting the cycloalkene.
  • the alicyclic epoxy compound has two or more cycloalkene oxide structures
  • the aliphatic rings constituting each cycloalkene oxide structure are condensed in a total of three or more rings via other aliphatic rings. It is intended to include a structure (in a fused ring of 3 or more rings, a ring structure in which two or more cycloalkene oxide structures are linked by condensation on the other aliphatic ring).
  • the alicyclic epoxy compound contains a cyclohexene oxide structure as a cycloalkene oxide structure. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • Suitable alicyclic epoxy compounds are compounds in which the number of cycloalkene oxide structures in the molecule is two, and have a condensed structure between cycloalkene oxide structures, or cycloalkene oxide. Examples thereof include compounds having a non-condensable cycloalkene oxide structure which does not have a condensed structure between structures. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the condensed structure of cycloalkene oxide structures has two cycloalkene oxide structures, and the aliphatic rings constituting each structure are condensed by sharing two or more atoms with each other. Point to.
  • the non-condensed cycloalkene oxide structure refers to a structure in which the aliphatic ring constituting the cycloalkene oxide structure does not have a structure condensed with other rings.
  • the alicyclic epoxy compound is preferably a compound represented by the following general formula (1). This is because the above composition is excellent in the balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability, and is also excellent in availability and storage stability. be.
  • Y 1 represents a divalent linking group having a direct bond or one or more atoms.
  • Examples of the linking group represented by Y 1 include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and a group in which a plurality of these are linked.
  • the "group in which a plurality of these are linked" is a group selected from a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group and an amide group, and is a group other than the divalent hydrocarbon group.
  • they can be groups bonded so as not to be adjacent to each other.
  • two or more groups of the same type may be combined, such as ester bond-divalent hydrocarbon group-ester bond-divalent hydrocarbon group.
  • the divalent hydrocarbon group a group obtained by removing one hydrogen atom from a monovalent hydrocarbon group having 1 to 20 carbon atoms can be used.
  • the hydrocarbon group having 1 to 20 monovalent carbon atoms include an aliphatic hydrocarbon group having 1 to 20 monovalent carbon atoms and an aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms.
  • the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be any hydrocarbon group that does not contain an aromatic hydrocarbon ring, for example, an alkyl group having 1 to 20 carbon atoms and 3 carbon atoms. Examples thereof include a cycloalkyl group having about 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms.
  • Alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-pentyl, tert-pentyl, cyclopentyl, hexyl, and the like.
  • Examples thereof include 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl, adamantyl and the like.
  • the cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms.
  • Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
  • the cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which the hydrogen atom of the alkyl group is replaced with a cycloalkyl group.
  • Examples of such a cycloalkylalkyl group having 4 to 20 carbon atoms include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl and the like.
  • alkenyl group having 2 to 20 carbon atoms examples include vinyl, ethylene, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, and the like.
  • 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl and 4,8,12-tetradecatorienylallyl, cyclopentaziniel, etc. Can be mentioned.
  • the monovalent aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms may be any as long as it contains an aromatic hydrocarbon ring and does not contain a heterocycle.
  • an aryl group having 6 to 20 carbon atoms. A group having 7 to 20 carbon atoms, which is a combination of an aryl group and the above-mentioned aliphatic hydrocarbon group, and the like can be mentioned.
  • the "aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms" defines the number of carbon atoms of the "aromatic hydrocarbon ring-containing group” instead of the "aromatic hydrocarbon". The same applies to other carbon atom numbers.
  • the aryl group having 6 to 20 carbon atoms is a group having an aromatic hydrocarbon ring and having aromaticity, and at least one of the carbon atoms on the aromatic hydrocarbon ring in the group has a cyclohexene oxide structure. It is a group to be bound.
  • Examples of the aryl group include monocyclic aromatic ring groups such as phenyl and trill groups (hereinafter, may be referred to as monocyclic aromatic hydrocarbon ring groups), naphthyl, anthracenyl, phenanthryl, fluorenyl, pyrenyl and the like.
  • a fused ring group of an aromatic ring (hereinafter, may be referred to as a fused aromatic hydrocarbon group), two or more monocyclic aromatic rings such as biphenyl and benzophenone, or a fused ring thereof is a single bond or a carbonyl.
  • Examples thereof include a group obtained by removing one or more hydrogen atoms from a compound bonded via a linking group such as a group (-CO-) or a sulfide group (-S-).
  • a group in which one or more hydrogen atoms in the aromatic hydrocarbon ring is substituted with an alkyl group, such as a tolyl group, is contained in the aryl group. Further, the tolyl group corresponds to a monocyclic aromatic hydrocarbon ring group.
  • one or two or more hydrogen atoms in the alkyl group are substituted with an aryl group, or the following general group.
  • Examples thereof include a divalent group represented by the formula (11).
  • Ar 1 and Ar 2 each independently represent an aryl group.
  • R 11 represents a divalent alkylene group having 1 to 10 carbon atoms. * Represents the joint location. )
  • the divalent alkylene group having 1 to 10 carbon atoms used in R 11 has a predetermined number of carbon atoms among the above-mentioned alkyl groups having 1 to 20 carbon atoms minus one hydrogen atom. Can be used.
  • the linking group represented by Y 1 is preferably a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or a group in which a plurality of these are linked.
  • a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group or a group in which a plurality of these are linked is preferable, and in particular, a divalent hydrocarbon group, an ester bond or a plurality of these are linked.
  • the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • a group in which one or more divalent hydrocarbon groups and one or two ester bonds are linked for example, a group in which an ester bond and a divalent hydrocarbon group are bonded; a divalent group. Examples thereof include a hydrocarbon group, an ester bond, a divalent hydrocarbon group, an ester bond, and a group in which a divalent hydrocarbon group is bonded in this order.
  • the number of carbon atoms of the linking group represented by Y 1 is preferably 20 or less, more preferably 1 or more and 15 or less, and particularly preferably 2 or more and 10 or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the hydrocarbon group used for Y 1 is preferably an aliphatic hydrocarbon group, and more preferably a group obtained by removing one hydrogen atom from an alkyl group, that is, an alkylene group. In particular, it is preferably a linear alkylene group. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability.
  • the hydrocarbon group used for Y 1 may be substituted or unsubstituted with one or more hydrogen atoms, but is preferably unsubstituted. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability.
  • Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxy-1-methylcyclohexyl-3 as compounds having two or more cycloalkene oxide structures.
  • examples of the compound having one cycloalkene oxide structure include 3,4-epoxycyclohexylmethylacrylate, 3,4-epoxycyclohexylmethylmethacrylate, and methyl 3,4-epoxycyclohexanecarboxylate.
  • alicyclic epoxy compounds include UVR6105, UVR6110 and UVR6128 manufactured by Union Carbite; Daicel Chemical Co., Ltd., Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 2000, Celoxide 3000, Cyclomer A200, Cyclomer M100, Cyclomer M101, Epolide GT-301, Epolide GT-302, Epolide 401, Epolide 403, ETHB, Epolide HD300; THI-DE, DE-102, DE-103 manufactured by JXTG Energy Co., Ltd. and the like can be mentioned.
  • the content of the alicyclic epoxy compound is 80 parts by mass or more, preferably 85 parts by mass or more, and particularly preferably 90 parts by mass or more, in 100 parts by mass of the cyclic ether component. It is preferably 95 parts by mass or more, particularly preferably 98 parts by mass or more, and particularly preferably 100 parts by mass, that is, it contains only an alicyclic epoxy compound as a cyclic ether component. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the content of the alicyclic epoxy compound is preferably 50 parts by mass or more and 95 parts by mass or less, particularly 60 parts by mass or more and 90 parts by mass or less, in a total of 100 parts by mass of the cyclic ether component and the hydroxyl group-containing component. It is preferably 70 parts by mass or more and 85 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the content of the alicyclic epoxy compound is preferably 1 part by mass or more, and more preferably 3 parts by mass or more and 50 parts by mass or less, particularly particularly, in 100 parts by mass of the solid content of the above composition. It is preferably 5 parts by mass or more and 45 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the solid content of the above composition indicates the total of all the components other than the solvent in the composition.
  • the content of the alicyclic epoxy compound is preferably 1 part by mass or more, preferably 3 parts by mass or more and 50 parts by mass or less, and particularly 5 parts by mass or more in 100 parts by mass of the composition. It is preferably 45 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the cyclic ether component may contain a cyclic ether compound other than the alicyclic epoxy compound (hereinafter, may be referred to as another cyclic ether compound).
  • the cyclic ether compound include an aromatic epoxy compound, an epoxy compound other than an alicyclic epoxy compound such as an aliphatic epoxy compound, and an oxetane compound.
  • the content of the other cyclic ether compound is preferably 18 parts by mass or less in 100 parts by mass of the cyclic ether component, and is preferably 1 part by mass or more and 15 parts by mass or less. Is preferable. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the aromatic epoxy compound has an aromatic ring and an epoxy group, and does not have a cycloalkene oxide structure.
  • aromatic epoxy compound examples include polyhydric phenol having at least one aromatic ring or polyglycidyl ether of an alkylene oxide adduct thereof, for example, bisphenol A, bisphenol F, bisphenol E, or alkylene oxide thereof. Examples thereof include glycidyl ether of the added compound and an epoxy novolak resin (phenol novolak type epoxy compound).
  • glycidyl ether of an aromatic compound having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol
  • poly of an aromatic compound having two or more alcoholic hydroxyl groups such as benzenedimethanol, benzenediethanol and benzenedibutanol.
  • Glycidyl ester of benzoic acids such as benzoic acid, toluic acid and naphthoic acid; styrene Examples thereof include an epoxidized product of oxide or divinylbenzene.
  • aromatic epoxy compound examples include those described in JP-A-2019-137727.
  • the aromatic epoxy compound is a compound having a bisphenol structure such as a bisphenol A type structure, a bisphenol F type structure, and a bisphenol E type structure.
  • a bisphenol structure such as a bisphenol A type structure, a bisphenol F type structure, and a bisphenol E type structure.
  • the content of the aromatic epoxy compound may be such that desired dimensional stability, adhesive strength and deep curability can be obtained.
  • the cyclic ether component may be used. It is preferably 18 parts by mass or less, and preferably 1 part by mass or more and 15 parts by mass or less in 100 parts by mass. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • (2-2) Aliphatic Epoxy Compound The above-mentioned aliphatic epoxy resin has an epoxy group and does not contain a cycloalkene oxide structure and an aromatic ring.
  • Examples of such an aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyvalent alcohols or alkylene oxide adducts thereof; polyglycidyl esters of aliphatic long-chain polybasic acids; glycidyl acrylates or glycidyl methacrylates synthesized by vinyl polymerization. Homopolymers; examples thereof include copolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate and other vinyl monomers.
  • Typical compounds include polyhydric alcohols such as glycidyl ether of diol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, and hexaglycidyl ether of dipentaerythritol, and propylene.
  • Polyglycidyl ether which is a polyether polyol obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as glycol, trimethylolpropane, and glycerin, and diglycidyl ester of aliphatic long-chain dibasic acid. Can be mentioned.
  • examples of the aliphatic epoxy compound include hydrogenated additives of aromatic epoxy compounds such as hydrogenated bisphenol A diglycidyl ether.
  • Examples of the aliphatic epoxy compound include cycloalkyls derived from epoxycycloalkyl rings such as 1,2-epoxy-4- (2-oxylanyl) cyclohexane adducts of 2,2-bis (hydroxymethyl) -1-butanol.
  • Examples thereof include compounds having a structure in which an oxylanyl group is directly bonded to a ring by a single bond as a constituent unit, and a structure in which epoxy groups of an epoxycycloalkyl ring are polymerized as a main chain structure.
  • Examples of commercially available products that can be suitably used as the above aliphatic epoxy compounds include those described in JP-A-2019-137727.
  • the content of the aliphatic epoxy compound may be such that desired dimensional stability, adhesive strength and deep curability can be obtained, and for example, the cyclic ether component may be obtained. It is preferably 18 parts by mass or less, and preferably 1 part by mass or more and 15 parts by mass or less in 100 parts by mass. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • Oxetane compound is a compound having an oxetaneyl group and no epoxy group.
  • examples of such an oxetane compound include those described in JP-A-2019-137727.
  • Cyclic ether component The content of the cyclic ether component is preferably 50 parts by mass or more and 95 parts by mass or less, particularly 60 parts by mass or more and 90 parts by mass in a total of 100 parts by mass of the cyclic ether component and the hydroxyl group-containing component. It is preferably 70 parts by mass or less, and particularly preferably 70 parts by mass or more and 85 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the content of the cyclic ether component is preferably 1 part by mass or more, and more preferably 3 parts by mass or more and 50 parts by mass or less, particularly 5 parts by mass, in 100 parts by mass of the solid content of the above composition. It is preferably 4 parts or more and 45 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the content of the cyclic ether component is preferably 50 parts by mass or more and 95 parts by mass or less, and particularly 60 parts by mass or more and 90 parts by mass or less in 100 parts by mass of the solid content excluding the filler of the above composition. It is preferable, and in particular, it is preferably 65 parts by mass or more and 85 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the solid content excluding the filler of the composition includes all the components other than the filler and the solvent of the composition.
  • the content of the cyclic ether component is preferably 1 part by mass or more, preferably 3 parts by mass or more and 50 parts by mass or less, and particularly 5 parts by mass or more and 45 parts by mass in 100 parts by mass of the composition. It is preferably less than or equal to a portion. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the hydroxyl group-containing component refers to a component that is one or more of compounds having a hydroxyl group. Even if it has a hydroxyl group, the component corresponding to the filler or photoacid generator described later is not included in the hydroxyl group-containing component.
  • the hydroxyl group of the compound having a hydroxyl group either an alcoholic hydroxyl group or a phenolic hydroxyl group can be used, but it is preferable that the hydroxyl group is an alcoholic hydroxyl group, that is, the compound having a hydroxyl group is an alcohol compound. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability. Further, the above composition is excellent in storage stability.
  • the hydroxyl group of the compound having a hydroxyl group may be any of a primary hydroxyl group, a secondary hydroxyl group, and a tertiary hydroxyl group, but preferably contains a primary hydroxyl group, and the number of hydroxyl groups in one molecule is two or more. In some cases, it is preferable that all the hydroxyl groups are primary hydroxyl groups. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability. Further, the above composition is excellent in storage stability.
  • the compound having a hydroxyl group may be an aromatic compound having an aromatic ring, but is preferably an aliphatic compound having no aromatic ring. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the compound having a hydroxyl group is preferably an aliphatic compound having an alcoholic hydroxyl group, that is, an aliphatic alcohol compound. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • such an aliphatic alcohol compound is a compound having an alcoholic hydroxyl group and neither an aromatic hydrocarbon ring nor an aromatic heterocycle, and is, for example, trimethylolpropane as a polyol monomer described later.
  • polyester polyol examples include Praxel 303 manufactured by Daicel Co., Ltd., which will be described later, and examples of the polyether polyol include polyethylene glycol described later.
  • the compound having a hydroxyl group may have one or more hydroxyl groups in one molecule, but is preferably a compound having two or more hydroxyl groups, that is, a polyol.
  • the compound having a hydroxyl group is preferably a compound having 3 or more hydroxyl groups, particularly preferably a compound having 3 or more and 10 or less hydroxyl groups, and particularly preferably 3 or less hydroxyl groups.
  • it is preferably a compound having 4 hydroxyl groups, and particularly preferably a compound having 3 hydroxyl groups. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the molecular weight of the compound having a hydroxyl group may be any as long as it can obtain desired dimensional stability, adhesive strength and deep curability, but is preferably 50 or more and 30,000 or less, and above all, 80 or more and 15 It is preferably 000 or less, more preferably 100 or more and 10,000 or less, particularly preferably 150 or more and 5,000 or less, and particularly preferably 200 or more and 3,000 or less. .. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability. In some cases, the molecular weight may be 1500 or less, 1000 or less, 500 or less, or 400 or less.
  • the molecular weight refers to the weight average molecular weight when the compound having a hydroxyl group has a repeating unit in the molecular structure.
  • the weight average molecular weight can be determined by gel permeation chromatography (GPC) as a standard polystyrene conversion value.
  • GPC gel permeation chromatography
  • Mw for example, GPC (LC-2000plus series) manufactured by JASCO Corporation is used, the elution solvent is tetrahydrofuran, and the polystyrene standard for calibration curve is Mw37200, 13700, 9490, 5430, 3120, 1010, 589 (manufactured by Toso).
  • the measurement column can be measured and obtained as KF-803L (manufactured by Showa Denko). Further, the measurement temperature can be 40 ° C. and the flow rate can be 1.0 mL / min.
  • the hydroxyl value (mgKOH / g) of the compound having a hydroxyl group may be any one that can obtain desired dimensional stability, adhesive strength and deep curability, and is, for example, 100 mgKOH / g or more and 2,000 mgKOH / g or less. It is preferably 150 mgKOH / g or more and 1,500 mgKOH / g or less, more preferably 250 mgKOH / g or more and 1,000 mgKOH / g or less, and more preferably 350 mgKOH / g or more and 800 mgKOH / g or less.
  • composition is preferably 400 mgKOH / g or more and 700 mgKOH / g or less, and more preferably 450 mgKOH / g or more and 600 mgKOH / g or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the number of carbon atoms between adjacent hydroxyl groups may be 1 or more, preferably 3 or more, particularly preferably 5 or more, and particularly particularly. It is preferably 6 or more. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the number of carbon atoms between adjacent hydroxyl groups refers to the number of carbon atoms that pass through the linking group connecting the hydroxyl groups so as to have the minimum number of atoms.
  • the number of carbon atoms between adjacent hydroxyl groups is 1 in the case of an ortho form, 2 in the case of a meta form, and 2 in the case of a para form. Is 3.
  • the number of carbon atoms between the adjacent hydroxyl groups indicates the number of combinations of hydroxyl groups having the minimum number of carbon atoms between the adjacent hydroxyl groups. ..
  • the number of carbon atoms between adjacent hydroxyl groups is 3.
  • Examples of the polyol used as a compound having a hydroxyl group include a (poly) ester polyol having an ester skeleton (preferably a polyester skeleton) in the molecule, and a (poly) ether having an ether skeleton (preferably a polyether skeleton) in the molecule.
  • Polyols, (poly) carbonate polyols having a carbonate skeleton (preferably polycarbonate skeleton) in the molecule, (poly) ester skeletons, (poly) ether skeletons, polyol monomers having no (poly) carbonate skeleton, etc. Can be mentioned.
  • the ester skeleton has a structure having an ester bond, and refers to, for example, a structure represented by the following general formula (A-1).
  • the polyester skeleton refers to a structure in which a plurality of ester bonds are linked by a group containing a carbon atom, and an example thereof includes a structure represented by the following general formula (A-1) in which na is 2 or more.
  • (Poly) ester polyol skeleton such as the formula (22) described later can be mentioned.
  • Ras is a divalent linking group having 1 to 20 carbon atoms
  • na is an integer of 1 or more.
  • L1 is -COO- or -OCO-.
  • na is 2 or more, a plurality.
  • the existing Ras may be the same or different from each other, and the plurality of L1s may be the same or different from each other. * Indicates a joint location.
  • the ether skeleton refers to a structure having an ether bond, for example, a structure represented by the following general formula (B1).
  • the polyether skeleton refers to a structure in which a plurality of ether bonds are linked by a group containing a carbon atom, and an example thereof is a structure represented by the following general formula (B-1) in which nb is 2 or more.
  • Rb is a divalent linking group having 1 to 20 carbon atoms, and nb is an integer of 1 or more. When nb is 2 or more, a plurality of Rbs existing may be the same or different from each other. * Indicates the joint location.
  • the carbonate skeleton refers to a structure having a carbonate bond, for example, a structure represented by the following general formula (C-1).
  • the polycarbonate skeleton refers to a structure in which a plurality of carbonate bonds are linked by a group containing a carbon atom, and an example thereof includes a structure represented by the following general formula (C-1) in which nc is 2 or more.
  • Rc is a divalent linking group having 1 to 20 carbon atoms, and nc is an integer of 1 or more. When nc is 2 or more, a plurality of Rc existing may be the same or different from each other. * Indicates the joint location.
  • the linking group represented by Ra, Rb and Rc is a divalent hydrocarbon group having 1 to 20 carbon atoms, or a divalent group in which the methylene group of the divalent hydrocarbon group is selected from the following group 1. Therefore, a group in which the divalent groups are substituted under the condition that they are not adjacent to each other can be mentioned.
  • the hydrocarbon group having 1 to 20 carbon atoms used for Ra, Rb and Rc can be the same as that used for Y 1 in the above general formula (1).
  • the polyol examples include a phenoxy resin, a bisphenol type high molecular weight epoxy resin, polybutadienes having a hydroxyl group, and an acrylic polyol.
  • the polyol is preferably a (poly) ester polyol, a (poly) ether polyol or a polyol monomer, and more preferably a (poly) ester polyol or a (poly) ether polyol. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the polyol monomer is a compound having no (poly) ester skeleton, (poly) ether skeleton, or (poly) carbonate skeleton, and for example, a compound represented by the following general formula (21) may be used. can.
  • R 1 represents a hydrocarbon group having n1 valence and 1 to 20 carbon atoms.
  • n1 represents an integer of 2 or more.
  • hydrocarbon group having 1 to 20 n1-valent carbon atoms used as R 1 a group obtained by removing n1-1 hydrogen atoms from the hydrocarbon group having 1 to 20 monovalent carbon atoms can be used. can.
  • the hydrocarbon group having a monovalent carbon atom number of 1 to 20 can be the same as that used for Y 1 in the above general formula (1).
  • the hydrocarbon group used for R 1 is preferably an aliphatic hydrocarbon group, and more preferably a group obtained by removing n1-1 hydrogen atoms from an alkyl group. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the number of carbon atoms of the hydrocarbon group used for R 1 may be 1 to 20, preferably 2 to 15, particularly preferably 3 to 10, and particularly 4 to 8. Is preferable. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • n1 may be 2 or more, and may be the same as those listed as the preferable number of hydroxyl groups of the compound having a hydroxyl group. Specifically, n1 is preferably 3 or more and 10 or less, preferably 3 or 4, and particularly preferably 3. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • polyol monomer examples include ethylene glycol, diethylene glycol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,3-propanediol, and 1,4-cyclohexanedimethanol.
  • Aromatic rings such as propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol, ditrimethylolpropane, mannitol, sorbitol, and pentaerythritol.
  • the polyol monomer examples include compounds having a bisphenol structure such as bisphenol A and bisphenol E, and compounds having an aromatic ring such as compounds having a biphenyl structure such as biphenol.
  • the (poly) ester polyol is a compound having a (poly) ester skeleton, and for example, a compound represented by the following general formula (22) can be used.
  • R 2 represents an n2-valent hydrocarbon group having 1 to 20 carbon atoms.
  • n2 represents an integer of 2 or more and represents X 2 is a group represented by the following general formula (22-1) independently of each other. At least one of X 2 is an integer in which n3 in the equation (22-1) is 1 or more.
  • R 3 represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
  • n3 represents an integer of 0 or 1 or more, and * represents a joint location.
  • n2-valent carbon atom number 1 to 20 hydrocarbon group used for R 2 a group obtained by removing n2-1 hydrogen atoms from the monovalent carbon atom number 1 to 20 carbon atom group may be used.
  • the hydrocarbon group having a monovalent carbon atom number of 1 to 20 can be the same as that used for Y 1 in the above general formula (1).
  • the hydrocarbon group used for R 2 is preferably an aliphatic hydrocarbon group, and more preferably a group obtained by removing n2-1 hydrogen atoms from an alkyl group. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the number of carbon atoms of the hydrocarbon group used for R 2 may be 1 to 20, preferably 2 to 15, particularly preferably 3 to 10, and particularly 3 to 8. Is preferable. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the plurality of existing R 3 and n 3 may be the same or different.
  • the hydrocarbon group used for R 3 is preferably an aliphatic hydrocarbon group, and more preferably a group obtained by removing one hydrogen atom from an alkyl group. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the number of carbon atoms of the hydrocarbon group used for R 3 may be 1 to 20, preferably 2 to 10, particularly preferably 3 to 8, and particularly 4 to 6. Is preferable. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • n2 may be 2 or more, and may be the same as those listed as the preferable number of hydroxyl groups of the compound having a hydroxyl group. Specifically, n2 is preferably 3 or more and 10 or less, preferably 3 or 4, and particularly preferably 3. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the n3 may be 0 or 1 or more, and the upper limit thereof may be 30 or less.
  • a plurality of n3s existing in one molecule may be the same or different.
  • the total amount of n3 in the compound represented by the general formula (22) is preferably 30 or less, more preferably 1 or more and 20 or less, and particularly 1 or more and 15 or less. It is particularly preferable that the amount is 1 or more and 10 or less, and particularly preferably 1 or more and 5 or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • polyester polyols including compounds represented by the general formula (22) and having a total of n3 of 2 or more, are a condensation polymer of a polyol and a polycarboxylic acid or a hydroxycarboxylic acid; ring-opening of the polyol and the lactones.
  • examples include polymers.
  • Examples of the polyol that can be used for synthesizing such a polyester polyol include the above-mentioned polyol monomer.
  • polycarboxylic acid and hydroxycarboxylic acid that can be used in the synthesis of polyester polyols include the compounds described in JP-A-2019-052231.
  • Examples of the (poly) ether polyol include a multimer of the above-mentioned polyol monomer; an addition reaction product of the polyol monomer and an alkylene oxide such as ethylene oxide; and a ring-opening polymer of a cyclic ether such as tetrahydrofuran.
  • a preferred polyether polyol having 3 or more hydroxyl groups includes a polyether polyol obtained by adding propylene oxide and / or ethylene oxide to a polyol monomer such as glycerin or trimethylolpropane.
  • Examples of the (poly) ether polyol include ditrimethylolpropane (4-functional) and dipentaerythritol (6-functional).
  • R 301 represents a hydrocarbon group having n 301 valence and 1 to 20 carbon atoms.
  • n 301 represents an integer of 2 or more.
  • Each of X 301 is a group represented by the following formula (23-1) independently. At least one of X 301 is an integer in which n5 or m5 in the equation (23-1) is 1 or more.
  • R 302 and R 303 each independently represent a divalent hydrocarbon group having 2 to 4 carbon atoms.
  • n5 and m5 independently represent an integer of 0 or 1 or more, and * represents a joint location.
  • n 301- valent hydrocarbon group having 1 to 20 carbon atoms used in R 301 a group obtained by removing n 301-1 hydrogen atoms from the monovalent hydrocarbon group having 1 to 20 carbon atoms is used. be able to.
  • the hydrocarbon group having a monovalent carbon atom number of 1 to 20 can be the same as that used for Y 1 in the above general formula (1).
  • the hydrocarbon group used for R 301 is preferably an aliphatic hydrocarbon group, and more preferably a group obtained by removing n301-1 hydrogen atoms from an alkyl group. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the number of carbon atoms of the hydrocarbon group used in R 301 may be 1 to 20, but preferably 2 to 15, particularly preferably 3 to 10, and particularly 3 to 8. Is preferable. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • R 302 and R 303 include an alkylene group.
  • R 302 is propylene and R 303 is ethylene.
  • the n 301 may be 2 or more, and may be the same as those listed as the preferable number of hydroxyl groups of the compound having a hydroxyl group.
  • n 301 is preferably 3 or more and 10 or less, preferably 3 or 4, and particularly preferably 3. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the total of n5 and m5 in the formula (23-1) is preferably 2 or more, more preferably 15 or more, and n5 in the compound represented by the general formula (23).
  • the total of m5 and m5 is preferably 45 or more. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • polycarbonate polyol examples include those obtained by using the above-mentioned polyol monomer and using a phosgene method, a carbonate exchange reaction, or the like.
  • polyester polyols examples include the products described in JP-A-2019-052231.
  • the content of the hydroxyl group-containing component may be any as long as it can obtain desired dimensional stability, adhesive strength and deep curability, but 1 mass in 100 parts by mass of the cyclic ether component and the hydroxyl group-containing component in total. It is preferably 5 parts by mass or more and 50 parts by mass or less, particularly preferably 5 parts by mass or more and 40 parts by mass or less, particularly preferably 10 parts by mass or more and 35 parts by mass or less, and particularly 15 parts by mass. It is preferably 30 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the content of the hydroxyl group-containing component may be any as long as it can obtain desired dimensional stability, adhesive strength and deep curability, but it should be 1 part by mass or more in 100 parts by mass of the solid content of the above composition. Is preferable, and in particular, it is preferably 2 parts by mass or more and 15 parts by mass or less, and particularly preferably 3 parts by mass or more and 10 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the content of the hydroxyl group-containing component may be one that can obtain desired dimensional stability, adhesive strength and deep curability, but is 1 part by mass or more in 100 parts by mass of the solid content excluding the filler of the above composition. It is preferably 50 parts by mass or less, particularly preferably 5 parts by mass or more and 40 parts by mass or less, particularly preferably 10 parts by mass or more and 35 parts by mass or less, and particularly preferably 15 parts by mass or more and 30 parts by mass. It is preferably less than or equal to parts by mass. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the content of the hydroxyl group-containing component may be any as long as it can obtain desired dimensional stability, adhesive strength and deep curability, but is preferably 1 part by mass or more in 100 parts by mass of the composition, and above all. It is preferably 2 parts by mass or more and 15 parts by mass or less, and particularly preferably 3 parts by mass or more and 10 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the filler is a granular material that does not dissolve in the above-mentioned cyclic ether component and hydroxyl group-containing component. Further, the filler has a small volume change due to a temperature change, and can impart dimensional stability to the cured product of the above composition.
  • the filler may be any filler that can obtain desired dimensional stability, adhesive strength and deep curability, but may be a filler having an average particle size of 1 ⁇ m or more and 100 ⁇ m or less (hereinafter, may be referred to as filler 1). It is preferable to include.
  • the average particle size of the filler 1 is preferably 2 ⁇ m or more and 50 ⁇ m or less, particularly preferably 3 ⁇ m or more and 30 ⁇ m or less, and particularly preferably 5 ⁇ m or more and 20 ⁇ m or less. When the average particle size is in the above range, the composition is excellent in the balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. Because it becomes.
  • the average particle size is also called the median diameter (D50), which means that when a certain particle size is divided into two, the large side and the small side have the same amount (volume basis), and laser diffraction / scattering. From the volume-based particle size distribution measured wet (solvent: water) by the method, it means the particle size cumulatively 50% from the side with the smaller particle size. For example, it can be measured using LA-950V2 (manufactured by HORIBA, Ltd .; particle measuring device, laser diffraction / scattering type).
  • the content of the filler 1 is preferably 80 parts by mass or more, particularly preferably 90 parts by mass or more, and particularly 95 parts by mass or more in 100 parts by mass of the entire filler. It is preferable, and in particular, it is preferably 98 parts by mass or more. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
  • the filler may be used in combination with a filler having an average particle size smaller than that of the filler 1 (hereinafter, may be referred to as a filler 2).
  • the average particle size of the filler 2 can be less than 1 ⁇ m, particularly preferably 1 nm or more and 500 nm or less, particularly preferably 5 nm or more and 100 nm or less, and particularly preferably 10 nm or more and 50 nm or less. Is preferable. This is because the composition has an excellent balance of dimensional stability, adhesive strength and deep curability, and easily adjusts dispersibility and coatability.
  • the content of the filler 2 is preferably 20 parts by mass or less in 100 parts by mass of the entire filler, and in particular, 0.1 parts by mass or more and 10 parts by mass. It is preferably 0.2 parts by mass or more, preferably 5 parts by mass or less, preferably 0.5 parts by mass or more and 2 parts by mass or less, and 0.8 parts by mass or more and 1.5 parts by mass. It is preferably less than or equal to a part. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
  • the average particle size of the filler that is, the average particle size (D50) of the entire filler contained in the composition may be 1 ⁇ m as long as it can obtain desired dimensional stability, adhesive strength and deep curability. It is preferably 100 ⁇ m or less, more preferably 2 ⁇ m or more and 50 ⁇ m or less, particularly preferably 3 ⁇ m or more and 30 ⁇ m or less, and particularly preferably 5 ⁇ m or more and 20 ⁇ m or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
  • the particle size (D1) of the filler that is, the particle size (D1) of the entire filler contained in the composition may be any as long as it can obtain desired dimensional stability, adhesive strength and deep curability. It is preferably 1 nm or more and less than 1 ⁇ m, particularly preferably 5 nm or more and 100 nm or less, and particularly preferably 10 nm or more and 50 nm or less. This is because the composition has an excellent balance of dimensional stability, adhesive strength and deep curability, and has excellent storage stability, and the dispersibility and coatability can be easily adjusted.
  • the particle size (D1) means a particle size that is cumulatively 1% from the side with the smaller particle size from the volume-based particle size distribution.
  • the refractive index of the filler may be any as long as it can obtain desired dimensional stability, adhesive strength and deep curability, but is preferably 1.2 or more and 2.0 or less, and above all, 1.3 or more. It is preferably 1.8 or less, and particularly preferably 1.4 or more and 1.6 or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in deep curability.
  • the method for measuring the refractive index can be measured based on, for example, JIS K 0062: 1992.
  • Such a filler may have particles such as inorganic particles (hereinafter, may be referred to as inorganic particles) and organic particles (hereinafter, may be referred to as organic particles). ..
  • inorganic particles inorganic particles
  • organic particles organic particles
  • constituent materials of the inorganic particles include metal oxides (eg, alumina, titania, etc.), metal hydroxides (eg, aluminum hydroxide, etc.), metal carbonates (eg, calcium carbonate, etc.), and metal sulfates (eg, calcium carbonate).
  • metal oxides eg, alumina, titania, etc.
  • metal hydroxides eg, aluminum hydroxide, etc.
  • metal carbonates eg, calcium carbonate, etc.
  • metal sulfates eg, calcium carbonate.
  • barium sulfate, etc. silica (eg, crystalline silica, molten silica, fumed silica, dry silica (Aerodil), etc.), glass powder, hollow filler (eg, glass hollow sphere, silica hollow sphere, alumina hollow sphere, etc.), etc.
  • the constituent materials of the inorganic particles are preferably silica, silicate, and glass powder, particularly preferably silica, and particularly, fused silica, fumed silica, and dry silica (Aerosil). Is preferable. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability.
  • Materials constituting the organic particles include polymethylmethacrylate, polyethylmethacrylate, methylmethacrylate-ethylmethacrylate copolymer, ethylmethacrylate-butylmethacrylate copolymer, methylmethacrylate-trimethylolpropanetrimethacrylate copolymer, and polyvinylchloride. , Polystyrene, chlorinated polyethylene, nylon, polysulfone, polyethersulfone, polycarbonate and the like. As the material constituting these organic nuclei, a crosslinked body obtained by copolymerizing a crosslinkable monomer is preferable. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability.
  • the filler may be composed of only particles, but preferably includes particles coated with a surface treatment layer, that is, particles having a surface treatment layer covering the particles and the surface of the particles. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
  • the surface treatment layer refers to a layer formed to cover the surface of the particles after the formation of the particles.
  • the surface treatment layer may cover the entire surface of the particles, or may cover only a part of the surface of the particles.
  • an agent that can stably bind to particles can be used, and for example, fatty acids, resin acids, fats and oils, surfactants, silicon oils, coupling agents (silane-based, coupling agents, etc.) can be used.
  • silane coupling agent is preferable. This is because the composition is excellent in the balance of dispersibility, dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability.
  • silane coupling agent examples include dimethyldichlorosilane, trimethylchlorosilane, dimethyldimethoxysilane, trimethylmethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, and hexyltriethoxysilane.
  • Silane-containing silane coupling agent styryl group-containing silane coupling agent such as p-styryltrimethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glyce Epoxy group-containing silane coupling agents such as sidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; methacrylic group-containing silanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane.
  • Acrylic group-containing silane coupling agents such as coupling agents and 3-acryloxypropyltrimethoxysilane; hexamethyldisilazane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3- Amino group-containing silane coupling agents such as aminopropyltrimethoxysilane, mercapto group-containing silane coupling agents such as 3-mercaptopropyltrimethoxysilane, isocyanate group-containing silane coupling agents such as 3-isocyanuspropyltriethoxysilane, etc. Can be mentioned.
  • a layer having a functional group such as an aromatic ring group such as an alkyl group and a phenyl group, a vinyl group, a styryl group, an epoxy group, a methacrylic group, an acrylic group, an amino group, a mercapto group and an isocyanate group is used.
  • a vinyl group, an epoxy group, a methacrylic group, an acrylic group and the like are preferable, and those having an epoxy group are particularly preferable.
  • the composition is excellent in the balance of dispersibility, dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
  • the content of the surface treatment layer may be any as long as it can obtain the desired dimensional stability, adhesive strength and deep curability, but the particles coated by the surface treatment layer, that is, the particles and the surface treatment layer are 100 in total.
  • the number of parts by mass may be 0.05 parts by mass or more and 10 parts by mass or less.
  • a direct treatment method for example, a dry method, a slurry method, a spray method, etc.
  • an integral blend method for example, a direct method, a masterbatch method, etc.
  • a dry concentrate method etc.
  • the content of the filler is 40 parts by mass or more with respect to 100 parts by mass in total of the cyclic ether component and the hydroxyl group-containing component, and more preferably 50 parts by mass or more and 1000 parts by mass or less, particularly 100 parts. It is preferably 7 parts by mass or more and 700 parts by mass or less, and particularly preferably 300 parts by mass or more and 500 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
  • the content of the filler is preferably 20 parts by mass or more, preferably 40 parts by mass or more and 98 parts by mass or less, and particularly 60 parts by mass or more, in 100 parts by mass of the solid content of the composition. It is preferably 95 parts by mass or less, and particularly preferably 70 parts by mass or more and 90 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
  • the content of the filler is preferably 20 parts by mass or more, preferably 40 parts by mass or more and 98 parts by mass or less, and particularly 60 parts by mass or more and 95 parts by mass or more in 100 parts by mass of the composition. It is preferably 70 parts by mass or more, and particularly preferably 90 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
  • Photoacid generator can generate an acid by irradiation with light to promote the polymerization reaction between cyclic ether components, cyclic ether components, and hydroxyl group-containing components.
  • the photoacid generator is a compound capable of generating an acid by irradiation with light.
  • the photoacid generator include a compound salt which is an onium salt or a derivative thereof, an oxime sulfonate compound, a halogen-containing compound, a diazoketone compound, a sulfone compound, a sulfonic acid compound, a diazomethane compound, a nitrobenzyl compound, a benzointosylate compound, and iron.
  • -Alene complex, acetophenone derivative compound and the like can be mentioned, and these can be used alone or in combination of two or more.
  • Examples of the double salt or a derivative thereof, which is an onium salt include salts of cations and anions represented by the following general formula (i).
  • the cation [A] m + is onium, and its structure can be expressed by, for example, the following general formula.
  • R 19 has an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms.
  • a represents an integer of 1 to 5.
  • the a R 19s are independent of each other and may be the same or different.
  • At least one of the a R 19s represents the organic group having an aromatic ring.
  • m a ⁇ q holds.
  • N N is treated as having a valence of 0.
  • anion [B] m- is preferably a halide complex, and its structure can be represented by, for example, the following general formula (iii). This is because the photoacid generator has excellent sensitivity.
  • L represents a metal or metalloid that is the central atom of the halide complex
  • B P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn or Co
  • X represents a halogen atom
  • b represents an integer of 3 to 7.
  • anion [LX b ] m- of the above general formula (iii) include tetrakis (pentafluorophenyl) borate [(C 6 F 5 ) 4 B] - , tetrafluoroborate (BF 4 ) - , and hexa. Fluorophosphate (PF 6 ) - , Hexafluoroantimonate (SbF 6 ) - , Hexafluoroarsenate (AsF 6 ) - , Hexachloroantimonate (SbCl 6 ) - , Tris (pentafluoromethyl) trifluorophosphate ion (FAP anion) ) Etc. can be mentioned.
  • anion [B] m- may have a structure represented by the following general formula (iv).
  • L, X and b are the same as above.
  • Other anions include perchlorate ion (ClO 4 ) - , trifluoromethyl sulfite ion (CF 3 SO 3 ) - , fluorosulfonic acid ion (FSO 3 ) - , toluene sulfonic acid anion, and trinitrobenzene. Examples thereof include sulfonic acid anion, camphor sulphonate, nonafluorobutane sulphonate, hexadecafluorooctan sulphonate, tetraarylborate and the like.
  • aromatic onium salts (a) to (c) among such onium salts. From these, one of them can be used alone, or two or more of them can be mixed and used.
  • Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate and the like.
  • Diaryl such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, trilucmiliodonium tetrakis (pentafluorophenyl) borate, etc.
  • photoacid generators include ( ⁇ 5-2,4-cyclopentadiene-1-yl) [(1,2,3,4,5,6- ⁇ )-(1-methylethyl) benzene].
  • -Iron-iron-arene complex such as hexafluorophosphate
  • aluminum complex such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salitylaldehidato) aluminum and silanol such as triphenylsilanol.
  • silanol such as triphenylsilanol.
  • photoacid generators include ( ⁇ 5-2,4-cyclopentadiene-1-yl) [(1,2,3,4,5,6- ⁇ )-(1-methylethyl) benzene].
  • -Iron-iron-arene complex such as hexafluorophosphate
  • aluminum complex such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salitylaldehidato) aluminum and silanol such as triphenylsilanol.
  • silanol such as triphenylsilanol.
  • the photoacid generator is preferably an aromatic iodonium salt, an aromatic sulfonium salt and an iron-alene complex, and among them, an aromatic sulfonium salt is particularly preferable.
  • an aromatic sulfonium salt is particularly preferable.
  • a triarylsulfonium salt having a structure in which three aromatic rings are bonded to a sulfur atom (S) is preferable, and a triarylsulfonium salt represented by the following general formula (6) is particularly preferable. .. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability.
  • R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 and R 30 are independently hydrogen atom, halogen atom, substituted or unsubstituted, respectively.
  • the methylene group represents a group substituted with a divalent group selected from the following group 2, and R 31 , R 32 , R 33 and R 34 are independently hydrogen atom, halogen atom, substituted or unsubstituted carbon.
  • An alkyl group having 1 to 10 atoms or a methylene group in the alkyl group is represented by a divalent group selected from the following group 2, and R 35 is a hydrogen atom, a halogen atom, a substituted or unsubstituted group.
  • R 121 , R 122 , R 123 , R 124 , R 125 , R 126 , R 127 , R 128 , R 129 , R 130 , R 131 , R 132 , R 133 , R 134 , R 136 , R. 137 , R 138 , R 139 , R 145 , R 146 , R 147 , R 148 and R 149 are each independently hydrogen atom, halogen atom, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted.
  • halogen atom used in the general formula (6) and the general formulas (6a) to (6c) include fluorine, chlorine, bromine, iodine and the like.
  • the substituted or unsubstituted alkyl group having 1 to 10 carbon atoms used in the general formula (6) and the general formulas (6a) to (6c) is a linear or branched alkyl group having 1 to 10 carbon atoms. Examples thereof include an alkyl group and a group in which a hydrogen atom in the alkyl group is substituted.
  • the linear or branched alkyl group having 1 to 10 carbon atoms for example, among the alkyl groups described in the above section "1. Cyclic ether component", those having a predetermined carbon atom number can be used. ..
  • Examples of the group that substitutes one or more of the hydrogen atoms in the alkyl group include a halogen atom and the like.
  • the substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms used in the above general formulas (6) and (6a) to (6c) is-.
  • Examples include groups to which O- is bound.
  • Substituents that may replace the alkyl group constituting the alkoxy group or its hydrogen atom include the substituted or unsubstituted alkyl used in the general formulas (6) and the general formulas (6a) to (6c). It can be the same as the group.
  • an ester bond (-CO-O- or -O-CO) is formed at the end on the bonding site side.
  • Any group having-) may be used, and examples thereof include a group in which an ester bond is bonded to a methylene group at the end on the bonding site side of the alkyl group.
  • the alkyl group constituting the ester group and the substituent that may replace the hydrogen atom thereof are substituted or unsubstituted groups used in the general formulas (6) and (6a) to (6c) R 21 . It can be similar to an alkyl group.
  • Examples of the q-valent anion represented by pAn q- in the general formula (6) include anions having a predetermined valence among those listed as the above-mentioned anions [B] m-.
  • Examples of the q-valent anion represented by pAn q- include tetrakis (pentafluorophenyl) borate [(C 6 F 5 ) 4 B] - , tetrafluoroborate (BF 4 ) - , and hexafluorophosphate (PF 6).
  • R 35 is preferably selected from the chemical formulas (6a) to (6c), and more preferably the chemical formula (6b). This is because the R 35 has the above-mentioned structure, so that the above-mentioned composition is excellent in the balance of dimensional stability, adhesive strength and deep curability.
  • R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 and R 34 are hydrogen atom, halogen atom, carbon.
  • R 121 , R 122 , R 123 , R 124 , R 125 , R 126 , R 127 , R 128 , R 129 , R 130 , R 131 , R 132 , R 133 , R 134 , R 136 , R 137 , R 138 , R 139 , R 140 , R 141 , R 142 , R 143 , R 144 , R 145 , R 146 , R 147 , R 148 and R 149 are hydrogen atoms, halogen atoms, and alkyl groups having 1 to 10 carbon atoms. Alternatively, it is preferably an alkoxy group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or a halogen atom. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability.
  • the content of the photoacid generator may be as long as it can obtain the desired dimensional stability, adhesive strength and deep curability, but it is 0. It is preferably 1 part by mass or more and 10 parts by mass or less, more preferably 0.5 part by mass or more and 7 parts by mass or less, and particularly preferably 1 part by mass or more and 5 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
  • the content of the photoacid generator is preferably 0.01 parts by mass or more and 4 parts by mass or less, and more preferably 0.05 parts by mass or more and 3 parts by mass or less in 100 parts by mass of the composition. It is preferably 0.1 part by mass or more and 1.5 part by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability.
  • the content of the photoacid generator is preferably 0.01 parts by mass or more and 4 parts by mass or less, and 0.05 parts by mass or more and 3 parts by mass or less in 100 parts by mass of the solid content of the above composition. It is more preferable, and it is particularly preferable that it is 0.1 part by mass or more and 1.5 part by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability.
  • the composition of the present disclosure may contain a solvent capable of dissolving or dispersing each of the above components, if necessary.
  • the solvent is liquid at 25 ° C. and under atmospheric pressure, and can disperse or dissolve each component of the composition. Further, the solvent does not react with each of the above components such as a cyclic ether component, a hydroxyl group-containing component, a filler, and a photoacid generator. Therefore, for example, those classified into a cyclic ether component and a hydroxyl group-containing component do not correspond to a solvent even if they are liquid at 25 ° C. under atmospheric pressure.
  • Examples of such a solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, propylene glycol monomethyl ether, and propylene glycol monomethyl.
  • Examples thereof include ether acetate, ethyl acetate, methanol, ethanol and isopropanol.
  • the content of the solvent may be any as long as it can obtain desired dimensional stability, adhesive strength and deep curability, but from the viewpoint of facilitating the use of the composition of the present disclosure as an adhesive, the above composition 100 Of the parts by mass, 10 parts by mass or less is preferable, 5 parts by mass or less is more preferable, and 1 part by mass or less is further preferable.
  • the composition preferably contains a silane coupling agent. This is because the above composition is superior in adhesive strength.
  • silane coupling agent a compound having an alkoxysilyl group can be used, and specific examples thereof include the silane coupling agent described in "3. Filler" above.
  • those having a functional group such as an aromatic ring group such as an alkyl group and a phenyl group, a vinyl group, a styryl group, an epoxy group, a methacrylic group, an acrylic group, an amino group, a mercapto group and an isocyanate group shall be used.
  • those having a vinyl group, an epoxy group, a methacrylic group, an acrylic group and the like are preferable, and those having an epoxy group are particularly preferable. This is because the composition is excellent in balance of dispersibility, dimensional stability, adhesive strength and deep curability, and in particular, is excellent in storage stability and adhesive strength.
  • the content of the silane coupling agent is preferably 0.1 part by mass or more and 15 parts by mass or less, and 0.5 parts by mass or more and 10 parts by mass with respect to 100 parts by mass in total of the cyclic ether component and the hydroxyl group-containing component. It is more preferably 0 parts by mass or less, and particularly preferably 0.8 parts by mass or more and 8 parts by mass or less. This is because the above composition is superior in adhesive strength.
  • the content of the silane coupling agent is preferably 0.01 parts by mass or more and 5 parts by mass or less, and more preferably 0.05 parts by mass or more and 3 parts by mass or less in 100 parts by mass of the composition. It is preferable, and it is particularly preferable that it is 0.1 part by mass or more and 2 parts by mass or less. This is because the above composition is superior in adhesive strength.
  • the content of the silane coupling agent is preferably 0.01 parts by mass or more and 5 parts by mass or less, and 0.05 parts by mass or more and 3 parts by mass or less in 100 parts by mass of the solid content of the above composition. It is more preferable, and particularly preferably 0.1 part by mass or more and 2 parts by mass or less. This is because the above composition is superior in adhesive strength.
  • the amount of the silane coupling agent used for the surface treatment shall not be included in the above-mentioned silane coupling amount.
  • the above composition contains a cyclic ether component, a hydroxyl group-containing component, a filler and a photoacid generator, and can further contain a solvent, but can also contain other components if necessary.
  • Such other components include colorants such as pigments and dyes, photosensitizers, defoamers, thickeners, tinctures, surfactants, leveling agents, flame retardants, plasticizers, stabilizers, etc. It can contain various resin additives such as polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow modifiers and adhesion promoters.
  • an ultraviolet absorber and an antioxidant a latent addition in which a phenolic hydroxyl group is protected by a protecting group and a function as an ultraviolet absorber or an antioxidant is exhibited by removing the protecting group by heating or the like. Agents can also be used. Examples of such latent additives include the latent additives described in International Publication No. WO2017 / 170465.
  • the total content of these other components can be 30 parts by mass or less in 100 parts by mass of the solid content of the composition of the present disclosure.
  • compositions of the present disclosure are preferably those that require dimensional stability, adhesive strength, and deep curability, and are preferably adhesives.
  • the adhesive is used for moving objects such as seismometers, work robots, health monitoring devices, unmanned driving devices, personal computers (for example, mobile personal computers, laptop personal computers, tablet personal computers), and mobile phones.
  • Inkjet ejection devices such as terminals, digital cameras and inkjet printers, storage area network devices such as routers and switches, local area network devices, mobile terminal base station devices, televisions, video cameras, video recorders, car navigation devices, pagers.
  • Electronic notebooks Electronic notebooks, electronic dictionaries, calculators, electronic game devices, game controllers, word processors, workstations, videophones, security TV monitors, electronic binoculars, POS (point of sale) terminals, medical devices (eg electronic thermometers, blood pressure monitors) , Blood glucose meter, electrocardiogram measuring device, ultrasonic diagnostic device, electronic endoscope), fish finder, various measuring devices, instruments / sensors (for example, vehicles, aircraft, marine instruments / sensors), flight simulator, head It is preferably for bonding electronic parts and optical parts used in mount displays, motion traces, motion tracking, motion controllers, PDRs (pedestrian position and orientation measurement), etc., and above all, for bonding optical parts. preferable.
  • the above composition can more effectively exert the effect of being excellent in dimensional stability, adhesive strength and deep curability.
  • the optical component include a component that transmits light, and examples thereof include a lens, a film, an optical waveguide, a prism, a prism sheet, and the like used for a display, a sensor, and the like.
  • Examples of electronic components include semiconductor elements, conductor materials including wiring, and the like.
  • the composition is preferably used for forming a cured product having a large thickness. This is because the above composition can more effectively exert the effect of being excellent in dimensional stability, adhesive strength and deep curability.
  • the thickness of the cured product can be, for example, 1 ⁇ m or more and 100 mm or less, but is preferably 50 ⁇ m or more, particularly preferably 200 ⁇ m or more, particularly preferably 500 ⁇ m or more, and particularly preferably 500 ⁇ m or more. In particular, it is preferably 1 mm or more, and particularly preferably 2 mm or more. This is because the above composition can more effectively exert the effect of being excellent in dimensional stability, adhesive strength and deep curability.
  • the thickness of the cured product is preferably 10 mm or less, more preferably 5 mm or less, and particularly preferably 3 mm or less. This is because the above composition can more effectively exert the effect of being excellent in dimensional stability, adhesive strength and deep curability.
  • the cured product of the present disclosure is a cured product of the above-mentioned composition.
  • the cured product of the present disclosure uses the above-mentioned composition. Since the contents of the above composition can be the same as the contents described in the above-mentioned "A. Composition" section, the description thereof is omitted here.
  • the cured product may contain a high molecular weight substance obtained by reacting the cyclic ether components with each other and / or the cyclic ether component with the hydroxyl group-containing component.
  • the plan view shape of the cured product can be appropriately set according to the intended use of the cured product, and may be, for example, a pattern shape such as a dot shape or a line shape.
  • the thickness of the cured product is set according to the intended use of the cured product, and may be, for example, 1 ⁇ m or more and 100 mm or less, but is preferably in the section of “A. Composition”. It can be the same as the above-mentioned preferable thickness of the cured product.
  • the uses and the like of the cured product can be the same as those described in the section of "A. Composition" above.
  • the method for producing the cured product is not particularly limited as long as it can form the cured product of the composition into a desired shape.
  • a manufacturing method for example, the manufacturing method described in the section "C. Manufacturing method of cured product" described later can be used.
  • the method for producing a cured product of the present disclosure includes a light irradiation step of irradiating the above-mentioned composition with light.
  • a light irradiation step of irradiating the above-mentioned composition with light is a step of the manufacturing method of the present disclosure.
  • This step is a step of irradiating the above composition with light.
  • the light irradiated to the composition may include light having a wavelength of 300 nm to 450 nm.
  • Examples of the light source for light irradiation include ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, light emitting diode (LED), and the like.
  • Laser light may be used as the light to be irradiated.
  • a light having a wavelength of 340 to 430 nm can be used as the laser light.
  • a light source in the visible to infrared region such as an argon ion laser, a helium neon laser, a YAG laser, and a semiconductor laser can also be used.
  • the composition can contain a sensitizing dye that absorbs the region from visible to infrared.
  • the method for producing the cured product may include other steps, if necessary, in addition to the light irradiation step.
  • Other steps include a development step of removing unpolymerized portions in the coating film of the composition to obtain a patterned cured product after the light irradiation step, and a post-baking process in which the cured product is heat-treated after the light irradiation step. Examples thereof include a step, a prebaking step of heat-treating the composition to remove the solvent in the composition before the light irradiation step, a step of forming a coating film of the composition before the light irradiation step, and the like. can.
  • a method for removing the unpolymerized portion in the development step for example, a method of applying an organic solvent to the unpolymerized portion can be mentioned.
  • the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like.
  • the timing of carrying out the development step may be after the curing step.
  • the heating conditions in the post-baking step may be any as long as they can improve the strength of the cured product obtained in the curing step, and can be, for example, 10 to 90 minutes at 100 ° C. or higher and 250 ° C. or lower.
  • the heating conditions in the prebaking step may be any one that can remove the solvent in the composition, and can be, for example, 70 ° C. or higher and 150 ° C. or lower for 30 seconds to 300 seconds.
  • the coating film can be formed on a substrate.
  • the base material can be appropriately set according to the intended use of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, wiring substrates, metals, paper, plastics, and the like. Further, the cured product may be formed on a base material and then peeled off from the base material and used, or may be transferred from the base material to another adherend and used.
  • the present disclosure is not limited to the above embodiment.
  • the above embodiment is an example, and any one having substantially the same structure as the technical idea described in the claims of the present disclosure and having the same effect and effect is the present invention. Included in the technical scope of the disclosure.
  • Examples and Comparative Examples According to the formulations shown in Tables 1 to 5 below, the cyclic ether component, the hydroxyl group-containing component, the filler, and the photoacid generator are mixed and stirred at 25 ° C. for 1 hour to obtain the compositions of each Example and Comparative Example. rice field. In addition, the following materials were used for each component. The blending amount in the table represents the mass part of each component.
  • (Hydroxy group-containing component) B1 Aliphatic compound (compound represented by the following formula B1 (total of l, m, n is 1 or more), alcoholic hydroxyl group, trifunctional, polyester polyol, Praxel 303 (polycaprolactone triol) manufactured by Daicel Co., Ltd., hydroxyl value 530-550 mgKOH / g, molecular weight 300, number of carbon atoms between adjacent hydroxyl groups is 6 or more)
  • B2 Aliphatic compound (compound represented by the following formula B2, alcoholic hydroxyl group, trifunctional, polyol monomer, trimethylolpropane, molecular weight 134, number of carbon atoms between adjacent hydroxyl groups is 3)
  • B3 Aromatic compound (compound represented by the following formula B3 (total of m and n is 1 or more), propylene oxide-modified bisphenol A, alcoholic hydroxyl group, bifunctional, polyether polyol, number of carbon atoms between adjacent
  • C1 Inorganic particles (silica, Admafuse (registered trademark) manufactured by Admatex, average particle size 10 ⁇ m, with surface treatment layer containing epoxy group)
  • C2 Inorganic particles (silica, Admafuse manufactured by Admatex, average particle size 20 ⁇ m, with surface treatment layer containing epoxy group)
  • C3 Inorganic particles (silica, Admafuse manufactured by Admatex, average particle size 10 ⁇ m, with surface treatment layer containing methacrylic group)
  • C4 Inorganic particles (silica, Admafuse manufactured by Admatex, average particle size 10 ⁇ m, no surface treatment)
  • C5 Inorganic particles (silica, VP-NKC-130 manufactured by Aerosil Japan, average particle size 16 nm, with surface treatment layer containing hexadecyl group)
  • the surface-treated layers in each of C1 to C3 and C5 were made of a silane coupling agent having a functional group described in the section of each filler.
  • compositions prepared in Examples and Comparative Examples were evaluated for dimensional stability, adhesive strength, deep curability and dispersibility.
  • compositions obtained in Examples and Comparative Examples are applied onto a glass substrate, and a 365 nm LED (LED lamp having a peak top at 365 nm within the range of 300 nm to 500 nm) with respect to the coating film, Aitec Co., Ltd. Irradiation was performed at 5000 mJ / cm 2 (integrated light intensity at a wavelength of 365 nm) with (manufactured by System) to obtain a cured product having a film thickness of 150 ⁇ m. Next, the cured product was peeled off from the glass substrate to obtain a measurement sample (film thickness 150 ⁇ m ⁇ width 4 mm ⁇ length 30 mm).
  • the obtained measurement sample was measured for heat ray expansion rate under the following conditions using TMA7100 manufactured by Hitachi High-Tech, and evaluated according to the following criteria.
  • the results are shown in Tables 1 to 5 below.
  • Measurement condition Measurement temperature: -20 ° C to 250 ° C
  • the sample shown in FIG. 1 was obtained by the following procedure.
  • the compositions obtained in Examples and Comparative Examples were applied onto an aluminum substrate 1 having a diameter of 25 mm ⁇ 50 mm in a circular shape having a diameter of about 3 mm.
  • a silicon sheet having a thickness of 1 mm was placed on both ends of the composition as spacers 4, a glass substrate 3 having the same shape as the aluminum substrate 1 was covered from above, and the glass substrate 3 was firmly fixed with a clip or the like.
  • the cured product of the aluminum substrate 1 is subjected to the evaluation sample 10 in which the aluminum substrate 1, the cured product 2 and the spacer 4 of the composition, and the glass substrate 3 are laminated in this order.
  • a compression test was conducted in which the glass substrate 3 was pushed in from above in the vertical direction to below in the vertical direction in parallel with the forming surface at a test speed of 5.0 mm / min, and the compressive yield stress was measured according to JIS K7181 (1994). The compressive yield stress was divided by the area of the adhesive surface between the cured product 2 and the aluminum substrate 3, and the compressive shear strength (MPa) was calculated and evaluated according to the following criteria. The results are shown in Tables 1 to 5. Note that X in FIG. 1 indicates a pushing force downward in the vertical direction.
  • compositions obtained in Examples and Comparative Examples were poured into a cylindrical glass container (diameter 10 mm) having a mold release treatment on the inside so as to have an arbitrary height.
  • the upper surface of the glass container was irradiated with a 365 nm LED (LED lamp having a peak top at 365 nm in the range of 300 nm to 500 nm, manufactured by Aitec System Co., Ltd.) at 5000 mJ / cm 2 (integrated light intensity at a wavelength of 365 nm).
  • the composition after light irradiation was taken out from the glass container, and the one not irradiated with light (back surface) was palpated to check for tack.
  • the height immediately before the tack appeared on the back surface was defined as the degree of deep curing of the composition, and was evaluated according to the following criteria.
  • the composition When evaluating a height of less than 1 mm, the composition is applied on a release film (TN-100 manufactured by Toyobo Co., Ltd.) with an arbitrary film thickness, cured under the above conditions, and the release film side is palpated. And evaluated. The results are shown in Tables 1 to 5.
  • compositions of Examples had good dimensional stability, adhesive strength and deep curability. Further, it was confirmed that the composition of the example exhibited excellent adhesive strength and deep curability even when the heat treatment was not performed after the exposure. It was also confirmed that the composition of the example had good dispersibility.

Abstract

The main purpose of the present disclosure is to provide a composition having excellent dimensional stability, adhesive strength, and deep curability. The present disclosure achieves the above purpose by providing a composition containing a cyclic ether component, a hydroxyl group-containing component, a filler, and a photoacid generator, the cyclic ether component containing an alicyclic epoxy compound, the alicyclic epoxy compound content being at least 80 mass parts relative to 100 mass parts of the cyclic ether component, and the filler content being at least 40 mass parts relative to a total of 100 mass parts of the cyclic ether component and the hydroxyl group-containing component.

Description

組成物、硬化物及び硬化物の製造方法Method for producing composition, cured product and cured product
 本開示は、組成物、その硬化物及び硬化物の製造方法に関する。 The present disclosure relates to a composition, a cured product thereof, and a method for producing the cured product.
 電子部品、光学部品等の接着に用いられる接着剤としては、反りの少なさ、寸法安定性が良好等の観点から硬化性樹脂と充填剤とを含む組成物が知られている。
 例えば、特許文献1では、エポキシ化合物と充填剤とを含む熱硬化性組成物が開示されている。また、特許文献2では、エポキシ樹脂と充填剤とを含む光硬化性組成物が開示されている。
As an adhesive used for adhering electronic parts, optical parts and the like, a composition containing a curable resin and a filler is known from the viewpoints of low warpage and good dimensional stability.
For example, Patent Document 1 discloses a thermosetting composition containing an epoxy compound and a filler. Further, Patent Document 2 discloses a photocurable composition containing an epoxy resin and a filler.
US2013/237018A1US2013 / 237018A1 特開2017-75205号公報JP-A-2017-75205
 近年の電子部品、光学部品の微細化等の進展により、特許文献1のような熱硬化性組成物を接着剤として用いた場合には、熱硬化時の加熱処理により、接着部分周辺の部材が熱劣化等を生じる場合があるとの不具合がある。
 特許文献2のような光硬化性組成物を接着剤として用いた場合には、熱劣化の不具合を低減できるが、深部硬化性が低く、厚みの大きい接着部の形成が困難となる場合がある。
Due to the recent progress in miniaturization of electronic parts and optical parts, when a thermosetting composition as in Patent Document 1 is used as an adhesive, the members around the bonded portion are removed by heat treatment during heat curing. There is a problem that heat deterioration may occur.
When a photocurable composition as in Patent Document 2 is used as an adhesive, the defect of thermal deterioration can be reduced, but the deep curability is low and it may be difficult to form a thick adhesive portion. ..
 本開示は、上記問題点に鑑みてなされたものであり、寸法安定性、接着力及び深部硬化性に優れた組成物を提供することを目的とする。 The present disclosure has been made in view of the above problems, and an object of the present disclosure is to provide a composition having excellent dimensional stability, adhesive strength and deep curability.
 本発明者は、鋭意検討を行い、特定の環状エーテル成分、水酸基含有成分、所定量の充填剤及び光酸発生剤を組み合わせることで、寸法安定性、接着力及び深部硬化性のバランスに優れた組成物を得られることを見出した。 The present inventor has made diligent studies, and by combining a specific cyclic ether component, a hydroxyl group-containing component, a predetermined amount of a filler and a photoacid generator, an excellent balance between dimensional stability, adhesive strength and deep curability is excellent. It has been found that the composition can be obtained.
 すなわち、本開示は、環状エーテル成分と、水酸基含有成分と、充填剤と、光酸発生剤と、を含む組成物であって、上記環状エーテル成分は、脂環式エポキシ化合物を含み、上記脂環式エポキシ化合物の含有量が、上記環状エーテル成分100質量部中に80質量部以上であり、上記充填剤の含有量が、上記環状エーテル成分及び上記水酸基含有成分の合計100質量部に対して、40質量部以上である組成物を提供する。 That is, the present disclosure is a composition containing a cyclic ether component, a hydroxyl group-containing component, a filler, and a photoacid generator, wherein the cyclic ether component contains an alicyclic epoxy compound and the above fat. The content of the cyclic epoxy compound is 80 parts by mass or more in 100 parts by mass of the cyclic ether component, and the content of the filler is 100 parts by mass in total of the cyclic ether component and the hydroxyl group-containing component. , 40 parts by mass or more are provided.
 本開示によれば、上記組成物は、寸法安定性、接着力及び深部硬化性のバランスに優れたものとなる。 According to the present disclosure, the above composition has an excellent balance of dimensional stability, adhesive strength and deep curability.
 本開示においては、上記充填剤の平均粒径が、1μm以上100μm以下であることが好ましい。上記組成物は、塗布性に優れたものとなるからである。 In the present disclosure, it is preferable that the average particle size of the filler is 1 μm or more and 100 μm or less. This is because the above composition has excellent coatability.
 本開示においては、上記充填剤が、表面処理層により被覆された粒子を含むことが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性、分散性のバランスに優れたものとなる。 In the present disclosure, it is preferable that the filler contains particles coated with a surface treatment layer. The above composition has an excellent balance of dimensional stability, adhesive strength, deep curability, and dispersibility.
 本開示においては、上記水酸基含有成分が、水酸基の数が3個以上の化合物を含むことが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 In the present disclosure, it is preferable that the hydroxyl group-containing component contains a compound having 3 or more hydroxyl groups. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 本開示においては、上記水酸基含有成分が、脂肪族アルコール化合物を含むことが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 In the present disclosure, it is preferable that the hydroxyl group-containing component contains an aliphatic alcohol compound. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 本開示においては、上記水酸基含有成分の含有量が、上記環状エーテル成分及び上記水酸基含有成分の合計100質量部中に、5質量部以上50質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、深部硬化性に優れたものとなるからである。 In the present disclosure, the content of the hydroxyl group-containing component is preferably 5 parts by mass or more and 50 parts by mass or less in a total of 100 parts by mass of the cyclic ether component and the hydroxyl group-containing component. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in deep curability.
 本開示においては、上記脂環式エポキシ化合物が、シクロアルケンオキサイド構造を2個以上有する化合物を含むことが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 In the present disclosure, it is preferable that the alicyclic epoxy compound contains a compound having two or more cycloalkene oxide structures. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 本開示においては、上記組成物が、接着剤であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスに優れるとの効果をより効果的に発揮できるからである。 In the present disclosure, it is preferable that the above composition is an adhesive. This is because the above composition can more effectively exert the effect of having an excellent balance of dimensional stability, adhesive strength and deep curability.
 本開示は、上述の組成物の硬化物を提供する。 The present disclosure provides a cured product of the above composition.
 本開示によれば、上述の組成物を用いて形成されたものであるため、寸法安定性、接着力に優れ、厚みの厚い場合でも優れた接着力の硬化物を容易に形成可能となる。 According to the present disclosure, since it is formed by using the above-mentioned composition, it is possible to easily form a cured product having excellent dimensional stability and adhesive strength and having excellent adhesive strength even when the thickness is thick.
 本開示は、上述の組成物に光照射する光照射工程を有する硬化物の製造方法を提供する。 The present disclosure provides a method for producing a cured product, which comprises a light irradiation step of irradiating the above-mentioned composition with light.
 本開示によれば、上述の組成物を用いて形成されたものであるため、十分に硬化した硬化物を得ることができる。 According to the present disclosure, since it is formed by using the above-mentioned composition, a sufficiently cured cured product can be obtained.
 本開示は、寸法安定性、接着力及び深部硬化性に優れた組成物を提供することができる。 The present disclosure can provide a composition excellent in dimensional stability, adhesive strength and deep curability.
図1(a)は、評価用サンプルをガラス基板側平面視した模式図であり、図1(b)は、図1(a)のA-A線断面図である。1 (a) is a schematic view of an evaluation sample viewed from a plan view on the glass substrate side, and FIG. 1 (b) is a sectional view taken along line AA of FIG. 1 (a).
 本開示は、組成物、それを用いた硬化物及び硬化物の製造方法に関するものである。 The present disclosure relates to a composition, a cured product using the composition, and a method for producing the cured product.
A.組成物
 まず、本開示の組成物について説明する。
 本開示の組成物は、環状エーテル成分と、水酸基含有成分と、充填剤と、光酸発生剤と、を含む組成物であって、上記環状エーテル成分は、脂環式エポキシ化合物を含み、上記脂環式エポキシ化合物の含有量が、上記環状エーテル成分100質量部中に80質量部以上であり、上記充填剤の含有量が、上記環状エーテル成分及び上記水酸基含有成分の合計100質量部に対して、40質量部以上であることを特徴とするものである。
A. Composition First, the composition of the present disclosure will be described.
The composition of the present disclosure is a composition containing a cyclic ether component, a hydroxyl group-containing component, a filler, and a photoacid generator, and the cyclic ether component contains an alicyclic epoxy compound and is described above. The content of the alicyclic epoxy compound is 80 parts by mass or more in 100 parts by mass of the cyclic ether component, and the content of the filler is 100 parts by mass in total of the cyclic ether component and the hydroxyl group-containing component. It is characterized by having 40 parts by mass or more.
 本開示によれば、寸法安定性、接着力及び深部硬化性のバランスに優れたものとなる。
 ここで、上述の各成分を組み合わせることにより、このような効果が得られる理由については定かではないが、以下のように推察される。
According to the present disclosure, the balance between dimensional stability, adhesive strength and deep curability is excellent.
Here, the reason why such an effect can be obtained by combining each of the above-mentioned components is not clear, but it is presumed as follows.
 すなわち、特定の環状エーテル成分を所定量、充填剤、水酸基含有成分及び光酸発生剤と組み合わせることにより、光酸発生剤から活性種が発生すると同時に光照射側から深部方向に速い速度で効率的に重合反応が進行する。その結果、塗膜の表面のみならず深部においても硬化反応を十分に進行させることが可能となり、上記組成物は優れた深部硬化性を発揮可能となる。
 また、深部硬化性が優れることで、上記組成物は、環状エーテル成分及び水酸基含有成分が十分に硬化した硬化物を形成すること、表面側と深部側とで硬化状態が均一な硬化物を形成すること等が可能となる。その結果、上記硬化物は、優れた寸法安定性及び接着力を有するものとなる。
 このようなことから、特定の各成分を組み合わせることにより、上記組成物は、寸法安定性、接着力及び深部硬化性のバランスに優れたものとなる。
That is, by combining a specific cyclic ether component with a predetermined amount, a filler, a hydroxyl group-containing component and a photoacid generator, active species are generated from the photoacid generator, and at the same time, it is efficient from the light irradiation side toward the deep part at a high speed. The polymerization reaction proceeds. As a result, the curing reaction can be sufficiently advanced not only on the surface of the coating film but also in the deep part, and the above composition can exhibit excellent deep curing property.
Further, due to the excellent deep curability, the above composition forms a cured product in which the cyclic ether component and the hydroxyl group-containing component are sufficiently cured, and forms a cured product having a uniform cured state on the surface side and the deep side. It becomes possible to do such things. As a result, the cured product has excellent dimensional stability and adhesive strength.
Therefore, by combining each specific component, the above composition has an excellent balance of dimensional stability, adhesive strength and deep curability.
 また、充填剤を所定量含むと、粘度が高くなり分散性や塗工性が低下する。これに対して、所定量の充填剤を特定の環状エーテル成分、水酸基含有成分及び光酸発生剤を組み合わせることにより、粘度の増加を抑制でき、上記組成物は、分散性や塗工性に優れたものとなる。
 更に、上記組成物は、上述のような優れた深部硬化性を発揮できることで、露光後に加熱処理を実施しない場合、又は、加熱処理における加熱温度が低温である場合でも、安定的に硬化し、優れた寸法安定性、接着力及び深部硬化性を発揮する。このため、上記組成物は、被接着体の劣化や変形が少なく、位置精度も優れたものとなる。
Further, when a predetermined amount of the filler is contained, the viscosity becomes high and the dispersibility and coatability deteriorate. On the other hand, by combining a predetermined amount of filler with a specific cyclic ether component, a hydroxyl group-containing component and a photoacid generator, an increase in viscosity can be suppressed, and the above composition is excellent in dispersibility and coatability. It will be.
Further, since the composition can exhibit the excellent deep curability as described above, the composition can be stably cured even when the heat treatment is not performed after the exposure or the heating temperature in the heat treatment is low. Demonstrates excellent dimensional stability, adhesive strength and deep curability. Therefore, the composition has less deterioration and deformation of the adherend, and has excellent positional accuracy.
 本開示の組成物は、特定の環状エーテル成分、水酸基含有成分、所定量の充填剤及び光酸発生剤を含むものである。
 以下、本開示の組成物の各成分について詳細に説明する。
The composition of the present disclosure comprises a specific cyclic ether component, a hydroxyl group-containing component, a predetermined amount of a filler and a photoacid generator.
Hereinafter, each component of the composition of the present disclosure will be described in detail.
1.環状エーテル成分
 環状エーテル成分は、環状エーテル基を有する化合物(以下、環状エーテル化合物と称する場合がある。)の1種又は2種以上である成分をいう。
 環状エーテル基としては、エーテル結合を環構造の中に少なくとも1つ有するものであればよく、エポキシ基、オキセタニル基等を挙げることができる。すなわち、環状エーテル化合物としては、エポキシ基を有するエポキシ化合物、オキセタニル基を有するオキセタン化合物を挙げることができる。
 なお、エポキシ化合物としては、エポキシ基を有する化合物全てを含むものであり、エポキシ基及びオキセタン基の両者を含むものはエポキシ化合物に該当するものとする。
1. 1. Cyclic ether component The cyclic ether component refers to a component that is one or more of a compound having a cyclic ether group (hereinafter, may be referred to as a cyclic ether compound).
The cyclic ether group may be any one having at least one ether bond in the ring structure, and examples thereof include an epoxy group and an oxetanyl group. That is, examples of the cyclic ether compound include an epoxy compound having an epoxy group and an oxetane compound having an oxetane group.
The epoxy compound includes all compounds having an epoxy group, and a compound containing both an epoxy group and an oxetane group corresponds to an epoxy compound.
 なお、環状エーテル基及び水酸基を有する化合物は、環状エーテル化合物に含まれるものとし、水酸基含有成分には該当しないものとする。
 また、環状エーテル基及びエチレン性不飽和基を有する化合物は、環状エーテル化合物に含まれるものとする。
 エチレン性不飽和基としては、アクリロイル基、メタクリロイル基、ビニル基等が挙げられる。
 また、環状エーテル基と共にアルコキシシリル基を有する化合物は、通常、シランカップリング剤に分類されるものであり、上記環状エーテル化合物には該当しないものとする。例えばγ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルメチルジエトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン等のエポキシ基と共にアルコキシシリル基を有する化合物は、通常、シランカップリング剤に分類されるものであり、エポキシ化合物には該当しないものとする。
 更に、充填剤として、環状エーテル基を有するものは、充填剤に分類されるものであり、環状エーテル成分には該当しないものとする。例えば、粒子の表面にエポキシ基を有するシランカップリング剤を結合させ、粒子の表面にエポキシ基が形成された表面処理層が形成されたものを用いることがある。このような充填剤として、粒子の表面にエポキシ基を有するものも、本開示における環状エーテル成分としてのエポキシ化合物に該当しないものとする。
 また、光酸発生剤として、環状エーテル基を有するものも、光酸発生剤に分類されるものであり、環状エーテル成分には該当しないものとする。
The compound having a cyclic ether group and a hydroxyl group shall be included in the cyclic ether compound and shall not correspond to the hydroxyl group-containing component.
Further, the compound having a cyclic ether group and an ethylenically unsaturated group shall be included in the cyclic ether compound.
Examples of the ethylenically unsaturated group include an acryloyl group, a methacryloyl group, and a vinyl group.
Further, a compound having an alkoxysilyl group together with a cyclic ether group is usually classified as a silane coupling agent, and does not correspond to the above cyclic ether compound. For example, compounds having an alkoxysilyl group together with an epoxy group such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are usually used. , It is classified as a silane coupling agent and does not correspond to an epoxy compound.
Further, as the filler, those having a cyclic ether group are classified as fillers and do not correspond to the cyclic ether component. For example, a silane coupling agent having an epoxy group may be bonded to the surface of the particles, and a surface treatment layer having an epoxy group formed on the surface of the particles may be used. Such a filler having an epoxy group on the surface of the particles does not fall under the epoxy compound as the cyclic ether component in the present disclosure.
Further, as the photoacid generator, those having a cyclic ether group are also classified as photoacid generators and do not correspond to the cyclic ether component.
 本開示において、環状エーテル成分は、エポキシ化合物として所定量の脂環式エポキシ化合物を含むものである。 In the present disclosure, the cyclic ether component contains a predetermined amount of an alicyclic epoxy compound as an epoxy compound.
(1)脂環式エポキシ化合物
 脂環式エポキシ化合物は、シクロアルケンオキサイド構造を有し、芳香族環を有しない化合物である。
 シクロアルケンオキサイド構造は、シクロヘキセン環含有化合物やシクロペンテン環含有化合物を酸化剤でエポキシ化することによって得られる、シクロヘキセンオキサイド構造やシクロペンテンオキサイド構造のように、脂肪族環とエポキシ環とが環構造の一部を共有する構造である。
 なお、脂環式エポキシ化合物は、シクロアルケンオキサイド構造のエポキシ基を有するものであればよい。従って、ジグリシジル4,5-エポキシシクロヘキサン-1,2-ジカルボキシレートのように、シクロアルケンオキサイド構造と脂肪族環と環構造の一部を共有しないエポキシ基とを有するものも、脂環式エポキシ化合物に該当する。
(1) Alicyclic Epoxy Compound The alicyclic epoxy compound is a compound having a cycloalkene oxide structure and no aromatic ring.
The cycloalkene oxide structure is obtained by epoxidizing a cyclohexene ring-containing compound or a cyclopentene ring-containing compound with an oxidizing agent. Like the cyclohexene oxide structure and the cyclopentene oxide structure, the aliphatic ring and the epoxy ring are one of the ring structures. It is a structure that shares a part.
The alicyclic epoxy compound may be any compound having an epoxy group having a cycloalkene oxide structure. Therefore, those having a cycloalkene oxide structure and an aliphatic ring and an epoxy group that does not share a part of the ring structure, such as diglycidyl 4,5-epoxycyclohexane-1,2-dicarboxylate, are also alicyclic epoxies. It corresponds to a compound.
 本開示においては、脂環式エポキシ化合物が、エポキシ基として、シクロアルケンオキサイド構造のみを有するものであることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 In the present disclosure, it is preferable that the alicyclic epoxy compound has only a cycloalkene oxide structure as an epoxy group. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 脂環式エポキシ化合物が有するシクロアルケンオキサイド構造の数としては1以上であればよいが、2個以上であること、すなわち、脂環式エポキシ化合物が、シクロアルケンオキサイド構造を2個以上有する化合物であることが好ましく、中でも2個以上4個以下であることが好ましく、特に、2個又は3個であることが好ましく、中でも特に、2個であることが好ましい。シクロアルケンオキサイド構造の数が上述の範囲であることで、上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 The number of cycloalkene oxide structures contained in the alicyclic epoxy compound may be 1 or more, but 2 or more, that is, the alicyclic epoxy compound is a compound having 2 or more cycloalkene oxide structures. It is preferably 2 or more, 4 or less, particularly preferably 2 or 3, and particularly preferably 2. When the number of cycloalkene oxide structures is in the above range, the above composition is excellent in the balance of dimensional stability, adhesive strength and deep curability, and in particular, excellent in adhesive strength and deep curability. Because it becomes.
 脂環式エポキシ化合物が有するシクロアルケンオキサイド構造としては、シクロアルケンを構成する炭素数により、シクロペンテンオキサイド構造(5員環)、シクロヘキセンオキサイド構造(6員環)等が挙げられる。脂環式エポキシ化合物が2個以上のシクロアルケンオキサイド構造を有する場合には、それぞれのシクロアルケンオキサイド構造を構成する脂肪族環が他の脂肪族環を介して合計3環以上で縮合している構造(3環以上の縮合環において、該他の脂肪族環への縮合によって2個以上のシクロアルケンオキサイド構造が連結された環構造)を含むものとする。
 本開示においては、上記脂環式エポキシ化合物が、シクロアルケンオキサイド構造として、シクロヘキセンオキサイド構造を含むものであることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
Examples of the cycloalkene oxide structure contained in the alicyclic epoxy compound include a cyclopentene oxide structure (5-membered ring) and a cyclohexene oxide structure (6-membered ring) depending on the number of carbon atoms constituting the cycloalkene. When the alicyclic epoxy compound has two or more cycloalkene oxide structures, the aliphatic rings constituting each cycloalkene oxide structure are condensed in a total of three or more rings via other aliphatic rings. It is intended to include a structure (in a fused ring of 3 or more rings, a ring structure in which two or more cycloalkene oxide structures are linked by condensation on the other aliphatic ring).
In the present disclosure, it is preferable that the alicyclic epoxy compound contains a cyclohexene oxide structure as a cycloalkene oxide structure. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 脂環式エポキシ化合物として好適なものとしては、分子中のシクロアルケンオキサイド構造の数が2個である化合物であって、且つ、シクロアルケンオキサイド構造同士の縮合構造を有するか、又は、シクロアルケンオキサイド構造同士の縮合構造を有しない、非縮合型シクロアルケンオキサイド構造を有する化合物が挙げられる。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。シクロアルケンオキサイド構造同士の縮合構造とは、シクロアルケンオキサイド構造を2つ有しており、それぞれの構造を構成する脂肪族環同士が互いと2個以上の原子を共有して縮合している構造を指す。また、非縮合型シクロアルケンオキサイド構造とは、シクロアルケンオキサイド構造を構成する脂肪族環が他の環と縮合した構造を有しない構造を指す。 Suitable alicyclic epoxy compounds are compounds in which the number of cycloalkene oxide structures in the molecule is two, and have a condensed structure between cycloalkene oxide structures, or cycloalkene oxide. Examples thereof include compounds having a non-condensable cycloalkene oxide structure which does not have a condensed structure between structures. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability. The condensed structure of cycloalkene oxide structures has two cycloalkene oxide structures, and the aliphatic rings constituting each structure are condensed by sharing two or more atoms with each other. Point to. Further, the non-condensed cycloalkene oxide structure refers to a structure in which the aliphatic ring constituting the cycloalkene oxide structure does not have a structure condensed with other rings.
 本開示においては、中でも、脂環式エポキシ化合物が、下記一般式(1)で表される化合物であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れ、入手容易性や保存安定性にも優れたものとなるからである。 In the present disclosure, the alicyclic epoxy compound is preferably a compound represented by the following general formula (1). This is because the above composition is excellent in the balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability, and is also excellent in availability and storage stability. be.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
(式中、Y1は、直接結合又は1以上の原子を有する二価の連結基を表す。) (In the formula, Y 1 represents a divalent linking group having a direct bond or one or more atoms.)
 Y1で表される連結基としては、例えば、二価の炭化水素基、カルボニル基、エーテル結合、エステル結合、カーボネート基、アミド基、及びこれらが複数連結した基等が挙げられる。
 また「これらが複数連結した基」とは、二価の炭化水素基、カルボニル基、エーテル結合、エステル結合、カーボネート基及びアミド基から選ばれる基のうち、二価の炭化水素基以外の基同士が、互いに隣接しないように結合した基とすることができる。
 また、エステル結合-二価の炭化水素基-エステル結合-二価の炭化水素基のように、同一種類の基を2以上組み合わせてもよい。
Examples of the linking group represented by Y 1 include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and a group in which a plurality of these are linked.
Further, the "group in which a plurality of these are linked" is a group selected from a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group and an amide group, and is a group other than the divalent hydrocarbon group. However, they can be groups bonded so as not to be adjacent to each other.
Further, two or more groups of the same type may be combined, such as ester bond-divalent hydrocarbon group-ester bond-divalent hydrocarbon group.
 上記二価の炭化水素基としては、一価の炭素原子数1~20の炭化水素基から1個の水素原子を除いた基を用いることができる。
 一価の炭素原子数1~20の炭化水素基としては、一価の炭素原子数1~20の脂肪族炭化水素基、炭素原子数6~20の芳香族炭化水素環含有基が挙げられる。
As the divalent hydrocarbon group, a group obtained by removing one hydrogen atom from a monovalent hydrocarbon group having 1 to 20 carbon atoms can be used.
Examples of the hydrocarbon group having 1 to 20 monovalent carbon atoms include an aliphatic hydrocarbon group having 1 to 20 monovalent carbon atoms and an aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms.
 一価の炭素原子数1~20の脂肪族炭化水素基としては、芳香族炭化水素環を含まない炭化水素基であればよく、例えば、炭素原子数1~20のアルキル基、炭素原子数3~20のシクロアルキル基、炭素原子数4~20のシクロアルキルアルキル基、炭素原子数2~20のアルケニル基等が挙げられる。
 炭素原子数1~20のアルキル基としては、メチル、エチル、プロピル、iso-プロピル、ブチル、sec-ブチル、tert-ブチル、iso-ブチル、アミル、iso-ペンチル、tert-ペンチル、シクロペンチル、ヘキシル、2-ヘキシル、3-ヘキシル、シクロヘキシル、4-メチルシクロヘキシル、ヘプチル、2-ヘプチル、3-ヘプチル、iso-ヘプチル、tert-ヘプチル、1-オクチル、iso-オクチル、tert-オクチル、アダマンチル等が挙げられる。
 炭素原子数3~20のシクロアルキル基とは、3~20の炭素原子を有する、飽和単環式又は飽和多環式アルキル基を意味する。前記炭素原子数3~20のシクロアルキル基としては、例えば、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル等が挙げられる。
 炭素原子数4~20のシクロアルキルアルキル基とは、アルキル基の水素原子が、シクロアルキル基で置換された炭素原子数4~20の基を意味する。このような炭素原子数4~20のシクロアルキルアルキル基としては、例えば、シクロプロピルメチル、2-シクロブチルエチル、3-シクロペンチルプロピル、4-シクロヘキシルブチル、シクロヘプチルメチル等が挙げられる。
 炭素原子数2~20のアルケニル基としては、例えば、ビニル、エチレン、2-プロペニル、3-ブテニル、2-ブテニル、4-ペンテニル、3-ペンテニル、2-ヘキセニル、3-ヘキセニル、5-ヘキセニル、2-ヘプテニル、3-ヘプテニル、4-ヘプテニル、3-オクテニル、3-ノネニル、4-デセニル、3-ウンデセニル、4-ドデセニル及び4,8,12-テトラデカトリエニルアリル、シクロペンタジニエル等が挙げられる。
The monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be any hydrocarbon group that does not contain an aromatic hydrocarbon ring, for example, an alkyl group having 1 to 20 carbon atoms and 3 carbon atoms. Examples thereof include a cycloalkyl group having about 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms.
Alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-pentyl, tert-pentyl, cyclopentyl, hexyl, and the like. Examples thereof include 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl, adamantyl and the like. ..
The cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which the hydrogen atom of the alkyl group is replaced with a cycloalkyl group. Examples of such a cycloalkylalkyl group having 4 to 20 carbon atoms include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl and the like.
Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, ethylene, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, and the like. 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl and 4,8,12-tetradecatorienylallyl, cyclopentaziniel, etc. Can be mentioned.
 一価の炭素原子数6~20の芳香族炭化水素環含有基としては、芳香族炭化水素環を含み、複素環を含まないものであればよく、例えば、炭素原子数6~20のアリール基、アリール基と上述の脂肪族炭化水素基とを組み合わせた炭素原子数7~20の基等が挙げられる。
 なお、本明細書において「炭素原子数6~20の芳香族炭化水素環含有基」とは、「芳香族炭化水素」ではなく「芳香族炭化水素環含有基」の炭素原子数を規定する。他の炭素原子数の場合も同様である。
 炭素原子数6~20のアリール基としては、芳香族炭化水素環を有し、芳香族性を有する基であり、基中における芳香族炭化水素環上の炭素原子の少なくとも一つがシクロヘキセンオキサイド構造と結合する基である。
 上記アリール基としては、フェニル、トリル基等の単環の芳香族環基(以下、単環芳香族炭化水素環基と称する場合がある。)、ナフチル、アントラセニル、フェナントリル、フルオレニル、ピレニル等の単環の芳香族環の縮合環基(以下、縮合芳香族炭化水素基と称する場合がある。)や、ビフェニル、ベンゾフェノン等の2以上の単環芳香族環又はその縮合環が、単結合、カルボニル基(-CO-)又はスルフィド基(-S-)等の連結基を介して結合した化合物から水素原子を1以上除いた基が挙げられる。
 なお、トリル基のように、芳香族炭化水素環中の水素原子の1つ又は2つ以上がアルキル基で置換された基は、アリール基に含まれるものである。また、トリル基は、単環芳香族炭化水素環基に該当するものである。
 アリール基と上述の脂肪族炭化水素基とを組み合わせた炭素原子数7~20の基としては、アルキル基中の水素原子の1つ又は2つ以上がアリール基で置換された基や、下記一般式(11)で表される二価の基等が挙げられる。
The monovalent aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms may be any as long as it contains an aromatic hydrocarbon ring and does not contain a heterocycle. For example, an aryl group having 6 to 20 carbon atoms. , A group having 7 to 20 carbon atoms, which is a combination of an aryl group and the above-mentioned aliphatic hydrocarbon group, and the like can be mentioned.
In the present specification, the "aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms" defines the number of carbon atoms of the "aromatic hydrocarbon ring-containing group" instead of the "aromatic hydrocarbon". The same applies to other carbon atom numbers.
The aryl group having 6 to 20 carbon atoms is a group having an aromatic hydrocarbon ring and having aromaticity, and at least one of the carbon atoms on the aromatic hydrocarbon ring in the group has a cyclohexene oxide structure. It is a group to be bound.
Examples of the aryl group include monocyclic aromatic ring groups such as phenyl and trill groups (hereinafter, may be referred to as monocyclic aromatic hydrocarbon ring groups), naphthyl, anthracenyl, phenanthryl, fluorenyl, pyrenyl and the like. A fused ring group of an aromatic ring (hereinafter, may be referred to as a fused aromatic hydrocarbon group), two or more monocyclic aromatic rings such as biphenyl and benzophenone, or a fused ring thereof is a single bond or a carbonyl. Examples thereof include a group obtained by removing one or more hydrogen atoms from a compound bonded via a linking group such as a group (-CO-) or a sulfide group (-S-).
A group in which one or more hydrogen atoms in the aromatic hydrocarbon ring is substituted with an alkyl group, such as a tolyl group, is contained in the aryl group. Further, the tolyl group corresponds to a monocyclic aromatic hydrocarbon ring group.
As a group having 7 to 20 carbon atoms in which an aryl group and the above-mentioned aliphatic hydrocarbon group are combined, one or two or more hydrogen atoms in the alkyl group are substituted with an aryl group, or the following general group. Examples thereof include a divalent group represented by the formula (11).
*-Ar1-R11-Ar2-*    (11) * -Ar 1- R 11- Ar 2- * (11)
(式中、Ar1、Ar2は、それぞれ独立に、アリール基を表し、
 R11は、炭素原子数1~10の二価のアルキレン基を表し、
 *は結合箇所を表す。)
(In the formula, Ar 1 and Ar 2 each independently represent an aryl group.
R 11 represents a divalent alkylene group having 1 to 10 carbon atoms.
* Represents the joint location. )
 R11に用いられる炭素原子数1~10の二価のアルキレン基としては、上述の炭素原子数1~20のアルキル基から水素原子を1つ除いた基のうち、所定の炭素原子数のものを用いることができる。 The divalent alkylene group having 1 to 10 carbon atoms used in R 11 has a predetermined number of carbon atoms among the above-mentioned alkyl groups having 1 to 20 carbon atoms minus one hydrogen atom. Can be used.
 本開示においては、Y1で表される連結基が、二価の炭化水素基、カルボニル基、エーテル結合、エステル結合、カーボネート基、アミド基、又はこれらが複数連結した基であることが好ましく、中でも、二価の炭化水素基、カルボニル基、エーテル結合、エステル結合、カーボネート基又はこれらが複数連結した基であることが好ましく、特に、二価の炭化水素基、エステル結合又はこれらが複数連結した基であることが好ましく、中でも特に、二価の炭化水素基及びエステル結合が連結した基であることが好ましく、中でも特に1個以上の二価の炭化水素基と、1個又は2個のエステル結合と、が連結した基であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
 なお、1個以上の二価の炭化水素基と、1個又は2個のエステル結合と、が連結した基としては、例えば、エステル結合と二価の炭化水素基とが結合した基;二価の炭化水素基、エステル結合、二価の炭化水素基、エステル結合及び二価の炭化水素基がこの順で結合した基等が挙げられる。
In the present disclosure, the linking group represented by Y 1 is preferably a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or a group in which a plurality of these are linked. Among them, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group or a group in which a plurality of these are linked is preferable, and in particular, a divalent hydrocarbon group, an ester bond or a plurality of these are linked. It is preferably a group, particularly preferably a divalent hydrocarbon group and a group in which an ester bond is linked, and particularly preferably one or more divalent hydrocarbon groups and one or two esters. Bonds and are preferably linked groups. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
As a group in which one or more divalent hydrocarbon groups and one or two ester bonds are linked, for example, a group in which an ester bond and a divalent hydrocarbon group are bonded; a divalent group. Examples thereof include a hydrocarbon group, an ester bond, a divalent hydrocarbon group, an ester bond, and a group in which a divalent hydrocarbon group is bonded in this order.
 Y1で表される連結基の炭素原子数としては、20以下であることが好ましく、中でも、1以上15以下であることが好ましく、特に、2以上10以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 The number of carbon atoms of the linking group represented by Y 1 is preferably 20 or less, more preferably 1 or more and 15 or less, and particularly preferably 2 or more and 10 or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 本開示においては、Y1に用いられる炭化水素基が、脂肪族炭化水素基であることが好ましく、中でも、アルキル基から水素原子を1つ除いた基、すなわち、アルキレン基であることが好ましく、特に、直鎖のアルキレン基であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなるからである。 In the present disclosure, the hydrocarbon group used for Y 1 is preferably an aliphatic hydrocarbon group, and more preferably a group obtained by removing one hydrogen atom from an alkyl group, that is, an alkylene group. In particular, it is preferably a linear alkylene group. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability.
 Y1に用いられる炭化水素基は水素原子の1又は2以上が置換されていても無置換であってもよいが、無置換であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなるからである。 The hydrocarbon group used for Y 1 may be substituted or unsubstituted with one or more hydrogen atoms, but is preferably unsubstituted. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability.
 上記脂環式エポキシ化合物としては、シクロアルケンオキサイド構造を2個以上有する化合物として、3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート、3,4-エポキシ-1-メチルシクロヘキシル-3,4-エポキシ-1-メチルヘキサンカルボキシレート、6-メチル-3,4-エポキシシクロヘキシルメチル-6-メチル-3,4-エポキシシクロヘキサンカルボキシレート、3,4-エポキシ-3-メチルシクロヘキシルメチル-3,4-エポキシ-3-メチルシクロヘキサンカルボキシレート、3,4-エポキシ-5-メチルシクロヘキシルメチル-3,4-エポキシ-5-メチルシクロヘキサンカルボキシレート、2-(3,4-エポキシシクロヘキシル-5,5-スピロ-3,4-エポキシ)シクロヘキサン-メタジオキサン、ビス(3,4-エポキシシクロヘキシルメチル)アジペート、メチレンビス(3,4-エポキシシクロヘキサン)、プロパン-2,2-ジイル-ビス(3,4-エポキシシクロヘキサン)、2,2-ビス(3,4-エポキシシクロヘキシル)プロパン、ジシクロペンタジエンジエポキサイド、エチレンビス(3,4-エポキシシクロヘキサンカルボキシレート)、エポキシヘキサヒドロフタル酸ジオクチル、エポキシヘキサヒドロフタル酸ジ-2-エチルヘキシル、1-エポキシエチル-3,4-エポキシシクロヘキサン、1,2-エポキシ-2-エポキシエチルシクロヘキサン、α-ピネンオキシド、ε-カプロラクトン変性3’,4’-エポキシシクロへキシルメチル 3,4-エポキシシクロヘキサンカルボキシレート等が挙げられる。 Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxy-1-methylcyclohexyl-3 as compounds having two or more cycloalkene oxide structures. , 4-Epoxy-1-methylhexanecarboxylate, 6-Methyl-3,4-Epoxycyclohexylmethyl-6-methyl-3,4-Epoxycyclohexanecarboxylate, 3,4-Epoxy-3-methylcyclohexylmethyl-3 , 4-Epoxy-3-methylcyclohexanecarboxylate, 3,4-Epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5) -Spiro-3,4-epoxy) cyclohexane-methodioxane, bis (3,4-epoxycyclohexylmethyl) adipate, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-) Epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadienediepoxyside, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, epoxyhexahydrophthalic acid Di-2-ethylhexyl, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinenoxide, ε-caprolactone modified 3', 4'-epoxycyclohexylmethyl 3 , 4-Epoxycyclohexanecarboxylate and the like.
 上記脂環式エポキシ化合物のうち、シクロアルケンオキサイド構造を1個有する化合物としては、例えば、3,4-エポキシシクロヘキシルメチルアクリレート、3,4-エポキシシクロヘキシルメチルメタクリレート、3,4-エポキシシクロヘキサンカルボン酸メチルエステル、ジシクロペンタジエンジエポキサイド、エポキシヘキサヒドロフタル酸ジオクチル、エポキシヘキサヒドロフタル酸ジ-2-エチルヘキシル、1-エポキシエチル-3,4-エポキシシクロヘキサン、1,2-エポキシ-2-エポキシエチルシクロヘキサン等が挙げられる。 Among the above alicyclic epoxy compounds, examples of the compound having one cycloalkene oxide structure include 3,4-epoxycyclohexylmethylacrylate, 3,4-epoxycyclohexylmethylmethacrylate, and methyl 3,4-epoxycyclohexanecarboxylate. Esters, dicyclopentadiene diepoxysides, dioctyl epoxyhexahydrophthalates, di-2-ethylhexyl epoxyhexahydrophthalates, 1-epoxyethyl-3,4-epoxycyclohexanes, 1,2-epoxy-2-epoxyethylcyclohexanes, etc. Can be mentioned.
 脂環式エポキシ化合物の市販品としては、ユニオンカーバイト社製UVR6105、UVR6110及びUVR6128;ダイセル化学株式会社製、セロキサイド2021P、セロキサイド2081、セロキサイド2083、セロキサイド2085、セロキサイド2000、セロキサイド3000、サイクロマーA200、サイクロマーM100、サイクロマーM101、エポリードGT-301、エポリードGT-302、エポリード401、エポリード403、ETHB、エポリードHD300;JXTGエネルギー社製THI-DE、DE-102、DE-103等が挙げられる。 Commercially available alicyclic epoxy compounds include UVR6105, UVR6110 and UVR6128 manufactured by Union Carbite; Daicel Chemical Co., Ltd., Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 2000, Celoxide 3000, Cyclomer A200, Cyclomer M100, Cyclomer M101, Epolide GT-301, Epolide GT-302, Epolide 401, Epolide 403, ETHB, Epolide HD300; THI-DE, DE-102, DE-103 manufactured by JXTG Energy Co., Ltd. and the like can be mentioned.
 脂環式エポキシ化合物の含有量は、環状エーテル成分100質量部中に、80質量部以上であり、85質量部以上であることが好ましく、中でも、90質量部以上であることが好ましく、特に、95質量部以上であることが好ましく、中でも特に、98質量部以上であることが好ましく、中でも特に、100質量部、すなわち、環状エーテル成分として脂環式エポキシ化合物のみを含むことが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 The content of the alicyclic epoxy compound is 80 parts by mass or more, preferably 85 parts by mass or more, and particularly preferably 90 parts by mass or more, in 100 parts by mass of the cyclic ether component. It is preferably 95 parts by mass or more, particularly preferably 98 parts by mass or more, and particularly preferably 100 parts by mass, that is, it contains only an alicyclic epoxy compound as a cyclic ether component. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 脂環式エポキシ化合物の含有量は、環状エーテル成分及び水酸基含有成分の合計100質量部中に、50質量部以上95質量部以下であることが好ましく、中でも、60質量部以上90質量部以下であることが好ましく、特に、70質量部以上85質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 The content of the alicyclic epoxy compound is preferably 50 parts by mass or more and 95 parts by mass or less, particularly 60 parts by mass or more and 90 parts by mass or less, in a total of 100 parts by mass of the cyclic ether component and the hydroxyl group-containing component. It is preferably 70 parts by mass or more and 85 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 脂環式エポキシ化合物の含有量は、上記組成物の固形分100質量部中に、1質量部以上であることが好ましく、中でも、3質量部以上50質量部以下であることが好ましく、特に、5質量部以上45質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
 なお、上記組成物の固形分とは、組成物中の溶剤以外の全ての成分の合計を示すものである。
The content of the alicyclic epoxy compound is preferably 1 part by mass or more, and more preferably 3 parts by mass or more and 50 parts by mass or less, particularly particularly, in 100 parts by mass of the solid content of the above composition. It is preferably 5 parts by mass or more and 45 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
The solid content of the above composition indicates the total of all the components other than the solvent in the composition.
 脂環式エポキシ化合物の含有量は、組成物100質量部中に、1質量部以上であることが好ましく、中でも、3質量部以上50質量部以下であることが好ましく、特に、5質量部以上45質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 The content of the alicyclic epoxy compound is preferably 1 part by mass or more, preferably 3 parts by mass or more and 50 parts by mass or less, and particularly 5 parts by mass or more in 100 parts by mass of the composition. It is preferably 45 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
(2)他の環状エーテル化合物
 環状エーテル成分は、脂環式エポキシ化合物以外の環状エーテル化合物(以下、他の環状エーテル化合物と称する場合がある。)を含むことができる。
 他の環状エーテル化合物としては、芳香族エポキシ化合物、脂肪族エポキシ化合物等の脂環式エポキシ化合物以外のエポキシ化合物、オキセタン化合物等が挙げられる。
 環状エーテル成分が他の環状エーテル化合物を含む場合、他の環状エーテル化合物の含有量は、環状エーテル成分100質量部中に、18質量部以下であることが好ましく、1質量部以上15質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
(2) Other Cyclic Ether Compound The cyclic ether component may contain a cyclic ether compound other than the alicyclic epoxy compound (hereinafter, may be referred to as another cyclic ether compound).
Examples of the cyclic ether compound include an aromatic epoxy compound, an epoxy compound other than an alicyclic epoxy compound such as an aliphatic epoxy compound, and an oxetane compound.
When the cyclic ether component contains another cyclic ether compound, the content of the other cyclic ether compound is preferably 18 parts by mass or less in 100 parts by mass of the cyclic ether component, and is preferably 1 part by mass or more and 15 parts by mass or less. Is preferable. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
(2-1)芳香族エポキシ化合物
 上記芳香族エポキシ化合物は、芳香族環及びエポキシ基を有し、シクロアルケンオキサイド構造を有しないものである。
 このような芳香族エポキシ化合物としては、例えば、少なくとも1個の芳香族環を有する多価フェノール又はそのアルキレンオキサイド付加物のポリグリシジルエーテル、例えばビスフェノールA、ビスフェノールF、ビスフェノールE又はこれらにアルキレンオキサイドを付加した化合物のグリシジルエーテル、及びエポキシノボラック樹脂(フェノールノボラック型エポキシ化合物)等が挙げられる。
 また、レゾルシノールやハイドロキノン、カテコール等の2個以上のフェノール性水酸基を有する芳香族化合物のグリシジルエーテル;ベンゼンジメタノールやベンゼンジエタノール、ベンゼンジブタノール等のアルコール性水酸基を2個以上有する芳香族化合物のポリグリシジルエーテル;フタル酸、テレフタル酸、トリメリット酸等の2個以上のカルボン酸を有する多塩基酸芳香族化合物のポリグリシジルエステル;安息香酸やトルイル酸、ナフトエ酸等の安息香酸類のグリシジルエステル;スチレンオキサイド又はジビニルベンゼンのエポキシ化物等が挙げられる。
(2-1) Aromatic Epoxy Compound The aromatic epoxy compound has an aromatic ring and an epoxy group, and does not have a cycloalkene oxide structure.
Examples of such an aromatic epoxy compound include polyhydric phenol having at least one aromatic ring or polyglycidyl ether of an alkylene oxide adduct thereof, for example, bisphenol A, bisphenol F, bisphenol E, or alkylene oxide thereof. Examples thereof include glycidyl ether of the added compound and an epoxy novolak resin (phenol novolak type epoxy compound).
In addition, glycidyl ether of an aromatic compound having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol; poly of an aromatic compound having two or more alcoholic hydroxyl groups such as benzenedimethanol, benzenediethanol and benzenedibutanol. Glycidyl ether; Polyglycidyl ester of a polybasic acid aromatic compound having two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid; Glycidyl ester of benzoic acids such as benzoic acid, toluic acid and naphthoic acid; styrene Examples thereof include an epoxidized product of oxide or divinylbenzene.
 上記芳香族エポキシ化合物として好適に使用できる市販品としては、例えば、特開2019-137727号公報等に記載されるものを挙げることができる。 Examples of commercially available products that can be suitably used as the aromatic epoxy compound include those described in JP-A-2019-137727.
 本開示においては、上記芳香族エポキシ化合物が、ビスフェノールA型構造、ビスフェノールF型構造、ビスフェノールE型構造等のビスフェノール構造を有する化合物であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 In the present disclosure, it is preferable that the aromatic epoxy compound is a compound having a bisphenol structure such as a bisphenol A type structure, a bisphenol F type structure, and a bisphenol E type structure. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 上記芳香族エポキシ化合物が環状エーテル成分に含まれる場合、芳香族エポキシ化合物の含有量は、所望の寸法安定性、接着力及び深部硬化性が得られるものであればよいが、例えば、環状エーテル成分100質量部中に、18質量部以下であることが好ましく、1質量部以上15質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 When the aromatic epoxy compound is contained in the cyclic ether component, the content of the aromatic epoxy compound may be such that desired dimensional stability, adhesive strength and deep curability can be obtained. For example, the cyclic ether component may be used. It is preferably 18 parts by mass or less, and preferably 1 part by mass or more and 15 parts by mass or less in 100 parts by mass. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
(2-2)脂肪族エポキシ化合物
 上記脂肪族エポキシ樹脂は、エポキシ基を有し、シクロアルケンオキサイド構造及び芳香族環を含まないものである。
 このような脂肪族エポキシ化合物としては、例えば、脂肪族多価アルコール又はそのアルキレンオキサイド付加物のポリグリシジルエーテル;脂肪族長鎖多塩基酸のポリグリシジルエステル;グリシジルアクリレート又はグリシジルメタクリレートのビニル重合により合成したホモポリマー;グリシジルアクリレート又はグリシジルメタクリレートとその他のビニルモノマーとのビニル重合により合成したコポリマー等が挙げられる。
 代表的な化合物として、ジオールのジグリシジルエーテル、グリセリンのトリグリシジルエーテル、トリメチロールプロパンのトリグリシジルエーテル、ソルビトールのテトラグリシジルエーテル、ジペンタエリスリトールのヘキサグリシジルエーテル等の、多価アルコールのグリシジルエーテル、プロピレングリコール、トリメチロールプロパン、グリセリン等の脂肪族多価アルコールに1種又は2種以上のアルキレンオキサイドを付加することによって得られるポリエーテルポリオールのポリグリシジルエーテル、及び脂肪族長鎖二塩基酸のジグリシジルエステルが挙げられる。
 更に、脂肪族高級アルコールのモノグリシジルエーテル、フェノール、クレゾール、ブチルフェノール、又はこれらにアルキレンオキサイドを付加することによって得られるポリエーテルアルコールのモノグリシジルエーテル、高級脂肪酸のグリシジルエステル、エポキシ化大豆油、エポキシステアリン酸オクチル、エポキシステアリン酸ブチル及びエポキシ化ポリブタジエン等が挙げられる。
 また、上記脂肪族エポキシ化合物として、水素添加ビスフェノールAジグリシジルエーテル等の芳香族エポキシ化合物の水素添加物も挙げられる。
 上記脂肪族エポキシ化合物としては、2,2-ビス(ヒドロキシメチル)-1-ブタノールの1,2-エポキシ-4-(2-オキシラニル)シクロヘキサン付加物等の、エポキシシクロアルキル環に由来するシクロアルキル環にオキシラニル基が直接単結合で結合した構造を構成単位として有し、エポキシシクロアルキル環のエポキシ基同士が重合した構造を主鎖構造として有する化合物も挙げられる。
(2-2) Aliphatic Epoxy Compound The above-mentioned aliphatic epoxy resin has an epoxy group and does not contain a cycloalkene oxide structure and an aromatic ring.
Examples of such an aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyvalent alcohols or alkylene oxide adducts thereof; polyglycidyl esters of aliphatic long-chain polybasic acids; glycidyl acrylates or glycidyl methacrylates synthesized by vinyl polymerization. Homopolymers; examples thereof include copolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate and other vinyl monomers.
Typical compounds include polyhydric alcohols such as glycidyl ether of diol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, and hexaglycidyl ether of dipentaerythritol, and propylene. Polyglycidyl ether, which is a polyether polyol obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as glycol, trimethylolpropane, and glycerin, and diglycidyl ester of aliphatic long-chain dibasic acid. Can be mentioned.
Further, monoglycidyl ethers of aliphatic higher alcohols, phenols, cresols, butylphenols, or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oils, epoxide stearers. Examples thereof include octyl acid, butyl epoxidated stearate, and epoxidized polybutadiene.
In addition, examples of the aliphatic epoxy compound include hydrogenated additives of aromatic epoxy compounds such as hydrogenated bisphenol A diglycidyl ether.
Examples of the aliphatic epoxy compound include cycloalkyls derived from epoxycycloalkyl rings such as 1,2-epoxy-4- (2-oxylanyl) cyclohexane adducts of 2,2-bis (hydroxymethyl) -1-butanol. Examples thereof include compounds having a structure in which an oxylanyl group is directly bonded to a ring by a single bond as a constituent unit, and a structure in which epoxy groups of an epoxycycloalkyl ring are polymerized as a main chain structure.
 上記脂肪族エポキシ化合物として好適に使用できる市販品としては、例えば、特開2019-137727号公報等に記載されるものを挙げることができる。 Examples of commercially available products that can be suitably used as the above aliphatic epoxy compounds include those described in JP-A-2019-137727.
 上記脂肪族エポキシ化合物が環状エーテル成分に含まれる場合、脂肪族エポキシ化合物の含有量は、所望の寸法安定性、接着力及び深部硬化性が得られるものであればよいが、例えば、環状エーテル成分100質量部中に、18質量部以下であることが好ましく、1質量部以上15質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 When the above aliphatic epoxy compound is contained in the cyclic ether component, the content of the aliphatic epoxy compound may be such that desired dimensional stability, adhesive strength and deep curability can be obtained, and for example, the cyclic ether component may be obtained. It is preferably 18 parts by mass or less, and preferably 1 part by mass or more and 15 parts by mass or less in 100 parts by mass. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
(2-3)オキセタン化合物
 上記オキセタン化合物は、オキセタニル基を有し、エポキシ基を有しない化合物である。
 このようなオキセタン化合物としては、例えば、特開2019-137727号公報等に記載されるものを挙げることができる。
(2-3) Oxetane compound The above-mentioned oxetane compound is a compound having an oxetaneyl group and no epoxy group.
Examples of such an oxetane compound include those described in JP-A-2019-137727.
(3)環状エーテル成分
 環状エーテル成分の含有量は、環状エーテル成分及び水酸基含有成分の合計100質量部中に、50質量部以上95質量部以下であることが好ましく、中でも、60質量部以上90質量部以下であることが好ましく、特に、70質量部以上85質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
(3) Cyclic ether component The content of the cyclic ether component is preferably 50 parts by mass or more and 95 parts by mass or less, particularly 60 parts by mass or more and 90 parts by mass in a total of 100 parts by mass of the cyclic ether component and the hydroxyl group-containing component. It is preferably 70 parts by mass or less, and particularly preferably 70 parts by mass or more and 85 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 環状エーテル成分の含有量は、上記組成物の固形分100質量部中に、1質量部以上であることが好ましく、中でも、3質量部以上50質量部以下であることが好ましく、特に、5質量部以上45質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 The content of the cyclic ether component is preferably 1 part by mass or more, and more preferably 3 parts by mass or more and 50 parts by mass or less, particularly 5 parts by mass, in 100 parts by mass of the solid content of the above composition. It is preferably 4 parts or more and 45 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 環状エーテル成分の含有量は、上記組成物の充填剤を除く固形分100質量部中に、50質量部以上95質量部以下であることが好ましく、中でも、60質量部以上90質量部以下であることが好ましく、特に、65質量部以上85質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
 なお、上記組成物の充填剤を除く固形分とは、上記組成物の充填剤及び溶剤以外の全ての成分を含むものである。
The content of the cyclic ether component is preferably 50 parts by mass or more and 95 parts by mass or less, and particularly 60 parts by mass or more and 90 parts by mass or less in 100 parts by mass of the solid content excluding the filler of the above composition. It is preferable, and in particular, it is preferably 65 parts by mass or more and 85 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
The solid content excluding the filler of the composition includes all the components other than the filler and the solvent of the composition.
 環状エーテル成分の含有量は、組成物100質量部中に、1質量部以上であることが好ましく、中でも、3質量部以上50質量部以下であることが好ましく、特に、5質量部以上45質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 The content of the cyclic ether component is preferably 1 part by mass or more, preferably 3 parts by mass or more and 50 parts by mass or less, and particularly 5 parts by mass or more and 45 parts by mass in 100 parts by mass of the composition. It is preferably less than or equal to a portion. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
2.水酸基含有成分
 水酸基含有成分としては、水酸基を有する化合物の1種又は2種以上である成分をいう。なお水酸基を有していても、後述する充填剤又は光酸発生剤に該当する成分は、水酸基含有成分には含まないものとする。
2. 2. Hydroxyl group-containing component The hydroxyl group-containing component refers to a component that is one or more of compounds having a hydroxyl group. Even if it has a hydroxyl group, the component corresponding to the filler or photoacid generator described later is not included in the hydroxyl group-containing component.
 水酸基を有する化合物の水酸基は、アルコール性水酸基、フェノール性水酸基のいずれも用いることができるが、アルコール性水酸基であること、すなわち、水酸基を有する化合物がアルコール化合物であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。また、上記組成物は、保存安定性に優れたものとなるからである。 As the hydroxyl group of the compound having a hydroxyl group, either an alcoholic hydroxyl group or a phenolic hydroxyl group can be used, but it is preferable that the hydroxyl group is an alcoholic hydroxyl group, that is, the compound having a hydroxyl group is an alcohol compound. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability. Further, the above composition is excellent in storage stability.
 水酸基を有する化合物の水酸基は、1級水酸基、2級水酸基、3級水酸基のいずれであってもよいが、1級水酸基を含むことが好ましく、1分子中の水酸基の数が2個以上である場合には、全ての水酸基が1級水酸基であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。また、上記組成物は、保存安定性に優れたものとなるからである。 The hydroxyl group of the compound having a hydroxyl group may be any of a primary hydroxyl group, a secondary hydroxyl group, and a tertiary hydroxyl group, but preferably contains a primary hydroxyl group, and the number of hydroxyl groups in one molecule is two or more. In some cases, it is preferable that all the hydroxyl groups are primary hydroxyl groups. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability. Further, the above composition is excellent in storage stability.
 水酸基を有する化合物は、芳香族環を有する芳香族化合物であってもよいが、芳香族環を有しない脂肪族化合物であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
 本開示においては、水酸基を有する化合物が、アルコール性水酸基を有する脂肪族化合物、すなわち、脂肪族アルコール化合物であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
 なお、このような脂肪族アルコール化合物としては、アルコール性水酸基を有し、芳香族炭化水素環及び芳香族複素環をいずれも有しない化合物であり、例えば、ポリオール単量体として後述するトリメチロールプロパン、ポリエステルポリオールとして後述するダイセル社製プラクセル303、ポリエーテルポリオールとして後述するポリエチレングリコール等が挙げられる。
The compound having a hydroxyl group may be an aromatic compound having an aromatic ring, but is preferably an aliphatic compound having no aromatic ring. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
In the present disclosure, the compound having a hydroxyl group is preferably an aliphatic compound having an alcoholic hydroxyl group, that is, an aliphatic alcohol compound. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
It should be noted that such an aliphatic alcohol compound is a compound having an alcoholic hydroxyl group and neither an aromatic hydrocarbon ring nor an aromatic heterocycle, and is, for example, trimethylolpropane as a polyol monomer described later. Examples of the polyester polyol include Praxel 303 manufactured by Daicel Co., Ltd., which will be described later, and examples of the polyether polyol include polyethylene glycol described later.
 水酸基を有する化合物は、1分子中の水酸基数が1個以上であればよいが、水酸基数が2個以上の化合物、すなわち、ポリオールであることが好ましい。
 中でも水酸基を有する化合物は、水酸基数が3個以上である化合物であることが好ましく、特に、水酸基数が3個以上10個以下である化合物であることが好ましく、中でも特に、水酸基数が3個又は4個の化合物であることが好ましく、中でも特に、水酸基数が3個の化合物であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
The compound having a hydroxyl group may have one or more hydroxyl groups in one molecule, but is preferably a compound having two or more hydroxyl groups, that is, a polyol.
Among them, the compound having a hydroxyl group is preferably a compound having 3 or more hydroxyl groups, particularly preferably a compound having 3 or more and 10 or less hydroxyl groups, and particularly preferably 3 or less hydroxyl groups. Alternatively, it is preferably a compound having 4 hydroxyl groups, and particularly preferably a compound having 3 hydroxyl groups. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 水酸基を有する化合物の分子量としては、所望の寸法安定性、接着力及び深部硬化性が得られるものであればよいが、例えば、50以上30,000以下であることが好ましく、中でも、80以上15,000以下であることが好ましく、中でも、100以上10,000以下であることが好ましく、中でも、150以上5,000以下であることが好ましく、中でも、200以上3,000以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。なお、分子量は、場合によっては、1500以下、或いは1000以下、或いは500以下、或いは400以下である場合もある。
 なお、分子量は、水酸基を有する化合物が分子構造中に繰り返し単位を有する場合には、重量平均分子量を指すものである。
 重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー(GPC)により、標準ポリスチレン換算値として求めることができる。重量平均分子量Mwは、例えば、日本分光製のGPC(LC-2000plusシリーズ)を用い、溶出溶剤をテトラヒドロフランとし、校正曲線用ポリスチレンスタンダードをMw37200、13700、9490、5430、3120、1010、589(東ソー製 TSKgel標準ポリスチレン)とし、測定カラムを、KF-803L(昭和電工製)として測定して得ることができる。また、測定温度は40℃とすることができ、流速は1.0mL/分とすることができる。
The molecular weight of the compound having a hydroxyl group may be any as long as it can obtain desired dimensional stability, adhesive strength and deep curability, but is preferably 50 or more and 30,000 or less, and above all, 80 or more and 15 It is preferably 000 or less, more preferably 100 or more and 10,000 or less, particularly preferably 150 or more and 5,000 or less, and particularly preferably 200 or more and 3,000 or less. .. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability. In some cases, the molecular weight may be 1500 or less, 1000 or less, 500 or less, or 400 or less.
The molecular weight refers to the weight average molecular weight when the compound having a hydroxyl group has a repeating unit in the molecular structure.
The weight average molecular weight can be determined by gel permeation chromatography (GPC) as a standard polystyrene conversion value. For the weight average molecular weight Mw, for example, GPC (LC-2000plus series) manufactured by JASCO Corporation is used, the elution solvent is tetrahydrofuran, and the polystyrene standard for calibration curve is Mw37200, 13700, 9490, 5430, 3120, 1010, 589 (manufactured by Toso). (TSKgel standard polystyrene), and the measurement column can be measured and obtained as KF-803L (manufactured by Showa Denko). Further, the measurement temperature can be 40 ° C. and the flow rate can be 1.0 mL / min.
 水酸基を有する化合物の水酸基価(mgKOH/g)としては、所望の寸法安定性、接着力及び深部硬化性が得られるものであればよいが、例えば、100mgKOH/g以上2,000mgKOH/g以下であることが好ましく、150mgKOH/g以上1,500mgKOH/g以下であることがより好ましく、250mgKOH/g以上1,000mgKOH/g以下であることが更に好ましく、中でも、350mgKOH/g以上800mgKOH/g以下であることが好ましく、中でも、400mgKOH/g以上700mgKOH/g以下であることが好ましく、中でも、450mgKOH/g以上600mgKOH/g以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 The hydroxyl value (mgKOH / g) of the compound having a hydroxyl group may be any one that can obtain desired dimensional stability, adhesive strength and deep curability, and is, for example, 100 mgKOH / g or more and 2,000 mgKOH / g or less. It is preferably 150 mgKOH / g or more and 1,500 mgKOH / g or less, more preferably 250 mgKOH / g or more and 1,000 mgKOH / g or less, and more preferably 350 mgKOH / g or more and 800 mgKOH / g or less. It is preferably 400 mgKOH / g or more and 700 mgKOH / g or less, and more preferably 450 mgKOH / g or more and 600 mgKOH / g or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 水酸基を有する化合物がポリオールである場合、隣接する水酸基間の炭素原子数としては、1以上であればよいが、3以上であることが好ましく、特に、5以上であることが好ましく、中でも特に、6以上であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
 なお、隣接する水酸基間の炭素原子数は、水酸基間を結ぶ連結基を最少の原子数となるように通過した際に通過することになる炭素原子数の数をいうものである。例えば、ベンゼン環に水酸基が2個結合したベンゼンジオールの、隣接する水酸基間の炭素原子数は、オルト体である場合は1であり、メタ体である場合は2であり、パラ体である場合は3である。
 また、水酸基を有する化合物が3個以上の水酸基を有する場合、上記隣接する水酸基間の炭素原子数は、隣接する水酸基間の炭素原子数が最小となる水酸基の組み合わせについての数を示すものである。例えば、ジペンタエリトリトールでは、隣接する水酸基間の炭素原子数は3である。
When the compound having a hydroxyl group is a polyol, the number of carbon atoms between adjacent hydroxyl groups may be 1 or more, preferably 3 or more, particularly preferably 5 or more, and particularly particularly. It is preferably 6 or more. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
The number of carbon atoms between adjacent hydroxyl groups refers to the number of carbon atoms that pass through the linking group connecting the hydroxyl groups so as to have the minimum number of atoms. For example, in a benzenediol having two hydroxyl groups bonded to a benzene ring, the number of carbon atoms between adjacent hydroxyl groups is 1 in the case of an ortho form, 2 in the case of a meta form, and 2 in the case of a para form. Is 3.
When the compound having a hydroxyl group has three or more hydroxyl groups, the number of carbon atoms between the adjacent hydroxyl groups indicates the number of combinations of hydroxyl groups having the minimum number of carbon atoms between the adjacent hydroxyl groups. .. For example, in dipentaerythritol, the number of carbon atoms between adjacent hydroxyl groups is 3.
 水酸基を有する化合物として用いられるポリオールとしては、例えば、分子内にエステル骨格(好ましくはポリエステル骨格)を有する(ポリ)エステルポリオール、分子内にエーテル骨格(好ましくはポリエーテル骨格)を有する(ポリ)エーテルポリオール、分子内にカーボネート骨格(好ましくはポリカーボネート骨格)を有する(ポリ)カーボネートポリオール、(ポリ)エステル骨格、(ポリ)エーテル骨格及び(ポリ)カーボネート骨格をいずれも有しない、ポリオール単量体等が挙げられる。本明細書において「(ポリ)エステル骨格を有する」の語は「エステル骨格を有する」に置き換え可能であり、「(ポリ)エーテル骨格を有する」や「(ポリ)カーボネート骨格を有する」についても同様である。 Examples of the polyol used as a compound having a hydroxyl group include a (poly) ester polyol having an ester skeleton (preferably a polyester skeleton) in the molecule, and a (poly) ether having an ether skeleton (preferably a polyether skeleton) in the molecule. Polyols, (poly) carbonate polyols having a carbonate skeleton (preferably polycarbonate skeleton) in the molecule, (poly) ester skeletons, (poly) ether skeletons, polyol monomers having no (poly) carbonate skeleton, etc. Can be mentioned. In the present specification, the term "having a (poly) ester skeleton" can be replaced with "having an ester skeleton", and the same applies to "having a (poly) ether skeleton" and "having a (poly) carbonate skeleton". Is.
 エステル骨格とはエステル結合を有する構造を有し、例えば下記一般式(A-1)で示される構造を指す。ポリエステル骨格とは、複数のエステル結合が炭素原子を含有する基で連結された構造を指し、一例として下記一般式(A-1)で示される構造においてnaが2以上である構造が挙げられるほか、後述する式(22)等の(ポリ)エステルポリオール骨格が挙げられる。 The ester skeleton has a structure having an ester bond, and refers to, for example, a structure represented by the following general formula (A-1). The polyester skeleton refers to a structure in which a plurality of ester bonds are linked by a group containing a carbon atom, and an example thereof includes a structure represented by the following general formula (A-1) in which na is 2 or more. , (Poly) ester polyol skeleton such as the formula (22) described later can be mentioned.
Figure JPOXMLDOC01-appb-C000002
(Raは炭素原子数が1~20である2価の連結基であり、naは1以上の整数である。L1は-COO-又は-OCO-である。naが2以上である場合、複数存在するRaは互いに同一であってもよく異なっていてもよく、複数存在するL1は互いに同一であってもよく異なっていてもよい。*は結合箇所を示す。)
Figure JPOXMLDOC01-appb-C000002
(Ra is a divalent linking group having 1 to 20 carbon atoms, na is an integer of 1 or more. L1 is -COO- or -OCO-. When na is 2 or more, a plurality. The existing Ras may be the same or different from each other, and the plurality of L1s may be the same or different from each other. * Indicates a joint location.)
 エーテル骨格とはエーテル結合を有する構造を指し、例えば下記一般式(B1)で示される構造を指す。ポリエーテル骨格とは複数のエーテル結合が炭素原子を含有する基で連結された構造を指し、一例として下記一般式(B-1)で示される構造においてnbが2以上である構造が挙げられる。 The ether skeleton refers to a structure having an ether bond, for example, a structure represented by the following general formula (B1). The polyether skeleton refers to a structure in which a plurality of ether bonds are linked by a group containing a carbon atom, and an example thereof is a structure represented by the following general formula (B-1) in which nb is 2 or more.
Figure JPOXMLDOC01-appb-C000003
(Rbは炭素原子数が1~20である2価の連結基であり、nbは1以上の整数である。nbが2以上である場合、複数存在するRbは互いに同一であってもよく異なっていてもよい。*は結合箇所を示す。)
Figure JPOXMLDOC01-appb-C000003
(Rb is a divalent linking group having 1 to 20 carbon atoms, and nb is an integer of 1 or more. When nb is 2 or more, a plurality of Rbs existing may be the same or different from each other. * Indicates the joint location.)
 カーボネート骨格とはカーボネート結合を有する構造を指し、例えば下記一般式(C-1)で表される構造を指す。ポリカーボネート骨格とは、複数のカーボネート結合が炭素原子を含有する基で連結された構造を指し、一例として下記一般式(C-1)で示される構造においてncが2以上である構造が挙げられる。 The carbonate skeleton refers to a structure having a carbonate bond, for example, a structure represented by the following general formula (C-1). The polycarbonate skeleton refers to a structure in which a plurality of carbonate bonds are linked by a group containing a carbon atom, and an example thereof includes a structure represented by the following general formula (C-1) in which nc is 2 or more.
Figure JPOXMLDOC01-appb-C000004
(Rcは炭素原子数が1~20である2価の連結基であり、ncは1以上の整数である。ncが2以上である場合、複数存在するRcは互いに同一であってもよく異なっていてもよい。*は結合箇所を示す。)
Figure JPOXMLDOC01-appb-C000004
(Rc is a divalent linking group having 1 to 20 carbon atoms, and nc is an integer of 1 or more. When nc is 2 or more, a plurality of Rc existing may be the same or different from each other. * Indicates the joint location.)
 Ra、Rb及びRcで表される連結基としては炭素原子数1~20の二価の炭化水素基、又は、当該二価の炭化水素基のメチレン基が下記群1から選ばれる二価の基により、当該二価の基が互いに隣り合わない条件で置換された基が挙げられる。Ra、Rb及びRcに用いられる炭素原子数1~20の炭化水素基としては、上述の一般式(1)中のY1に用いられるものと同様とすることができる。
群1:-O-、-S-、-NR’-、-NR’-(C=O)-O-、-CO-、-(C=O)-O-、-O-(C=O)-、-O-(C=O)-O-、-SiR’2
 R’は水素原子又は炭素原子数1~10のアルキル基を表す。)
The linking group represented by Ra, Rb and Rc is a divalent hydrocarbon group having 1 to 20 carbon atoms, or a divalent group in which the methylene group of the divalent hydrocarbon group is selected from the following group 1. Therefore, a group in which the divalent groups are substituted under the condition that they are not adjacent to each other can be mentioned. The hydrocarbon group having 1 to 20 carbon atoms used for Ra, Rb and Rc can be the same as that used for Y 1 in the above general formula (1).
Group 1: -O-, -S-, -NR'-, -NR'-(C = O) -O-, -CO-,-(C = O) -O-, -O- (C = O) ) -, - O- (C = O) -O -, - SiR '2 -
R'represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. )
 ポリオールとしては、フェノキシ樹脂、ビスフェノール型高分子エポキシ樹脂、水酸基を有するポリブタジエン類、アクリルポリオールなども挙げられる。
 本開示においては、ポリオールが、(ポリ)エステルポリオール、(ポリ)エーテルポリオール又はポリオール単量体であることが好ましく、中でも、(ポリ)エステルポリオール又は(ポリ)エーテルポリオールであることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
Examples of the polyol include a phenoxy resin, a bisphenol type high molecular weight epoxy resin, polybutadienes having a hydroxyl group, and an acrylic polyol.
In the present disclosure, the polyol is preferably a (poly) ester polyol, a (poly) ether polyol or a polyol monomer, and more preferably a (poly) ester polyol or a (poly) ether polyol. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 ポリオール単量体としては、(ポリ)エステル骨格、(ポリ)エーテル骨格及び(ポリ)カーボネート骨格をいずれも有しない化合物であり、例えば、下記一般式(21)で表される化合物を用いることができる。 The polyol monomer is a compound having no (poly) ester skeleton, (poly) ether skeleton, or (poly) carbonate skeleton, and for example, a compound represented by the following general formula (21) may be used. can.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
(式中、R1は、n1価の炭素原子数1~20の炭化水素基を表し、
 n1は、2以上の整数を表す。)
(In the formula, R 1 represents a hydrocarbon group having n1 valence and 1 to 20 carbon atoms.
n1 represents an integer of 2 or more. )
 R1として用いられるn1価の炭素原子数1~20の炭化水素基としては、一価の炭素原子数1~20の炭化水素基からn1-1個の水素原子を除いた基を用いることができる。 As the hydrocarbon group having 1 to 20 n1-valent carbon atoms used as R 1 , a group obtained by removing n1-1 hydrogen atoms from the hydrocarbon group having 1 to 20 monovalent carbon atoms can be used. can.
 一価の炭素原子数1~20の炭化水素基としては、上述の一般式(1)中のY1に用いられるものと同様とすることができる。 The hydrocarbon group having a monovalent carbon atom number of 1 to 20 can be the same as that used for Y 1 in the above general formula (1).
 R1に用いられる炭化水素基は、脂肪族炭化水素基であることが好ましく、中でも、アルキル基からn1-1個の水素原子を除いた基であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
 R1に用いられる炭化水素基の炭素原子数は、1~20であればよいが、2~15であることが好ましく、中でも、3~10であることが好ましく、特に、4~8であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
The hydrocarbon group used for R 1 is preferably an aliphatic hydrocarbon group, and more preferably a group obtained by removing n1-1 hydrogen atoms from an alkyl group. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
The number of carbon atoms of the hydrocarbon group used for R 1 may be 1 to 20, preferably 2 to 15, particularly preferably 3 to 10, and particularly 4 to 8. Is preferable. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 n1としては、2以上であればよく、水酸基を有する化合物の好ましい水酸基数として挙げたものと同様とすることができる。具体的には、n1は、3以上10以下であることが好ましく、3又は4であることが好ましく、特に、3であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 The n1 may be 2 or more, and may be the same as those listed as the preferable number of hydroxyl groups of the compound having a hydroxyl group. Specifically, n1 is preferably 3 or more and 10 or less, preferably 3 or 4, and particularly preferably 3. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 ポリオール単量体としては、具体的には、エチレングリコール、ジエチレングリコール、1,2-プロパンジオール、2-メチル-1,3-プロパンジオール、1,3-プロパンジオール、1,4-シクロヘキサンジメタノール、プロピレングリコール、ジプロピレングリコール、グリセリン、トリメチロールプロパン、1,3-ジヒドロキシアセトン、ヘキシレングリコール、1,2,6-ヘキサントリオール、ジトリメチロールプロパン、マンニトール、ソルビトール、及びペンタエリスリトール等の芳香族環を有しない脂肪族ポリオールが挙げられる。
 ポリオール単量体としては、ビスフェノールA、ビスフェノールE等のビスフェノール構造を有する化合物、ビフェノール等のビフェニル構造を有する化合物等の芳香族環を有する化合物も挙げられる。
Specific examples of the polyol monomer include ethylene glycol, diethylene glycol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,3-propanediol, and 1,4-cyclohexanedimethanol. Aromatic rings such as propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol, ditrimethylolpropane, mannitol, sorbitol, and pentaerythritol. Examples include aliphatic polyols that do not have.
Examples of the polyol monomer include compounds having a bisphenol structure such as bisphenol A and bisphenol E, and compounds having an aromatic ring such as compounds having a biphenyl structure such as biphenol.
 (ポリ)エステルポリオールとしては、(ポリ)エステル骨格を有する化合物であり、例えば、下記一般式(22)で表される化合物を用いることができる。 The (poly) ester polyol is a compound having a (poly) ester skeleton, and for example, a compound represented by the following general formula (22) can be used.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
(式中、R2は、n2価の炭素原子数1~20の炭化水素基を表し、
 n2は、2以上の整数を表し、
 X2は、それぞれ独立に、下記一般式(22-1)で表される基であり、
 X2の少なくとも1つは、式(22-1)中のn3が1以上の整数である。)
(In the formula, R 2 represents an n2-valent hydrocarbon group having 1 to 20 carbon atoms.
n2 represents an integer of 2 or more and represents
X 2 is a group represented by the following general formula (22-1) independently of each other.
At least one of X 2 is an integer in which n3 in the equation (22-1) is 1 or more. )
*-O-(CO-R3-O)n3-H     (22-1) * -O- (CO-R 3- O) n3-H (22-1)
(式中、R3は、二価の炭素原子数1~20の炭化水素基を表し、
 n3は、0又は1以上の整数を表し、*は結合箇所を表す。)
(In the formula, R 3 represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
n3 represents an integer of 0 or 1 or more, and * represents a joint location. )
 R2に用いられるn2価の炭素原子数1~20の炭化水素基としては、一価の炭素原子数1~20の炭化水素基からn2-1個の水素原子を除いた基を用いることができる。一価の炭素原子数1~20の炭化水素基については、上述の一般式(1)中のY1に用いられるものと同様とすることができる。 As the n2-valent carbon atom number 1 to 20 hydrocarbon group used for R 2 , a group obtained by removing n2-1 hydrogen atoms from the monovalent carbon atom number 1 to 20 carbon atom group may be used. can. The hydrocarbon group having a monovalent carbon atom number of 1 to 20 can be the same as that used for Y 1 in the above general formula (1).
 R2に用いられる炭化水素基は、脂肪族炭化水素基であることが好ましく、中でも、アルキル基からn2-1個の水素原子を除いた基であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
 R2に用いられる炭化水素基の炭素原子数は、1~20であればよいが、2~15であることが好ましく、中でも、3~10であることが好ましく、特に、3~8であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
The hydrocarbon group used for R 2 is preferably an aliphatic hydrocarbon group, and more preferably a group obtained by removing n2-1 hydrogen atoms from an alkyl group. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
The number of carbon atoms of the hydrocarbon group used for R 2 may be 1 to 20, preferably 2 to 15, particularly preferably 3 to 10, and particularly 3 to 8. Is preferable. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 式(22)に表される化合物において、式(22-1)で表される基が複数存在する場合、複数存在するR3及びn3はそれぞれ同一であっても異なっていてもよい。
 R3に用いられる炭化水素基は、脂肪族炭化水素基であることが好ましく、中でも、アルキル基から1個の水素原子を除いた基であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
 R3に用いられる炭化水素基の炭素原子数は、1~20であればよいが、2~10であることが好ましく、中でも、3~8であることが好ましく、特に、4~6であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
In the compound represented by the formula (22), when a plurality of groups represented by the formula (22-1) are present, the plurality of existing R 3 and n 3 may be the same or different.
The hydrocarbon group used for R 3 is preferably an aliphatic hydrocarbon group, and more preferably a group obtained by removing one hydrogen atom from an alkyl group. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
The number of carbon atoms of the hydrocarbon group used for R 3 may be 1 to 20, preferably 2 to 10, particularly preferably 3 to 8, and particularly 4 to 6. Is preferable. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 n2としては、2以上であればよく、水酸基を有する化合物の好ましい水酸基数として挙げたものと同様とすることができる。具体的には、n2は、3以上10以下であることが好ましく、3又は4であることが好ましく、特に、3であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 The n2 may be 2 or more, and may be the same as those listed as the preferable number of hydroxyl groups of the compound having a hydroxyl group. Specifically, n2 is preferably 3 or more and 10 or less, preferably 3 or 4, and particularly preferably 3. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 n3としては、0又は1以上であればよく、その上限は、30以下とすることができる。一分子中に複数存在するn3は同一であっても異なっていてもよい。
 本開示においては、一般式(22)で表される化合物中のn3の合計が、30以下であることが好ましく、中でも、1以上20以下であることが好ましく、特に、1以上15以下であることが好ましく、中でも特に、1以上10以下であることが好ましく、中でも特に、1以上5以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
The n3 may be 0 or 1 or more, and the upper limit thereof may be 30 or less. A plurality of n3s existing in one molecule may be the same or different.
In the present disclosure, the total amount of n3 in the compound represented by the general formula (22) is preferably 30 or less, more preferably 1 or more and 20 or less, and particularly 1 or more and 15 or less. It is particularly preferable that the amount is 1 or more and 10 or less, and particularly preferably 1 or more and 5 or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 一般式(22)で表されn3の合計が2以上である化合物も含め、ポリエステルポリオールの例としては、ポリオールと、ポリカルボン酸又はヒドロキシカルボン酸との縮合重合体;ポリオールとラクトン類の開環重合体等が挙げられる。
 このようなポリエステルポリオールの合成に用いることができるポリオールとしては、例えば、上述のポリオール単量体が挙げられる。
 ポリエステルポリオールの合成に用いることができるポリカルボン酸、ヒドロキシカルボン酸としては、例えば、特開2019-052231号公報に記載の化合物が挙げられる。
 ポリエステルポリオールの合成に用いることができるラクトン類についても、特開2019-052231号公報に記載の化合物が挙げられ、具体的には、ε-カプロラクトン、δ-バレロラクトン、及びγ-ブチロラクトンが挙げられ、中でも、ε-カプロラクトンを好ましく用いることができる。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
Examples of polyester polyols, including compounds represented by the general formula (22) and having a total of n3 of 2 or more, are a condensation polymer of a polyol and a polycarboxylic acid or a hydroxycarboxylic acid; ring-opening of the polyol and the lactones. Examples include polymers.
Examples of the polyol that can be used for synthesizing such a polyester polyol include the above-mentioned polyol monomer.
Examples of the polycarboxylic acid and hydroxycarboxylic acid that can be used in the synthesis of polyester polyols include the compounds described in JP-A-2019-052231.
Examples of the lactones that can be used for the synthesis of the polyester polyol include the compounds described in JP-A-2019-052231, and specific examples thereof include ε-caprolactone, δ-valerolactone, and γ-butyrolactone. Above all, ε-caprolactone can be preferably used. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 (ポリ)エーテルポリオールとしては、上述のポリオール単量体の多量体;ポリオール単量体と、エチレンオキサイド等のアルキレンオキサイドとの付加反応体;テトラヒドロフランなどの環状エーテルの開環重合体が挙げられる。例えば、水酸基が3以上であって好ましいポリエーテルポリオールとしては、グリセリン又はトリメチロールプロパンなどのポリオール単量体にプロピレンオキサイド及び/又はエチレンオキサイドを付加して得られるポリエーテルポリオールが挙げられる。
 (ポリ)エーテルポリオールとしては、ジトリメチロールプロパン(4官能)、ジペンタエリスリトール(6官能)等が挙げられる。
Examples of the (poly) ether polyol include a multimer of the above-mentioned polyol monomer; an addition reaction product of the polyol monomer and an alkylene oxide such as ethylene oxide; and a ring-opening polymer of a cyclic ether such as tetrahydrofuran. For example, a preferred polyether polyol having 3 or more hydroxyl groups includes a polyether polyol obtained by adding propylene oxide and / or ethylene oxide to a polyol monomer such as glycerin or trimethylolpropane.
Examples of the (poly) ether polyol include ditrimethylolpropane (4-functional) and dipentaerythritol (6-functional).
 (ポリ)エーテルポリオールの好適な例の一つとして、以下の式(23)で表される化合物が挙げられる。 As one of the preferable examples of the (poly) ether polyol, a compound represented by the following formula (23) can be mentioned.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
(式中、R301は、n301価の炭素原子数1~20の炭化水素基を表し、
 n301は、2以上の整数を表し、
 X301は、それぞれ独立に、下記式(23-1)で表される基であり、
 X301の少なくとも1つは、式(23-1)中のn5又はm5が1以上の整数である。)
(In the formula, R 301 represents a hydrocarbon group having n 301 valence and 1 to 20 carbon atoms.
n 301 represents an integer of 2 or more.
Each of X 301 is a group represented by the following formula (23-1) independently.
At least one of X 301 is an integer in which n5 or m5 in the equation (23-1) is 1 or more. )
*-O(-R302-O)n5(-R303-O)m5-H     (23-1) * -O (-R 302- O) n5 (-R 303- O) m5-H (23-1)
(式中、R302及びR303はそれぞれ独立に、二価の炭素原子数2~4の炭化水素基を表し、
 n5及びm5はそれぞれ独立に、0又は1以上の整数を表し、*は結合箇所を表す。)
(In the formula, R 302 and R 303 each independently represent a divalent hydrocarbon group having 2 to 4 carbon atoms.
n5 and m5 independently represent an integer of 0 or 1 or more, and * represents a joint location. )
 R301に用いられるn301価の炭素原子数1~20の炭化水素基としては、一価の炭素原子数1~20の炭化水素基からn301-1個の水素原子を除いた基を用いることができる。一価の炭素原子数1~20の炭化水素基については、上述の一般式(1)中のY1に用いられるものと同様とすることができる。 As the n 301- valent hydrocarbon group having 1 to 20 carbon atoms used in R 301 , a group obtained by removing n 301-1 hydrogen atoms from the monovalent hydrocarbon group having 1 to 20 carbon atoms is used. be able to. The hydrocarbon group having a monovalent carbon atom number of 1 to 20 can be the same as that used for Y 1 in the above general formula (1).
 R301に用いられる炭化水素基は、脂肪族炭化水素基であることが好ましく、中でも、アルキル基からn301-1個の水素原子を除いた基であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
 R301に用いられる炭化水素基の炭素原子数は、1~20であればよいが、2~15であることが好ましく、中でも、3~10であることが好ましく、特に、3~8であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
The hydrocarbon group used for R 301 is preferably an aliphatic hydrocarbon group, and more preferably a group obtained by removing n301-1 hydrogen atoms from an alkyl group. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
The number of carbon atoms of the hydrocarbon group used in R 301 may be 1 to 20, but preferably 2 to 15, particularly preferably 3 to 10, and particularly 3 to 8. Is preferable. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 R302及びR303としては、アルキレン基が好適に挙げられる。例えば後述するB5はR302がプロピレン、R303がエチレンである。
 n301としては、2以上であればよく、水酸基を有する化合物の好ましい水酸基数として挙げたものと同様とすることができる。具体的には、n301は、3以上10以下であることが好ましく、3又は4であることが好ましく、特に、3であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
Preferred examples of R 302 and R 303 include an alkylene group. For example, in B5 described later, R 302 is propylene and R 303 is ethylene.
The n 301 may be 2 or more, and may be the same as those listed as the preferable number of hydroxyl groups of the compound having a hydroxyl group. Specifically, n 301 is preferably 3 or more and 10 or less, preferably 3 or 4, and particularly preferably 3. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 本開示においては、式(23-1)中のn5及びm5の合計が、2以上であることが好ましく、中でも15以上であることが好ましく、一般式(23)で表される化合物中のn5及びm5の合計は、45以上であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 In the present disclosure, the total of n5 and m5 in the formula (23-1) is preferably 2 or more, more preferably 15 or more, and n5 in the compound represented by the general formula (23). The total of m5 and m5 is preferably 45 or more. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 ポリカーボネートポリオールとしては、上述のポリオール単量体を用い、ホスゲン法、カーボネート交換反応等を用いて得られるものが挙げられる。 Examples of the polycarbonate polyol include those obtained by using the above-mentioned polyol monomer and using a phosgene method, a carbonate exchange reaction, or the like.
 ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオールの市販品としては、例えば特開2019-052231号公報に記載の製品が挙げられる。 Examples of commercially available products of polyester polyols, polyether polyols, and polycarbonate polyols include the products described in JP-A-2019-052231.
 水酸基含有成分の含有量としては、所望の寸法安定性、接着力及び深部硬化性が得られるものであればよいが、上記環状エーテル成分及び上記水酸基含有成分の合計100質量部中に、1質量部以上50質量部以下であることが好ましく、中でも、5質量部以上40質量部以下であることが好ましく、特に、10質量部以上35質量部以下であることが好ましく、中でも特に、15質量部以上30質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 The content of the hydroxyl group-containing component may be any as long as it can obtain desired dimensional stability, adhesive strength and deep curability, but 1 mass in 100 parts by mass of the cyclic ether component and the hydroxyl group-containing component in total. It is preferably 5 parts by mass or more and 50 parts by mass or less, particularly preferably 5 parts by mass or more and 40 parts by mass or less, particularly preferably 10 parts by mass or more and 35 parts by mass or less, and particularly 15 parts by mass. It is preferably 30 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 水酸基含有成分の含有量としては、所望の寸法安定性、接着力及び深部硬化性が得られるものであればよいが、上記組成物の固形分100質量部中に、1質量部以上であることが好ましく、中でも、2質量部以上15質量部以下であることが好ましく、特に、3質量部以上10質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 The content of the hydroxyl group-containing component may be any as long as it can obtain desired dimensional stability, adhesive strength and deep curability, but it should be 1 part by mass or more in 100 parts by mass of the solid content of the above composition. Is preferable, and in particular, it is preferably 2 parts by mass or more and 15 parts by mass or less, and particularly preferably 3 parts by mass or more and 10 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 水酸基含有成分の含有量は、所望の寸法安定性、接着力及び深部硬化性が得られるものであればよいが、上記組成物の充填剤を除く固形分100質量部中に、1質量部以上50質量部以下であることが好ましく、中でも、5質量部以上40質量部以下であることが好ましく、特に、10質量部以上35質量部以下であることが好ましく、中でも特に、15質量部以上30質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 The content of the hydroxyl group-containing component may be one that can obtain desired dimensional stability, adhesive strength and deep curability, but is 1 part by mass or more in 100 parts by mass of the solid content excluding the filler of the above composition. It is preferably 50 parts by mass or less, particularly preferably 5 parts by mass or more and 40 parts by mass or less, particularly preferably 10 parts by mass or more and 35 parts by mass or less, and particularly preferably 15 parts by mass or more and 30 parts by mass. It is preferably less than or equal to parts by mass. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
 水酸基含有成分の含有量としては、所望の寸法安定性、接着力及び深部硬化性が得られるものであればよいが、組成物100質量部中に、1質量部以上であることが好ましく、中でも、2質量部以上15質量部以下であることが好ましく、特に、3質量部以上10質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。 The content of the hydroxyl group-containing component may be any as long as it can obtain desired dimensional stability, adhesive strength and deep curability, but is preferably 1 part by mass or more in 100 parts by mass of the composition, and above all. It is preferably 2 parts by mass or more and 15 parts by mass or less, and particularly preferably 3 parts by mass or more and 10 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
3.充填剤
 充填剤は、上述の環状エーテル成分及び水酸基含有成分中に溶解しない粒状のものである。
 また、充填剤は、温度変化による体積変化が小さく、上記組成物の硬化物に寸法安定性を付与できるものである。
3. 3. Filler The filler is a granular material that does not dissolve in the above-mentioned cyclic ether component and hydroxyl group-containing component.
Further, the filler has a small volume change due to a temperature change, and can impart dimensional stability to the cured product of the above composition.
 充填剤としては、所望の寸法安定性、接着力及び深部硬化性が得られるものであればよいが、平均粒径1μm以上100μm以下の充填剤(以下、充填剤1と称する場合がある。)を含むことが好ましい。
 充填剤1の平均粒径としては、2μm以上50μm以下であることが好ましく、特に、3μm以上30μm以下であることが好ましく、中でも特に、5μm以上20μm以下であることが好ましい。上記平均粒径が上述の範囲であることで、上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、寸法安定性及び深部硬化性に優れたものとなるからである。また、保存安定性、分散性や塗工性等に優れたものとなるからである。
 なお、平均粒径は、メジアン径(D50)とも呼ばれ、ある粒子径から2つに分けたとき、大きい側と小さい側が等量(体積基準)となる径のことであり、レーザー回折・散乱法によって湿式(溶媒:水)で測定した体積基準の粒度分布から、粒子径が小さい側から累積して50%となる粒子径を意味する。例えば、LA-950V2(堀場製作所製;粒子測定装置、レーザー回折/散乱式)を用いて測定することができる。
The filler may be any filler that can obtain desired dimensional stability, adhesive strength and deep curability, but may be a filler having an average particle size of 1 μm or more and 100 μm or less (hereinafter, may be referred to as filler 1). It is preferable to include.
The average particle size of the filler 1 is preferably 2 μm or more and 50 μm or less, particularly preferably 3 μm or more and 30 μm or less, and particularly preferably 5 μm or more and 20 μm or less. When the average particle size is in the above range, the composition is excellent in the balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. Because it becomes. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
The average particle size is also called the median diameter (D50), which means that when a certain particle size is divided into two, the large side and the small side have the same amount (volume basis), and laser diffraction / scattering. From the volume-based particle size distribution measured wet (solvent: water) by the method, it means the particle size cumulatively 50% from the side with the smaller particle size. For example, it can be measured using LA-950V2 (manufactured by HORIBA, Ltd .; particle measuring device, laser diffraction / scattering type).
 充填剤1の含有量としては、充填剤全体100質量部中に、80質量部以上であることが好ましく、中でも、90質量部以上であることが好ましく、特に、95質量部以上であることが好ましく、中でも特に、98質量部以上であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、寸法安定性及び深部硬化性に優れたものとなるからである。また、保存安定性、分散性や塗工性等に優れたものとなるからである。 The content of the filler 1 is preferably 80 parts by mass or more, particularly preferably 90 parts by mass or more, and particularly 95 parts by mass or more in 100 parts by mass of the entire filler. It is preferable, and in particular, it is preferably 98 parts by mass or more. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
 充填剤は、充填剤1より平均粒径の小さい充填剤(以下、充填剤2と称する場合がある。)を組み合わせて用いてもよい。
 充填剤2の平均粒径としては、1μm未満とすることができ、中でも、1nm以上500nm以下であることが好ましく、特に、5nm以上100nm以下であることが好ましく、特に、10nm以上50nm以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスに優れたものとしつつ、分散性や塗工性の調整が容易となるからである。
The filler may be used in combination with a filler having an average particle size smaller than that of the filler 1 (hereinafter, may be referred to as a filler 2).
The average particle size of the filler 2 can be less than 1 μm, particularly preferably 1 nm or more and 500 nm or less, particularly preferably 5 nm or more and 100 nm or less, and particularly preferably 10 nm or more and 50 nm or less. Is preferable. This is because the composition has an excellent balance of dimensional stability, adhesive strength and deep curability, and easily adjusts dispersibility and coatability.
 充填剤1及び充填剤2を併用する場合、充填剤2の含有量としては、充填剤全体100質量部中に、20質量部以下であることが好ましく、中でも、0.1質量部以上10質量部以下であることが好ましく、0.2質量部以上5質量部以下であることが好ましく、0.5質量部以上2質量部以下であることが好ましく、0.8質量部以上1.5質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、寸法安定性及び深部硬化性に優れたものとなるからである。また、保存安定性、分散性や塗工性等に優れたものとなるからである。 When the filler 1 and the filler 2 are used in combination, the content of the filler 2 is preferably 20 parts by mass or less in 100 parts by mass of the entire filler, and in particular, 0.1 parts by mass or more and 10 parts by mass. It is preferably 0.2 parts by mass or more, preferably 5 parts by mass or less, preferably 0.5 parts by mass or more and 2 parts by mass or less, and 0.8 parts by mass or more and 1.5 parts by mass. It is preferably less than or equal to a part. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
 充填剤の平均粒径、すなわち、組成物に含まれる充填剤全体の平均粒径(D50)としては、所望の寸法安定性、接着力及び深部硬化性が得られるものであればよいが、1μm以上100μm以下であることが好ましく、中でも、2μm以上50μm以下であることが好ましく、特に、3μm以上30μm以下であることが好ましく、中でも特に、5μm以上20μm以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、寸法安定性及び深部硬化性に優れたものとなるからである。また、保存安定性、分散性や塗工性等に優れたものとなるからである。 The average particle size of the filler, that is, the average particle size (D50) of the entire filler contained in the composition may be 1 μm as long as it can obtain desired dimensional stability, adhesive strength and deep curability. It is preferably 100 μm or less, more preferably 2 μm or more and 50 μm or less, particularly preferably 3 μm or more and 30 μm or less, and particularly preferably 5 μm or more and 20 μm or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
 充填剤の粒径(D1)、すなわち、組成物に含まれる充填剤全体の粒径(D1)としては、所望の寸法安定性、接着力及び深部硬化性が得られるものであればよいが、1nm以上1μm未満であることが好ましく、中でも5nm以上100nm以下であることが好ましく、特に、10nm以上50nm以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスに優れたものとしつつ、保存安定性に優れ、分散性や塗工性の調整容易なものとなるからである。なお、粒径(D1)は、体積基準の粒度分布から、粒子径が小さい側から累積して1%となる粒子径を意味する。 The particle size (D1) of the filler, that is, the particle size (D1) of the entire filler contained in the composition may be any as long as it can obtain desired dimensional stability, adhesive strength and deep curability. It is preferably 1 nm or more and less than 1 μm, particularly preferably 5 nm or more and 100 nm or less, and particularly preferably 10 nm or more and 50 nm or less. This is because the composition has an excellent balance of dimensional stability, adhesive strength and deep curability, and has excellent storage stability, and the dispersibility and coatability can be easily adjusted. The particle size (D1) means a particle size that is cumulatively 1% from the side with the smaller particle size from the volume-based particle size distribution.
 充填剤の屈折率としては、所望の寸法安定性、接着力及び深部硬化性が得られるものであればよいが、1.2以上2.0以下であることが好ましく、中でも、1.3以上1.8以下であることが好ましく、特に、1.4以上1.6以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、深部硬化性に優れたものとなるからである。
 なお、屈折率の測定方法は、例えば、JIS K 0062:1992に基づいて測定できる。
The refractive index of the filler may be any as long as it can obtain desired dimensional stability, adhesive strength and deep curability, but is preferably 1.2 or more and 2.0 or less, and above all, 1.3 or more. It is preferably 1.8 or less, and particularly preferably 1.4 or more and 1.6 or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in deep curability.
The method for measuring the refractive index can be measured based on, for example, JIS K 0062: 1992.
 このような充填剤としては、無機物の粒子(以下、無機粒子と称する場合がある。)、有機物の粒子(以下、有機粒子と称する場合がある。)等の粒子を有するものとすることができる。
 本開示においては、充填剤が、無機粒子を有するものであることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、寸法安定性及び深部硬化性に優れたものとなるからである。
Such a filler may have particles such as inorganic particles (hereinafter, may be referred to as inorganic particles) and organic particles (hereinafter, may be referred to as organic particles). ..
In the present disclosure, it is preferable that the filler has inorganic particles. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability.
 無機粒子の構成材料としては、例えば、金属酸化物(例えば、アルミナ、チタニアなど)、金属水酸化物(例えば、水酸化アルミニウムなど)、金属炭酸塩(例えば、炭酸カルシウムなど)、金属硫酸塩(例えば、硫酸バリウムなど)、シリカ(例えば、結晶性シリカ、溶融シリカ、フュームドシリカ、乾式シリカ(アエロジル)など)、ガラスパウダー、中空フィラー(例えば、ガラス中空球、シリカ中空球、アルミナ中空球など)、ケイ酸塩(例えば、珪砂、珪藻土、マイカ、クレー、カオリン、タルクなど)、フッ化物(例えば、ホタル石など)、リン酸塩(例えば、リン酸カルシウムなど)、粘土鉱物(例えば、スメクタイトなど)などが挙げられる。
 本開示においては、無機粒子の構成材料が、シリカ、ケイ酸塩、ガラスパウダーであることが好ましく、中でも、シリカであることが好ましく、中でも特に、溶融シリカ、フュームドシリカ、乾式シリカ(アエロジル)であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、寸法安定性及び深部硬化性に優れたものとなるからである。
Examples of the constituent materials of the inorganic particles include metal oxides (eg, alumina, titania, etc.), metal hydroxides (eg, aluminum hydroxide, etc.), metal carbonates (eg, calcium carbonate, etc.), and metal sulfates (eg, calcium carbonate). For example, barium sulfate, etc.), silica (eg, crystalline silica, molten silica, fumed silica, dry silica (Aerodil), etc.), glass powder, hollow filler (eg, glass hollow sphere, silica hollow sphere, alumina hollow sphere, etc.), etc. ), Silicates (eg, silica sand, diatomaceous soil, mica, clay, kaolin, talc, etc.), fluorides (eg, firefly stones, etc.), phosphates (eg, calcium phosphate, etc.), clay minerals (eg, smectite, etc.) And so on.
In the present disclosure, the constituent materials of the inorganic particles are preferably silica, silicate, and glass powder, particularly preferably silica, and particularly, fused silica, fumed silica, and dry silica (Aerosil). Is preferable. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability.
 有機粒子を構成する材料としては、ポリメチルメタクリレート、ポリエチルメタクリレート、メチルメタクリレート-エチルメタクリレート共重合体、エチルメタクリレート-ブチルメタクリレート共重合体、メチルメタクリレート-トリメチロールプロパントリメタクリレート共重合体、ポリ塩化ビニル、ポリスチレン、塩素化ポリエチレン、ナイロン、ポリサルホン、ポリエーテルサルホン、ポリカーボネート等が挙げられる。これらの有機核を構成する材料としては、架橋性単量体を共重合させた架橋体であるのが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、寸法安定性により優れたものとなるからである。 Materials constituting the organic particles include polymethylmethacrylate, polyethylmethacrylate, methylmethacrylate-ethylmethacrylate copolymer, ethylmethacrylate-butylmethacrylate copolymer, methylmethacrylate-trimethylolpropanetrimethacrylate copolymer, and polyvinylchloride. , Polystyrene, chlorinated polyethylene, nylon, polysulfone, polyethersulfone, polycarbonate and the like. As the material constituting these organic nuclei, a crosslinked body obtained by copolymerizing a crosslinkable monomer is preferable. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability.
 充填剤は、粒子のみからなるものであってもよいが、表面処理層により被覆された粒子、すなわち、粒子及び粒子表面を被覆する表面処理層を有するものを含むことが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、寸法安定性及び深部硬化性に優れたものとなるからである。また、保存安定性、分散性や塗工性等に優れたものとなるからである。 The filler may be composed of only particles, but preferably includes particles coated with a surface treatment layer, that is, particles having a surface treatment layer covering the particles and the surface of the particles. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
 表面処理層とは、粒子の形成後に、粒子の表面を被覆するために形成される層を指す。表面処理層は粒子表面の全体を被覆していてもよいし、粒子表面の一部のみを被覆していてもよい。表面処理層を形成する表面処理剤としては、粒子と安定的に結合可能なものを用いることができ、例えば、脂肪酸、樹脂酸、油脂、界面活性剤、シリコンオイル、カップリング剤(シラン系、チタン系、リン酸系、カルボン酸系等)が挙げられるが、中でも、シランカップリング剤であることが好ましい。上記組成物は、分散性、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、寸法安定性及び深部硬化性に優れたものとなるからである。 The surface treatment layer refers to a layer formed to cover the surface of the particles after the formation of the particles. The surface treatment layer may cover the entire surface of the particles, or may cover only a part of the surface of the particles. As the surface treatment agent for forming the surface treatment layer, an agent that can stably bind to particles can be used, and for example, fatty acids, resin acids, fats and oils, surfactants, silicon oils, coupling agents (silane-based, coupling agents, etc.) can be used. (Titanium-based, phosphoric acid-based, carboxylic acid-based, etc.) can be mentioned, but among them, a silane coupling agent is preferable. This is because the composition is excellent in the balance of dispersibility, dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability.
 シランカップリング剤としては、ジメチルジクロロシラン、トリメチルクロロシラン、ジメチルジメトキシシラン、トリメチルメトキシシラン、ジメチルジエトキシシラン、n-プロピルトリメトキシシラン、n-プロピルトリエトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、ポリジメチルシロキサン等のアルキル基含有シランカップリング剤;フェニルトリクロロシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン等のフェニル基含有シランカップリング剤;ビニルトリメトキシシラン、ビニルトリエトキシシラン等のビニル基含有シランカップリング剤;p-スチリルトリメトキシシラン等のスチリル基含有シランカップリング剤;2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシラン等のエポキシ基含有シランカップリング剤;3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルトリメトキシシラン等のメタクリル基含有シランカップリング剤、3-アクリロキシプロピルトリメトキシシラン等のアクリル基含有シランカップリング剤;ヘキサメチルジシラザン、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン等のアミノ基含有シランカップリング剤、3-メルカプトプロピルトリメトキシシラン等のメルカプト基含有シランカップリング剤、3-イソシアネートプロピルトリエトキシシラン等のイソシアネート基含有シランカップリング剤等が挙げられる。 Examples of the silane coupling agent include dimethyldichlorosilane, trimethylchlorosilane, dimethyldimethoxysilane, trimethylmethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, and hexyltriethoxysilane. , Polydimethylsiloxane and other alkyl group-containing silane coupling agents; phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane and other phenyl group-containing silane coupling agents; vinyltrimethoxysilane, vinyltriethoxysilane and other vinyl groups. Silane-containing silane coupling agent; styryl group-containing silane coupling agent such as p-styryltrimethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glyce Epoxy group-containing silane coupling agents such as sidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; methacrylic group-containing silanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane. Acrylic group-containing silane coupling agents such as coupling agents and 3-acryloxypropyltrimethoxysilane; hexamethyldisilazane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3- Amino group-containing silane coupling agents such as aminopropyltrimethoxysilane, mercapto group-containing silane coupling agents such as 3-mercaptopropyltrimethoxysilane, isocyanate group-containing silane coupling agents such as 3-isocyanuspropyltriethoxysilane, etc. Can be mentioned.
 表面処理層としては、アルキル基、フェニル基等の芳香族環基、ビニル基、スチリル基、エポキシ基、メタクリル基、アクリル基、アミノ基、メルカプト基、イソシアネート基等の官能基を有するものを用いることができ、中でも、ビニル基、エポキシ基、メタクリル基、アクリル基等を有するものであることが好ましく、特に、エポキシ基を有するものであることが好ましい。上記組成物は、分散性、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、寸法安定性及び深部硬化性に優れたものとなるからである。また、保存安定性、分散性や塗工性等に優れたものとなるからである。 As the surface treatment layer, a layer having a functional group such as an aromatic ring group such as an alkyl group and a phenyl group, a vinyl group, a styryl group, an epoxy group, a methacrylic group, an acrylic group, an amino group, a mercapto group and an isocyanate group is used. Among them, those having a vinyl group, an epoxy group, a methacrylic group, an acrylic group and the like are preferable, and those having an epoxy group are particularly preferable. This is because the composition is excellent in the balance of dispersibility, dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
 表面処理層の含有量としては、所望の寸法安定性、接着力及び深部硬化性が得られるものであればよいが、表面処理層により被覆された粒子、すなわち、粒子及び表面処理層の合計100質量部中に、0.05質量部以上10質量部以下とすることができる。 The content of the surface treatment layer may be any as long as it can obtain the desired dimensional stability, adhesive strength and deep curability, but the particles coated by the surface treatment layer, that is, the particles and the surface treatment layer are 100 in total. The number of parts by mass may be 0.05 parts by mass or more and 10 parts by mass or less.
 表面処理層の形成方法としては、直接処理法(例えば乾式法、スラリー法、スプレー法等)、インテグラルブレンド法(例えば直接法、マスターバッチ法等)、ドライコンセントレート法等の公知の方法を使用できる。 As a method for forming the surface treatment layer, known methods such as a direct treatment method (for example, a dry method, a slurry method, a spray method, etc.), an integral blend method (for example, a direct method, a masterbatch method, etc.), a dry concentrate method, etc. are used. Can be used.
 充填剤の含有量は、環状エーテル成分及び水酸基含有成分の合計100質量部に対して、40質量部以上であるが、中でも、50質量部以上1000質量部以下であることが好ましく、特に、100質量部以上700質量部以下であることが好ましく、中でも特に、300質量部以上500質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、寸法安定性及び深部硬化性に優れたものとなるからである。また、保存安定性、分散性や塗工性等に優れたものとなるからである。 The content of the filler is 40 parts by mass or more with respect to 100 parts by mass in total of the cyclic ether component and the hydroxyl group-containing component, and more preferably 50 parts by mass or more and 1000 parts by mass or less, particularly 100 parts. It is preferably 7 parts by mass or more and 700 parts by mass or less, and particularly preferably 300 parts by mass or more and 500 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
 充填剤の含有量は、組成物の固形分100質量部中に、20質量部以上であることが好ましく、中でも、40質量部以上98質量部以下であることが好ましく、特に、60質量部以上95質量部以下であることが好ましく、特に、70質量部以上90質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、寸法安定性及び深部硬化性に優れたものとなるからである。また、保存安定性、分散性や塗工性等に優れたものとなるからである。 The content of the filler is preferably 20 parts by mass or more, preferably 40 parts by mass or more and 98 parts by mass or less, and particularly 60 parts by mass or more, in 100 parts by mass of the solid content of the composition. It is preferably 95 parts by mass or less, and particularly preferably 70 parts by mass or more and 90 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
 充填剤の含有量は、組成物100質量部中に、20質量部以上であることが好ましく、中でも、40質量部以上98質量部以下であることが好ましく、特に、60質量部以上95質量部以下であることが好ましく、特に、70質量部以上90質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、寸法安定性及び深部硬化性に優れたものとなるからである。また、保存安定性、分散性や塗工性等に優れたものとなるからである。 The content of the filler is preferably 20 parts by mass or more, preferably 40 parts by mass or more and 98 parts by mass or less, and particularly 60 parts by mass or more and 95 parts by mass or more in 100 parts by mass of the composition. It is preferably 70 parts by mass or more, and particularly preferably 90 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in dimensional stability and deep curability. In addition, it is excellent in storage stability, dispersibility, coatability, and the like.
4.光酸発生剤
 光酸発生剤は、光照射により、酸を発生して、環状エーテル成分同士、環状エーテル成分及び水酸基含有成分の高分子化反応を促進可能なものである。
4. Photoacid generator A photoacid generator can generate an acid by irradiation with light to promote the polymerization reaction between cyclic ether components, cyclic ether components, and hydroxyl group-containing components.
 上記光酸発生剤は、光照射により酸を発生させることが可能な化合物である。
 上記光酸発生剤としては、オニウム塩である複塩又はその誘導体、或いはオキシムスルホネート化合物、ハロゲン含有化合物、ジアゾケトン化合物、スルホン化合物、スルホン酸化合物、ジアゾメタン化合物、ニトロベンジル化合物、ベンゾイントシレート化合物、鉄-アレーン錯体、アセトフェノン誘導体化合物等が挙げられ、これらは単独で又は2種以上を混合して使用することができる。
The photoacid generator is a compound capable of generating an acid by irradiation with light.
Examples of the photoacid generator include a compound salt which is an onium salt or a derivative thereof, an oxime sulfonate compound, a halogen-containing compound, a diazoketone compound, a sulfone compound, a sulfonic acid compound, a diazomethane compound, a nitrobenzyl compound, a benzointosylate compound, and iron. -Alene complex, acetophenone derivative compound and the like can be mentioned, and these can be used alone or in combination of two or more.
 オニウム塩である複塩又はその誘導体としては、例えば、下記一般式(i)で表される陽イオンと陰イオンの塩が挙げられる。 Examples of the double salt or a derivative thereof, which is an onium salt, include salts of cations and anions represented by the following general formula (i).
[A]m+[B]m-  (i) [A] m + [B] m- (i)
 ここで、陽イオン[A]m+はオニウムであり、その構造は、例えば、下記一般式で表すことができる。 Here, the cation [A] m + is onium, and its structure can be expressed by, for example, the following general formula.
[(R19aQ]m+  (ii) [(R 19 ) a Q] m + (ii)
 上記一般式(ii)中、R19は炭素原子数が1~60であり、炭素原子以外の原子をいくつ含んでいてもよい有機基を表す。
 aは1~5の整数を表す。
 a個のR19は各々独立で、同一でも異なっていてもよい。
 a個のR19のうち、少なくとも1つが、芳香族環を有する上記有機基を表す。
 QはS、N、Se、Te、P、As、Sb、Bi、O、I、Br、Cl、F及びN=Nからなる群から選ばれる原子又は原子団を表す。また、陽イオン[A]m+中のQの原子価をqとしたとき、m=a-qなる関係が成り立つことが必要である。ただし、N=Nは原子価0として扱う。
In the above general formula (ii), R 19 has an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms.
a represents an integer of 1 to 5.
The a R 19s are independent of each other and may be the same or different.
At least one of the a R 19s represents the organic group having an aromatic ring.
Q represents an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F and N = N. Further, when the valence of Q in the cation [A] m + is q, it is necessary that the relationship m = a−q holds. However, N = N is treated as having a valence of 0.
 また、陰イオン[B]m-は、ハロゲン化物錯体であることが好ましく、その構造は、例えば、下記一般式(iii)で表すことができる。光酸発生剤が、感度に優れたものとなるからである。 Further, the anion [B] m- is preferably a halide complex, and its structure can be represented by, for example, the following general formula (iii). This is because the photoacid generator has excellent sensitivity.
[LXbm-  (iii) [LX b ] m- (iii)
 上記一般式(iii)中、Lはハロゲン化物錯体の中心原子である金属又は半金属(Metalloid)を表し、B、P、As、Sb、Fe、Sn、Bi、Al、Ca、In、Ti、Zn、Sc、V、Cr、Mn又はCoである。
 Xはハロゲン原子を表す。
 bは3~7の整数を表す。また、陰イオン[B]m-中のLの原子価をpとしたとき、m=b-pなる関係が成り立つことが必要である。
In the above general formula (iii), L represents a metal or metalloid that is the central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn or Co.
X represents a halogen atom.
b represents an integer of 3 to 7. Further, when the valence of L in the anion [B] m- is p, it is necessary that the relationship m = bp is established.
 上記一般式(iii)の陰イオン[LXbm-の具体例としては、テトラキス(ペンタフルオロフェニル)ボレート[(C654B]-、テトラフルオロボレート(BF4-、ヘキサフルオロホスフェート(PF6-、ヘキサフルオロアンチモネート(SbF6-、ヘキサフルオロアルセネート(AsF6-、ヘキサクロロアンチモネート(SbCl6-、トリス(ペンタフルオロメチル)トリフルオロリン酸イオン(FAPアニオン)等が挙げられる。 Specific examples of the anion [LX b ] m- of the above general formula (iii) include tetrakis (pentafluorophenyl) borate [(C 6 F 5 ) 4 B] - , tetrafluoroborate (BF 4 ) - , and hexa. Fluorophosphate (PF 6 ) - , Hexafluoroantimonate (SbF 6 ) - , Hexafluoroarsenate (AsF 6 ) - , Hexachloroantimonate (SbCl 6 ) - , Tris (pentafluoromethyl) trifluorophosphate ion (FAP anion) ) Etc. can be mentioned.
 また、陰イオン[B]m-は、下記一般式(iv)で表される構造であってもよい。 Further, the anion [B] m- may have a structure represented by the following general formula (iv).
[LXb-1(OH)]m-  (iv) [LX b-1 (OH)] m- (iv)
 ここで、L、X及びbは上記と同様である。
 また、その他の陰イオンとしては、過塩素酸イオン(ClO4-、トリフルオロメチル亜硫酸イオン(CF3SO3-、フルオロスルホン酸イオン(FSO3-、トルエンスルホン酸陰イオン、トリニトロベンゼンスルホン酸陰イオン、カンファースルフォネート、ノナフロロブタンスルフォネート、ヘキサデカフロロオクタンスルフォネート、テトラアリールボレート等が挙げられる。
Here, L, X and b are the same as above.
Other anions include perchlorate ion (ClO 4 ) - , trifluoromethyl sulfite ion (CF 3 SO 3 ) - , fluorosulfonic acid ion (FSO 3 ) - , toluene sulfonic acid anion, and trinitrobenzene. Examples thereof include sulfonic acid anion, camphor sulphonate, nonafluorobutane sulphonate, hexadecafluorooctan sulphonate, tetraarylborate and the like.
 本開示においては、このようなオニウム塩の中でも、下記の(イ)~(ハ)の芳香族オニウム塩を使用することが特に有効である。これらの中から、その1種を単独で、又は2種以上を混合して使用することができる。 In the present disclosure, it is particularly effective to use the following aromatic onium salts (a) to (c) among such onium salts. From these, one of them can be used alone, or two or more of them can be mixed and used.
(イ)フェニルジアゾニウムヘキサフルオロホスフェート、4-メトキシフェニルジアゾニウムヘキサフルオロアンチモネート、4-メチルフェニルジアゾニウムヘキサフルオロホスフェート等のアリールジアゾニウム塩 (A) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate and the like.
(ロ)ジフェニルヨードニウムヘキサフルオロアンチモネート、ジ(4-メチルフェニル)ヨードニウムヘキサフルオロホスフェート、ジ(4-tert-ブチルフェニル)ヨードニウムヘキサフルオロホスフェート、トリルクミルヨードニウムテトラキス(ペンタフルオロフェニル)ボレート等のジアリールヨードニウム塩 (B) Diaryl such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, trilucmiliodonium tetrakis (pentafluorophenyl) borate, etc. Iodium salt
(ハ)下記群I又は群IIで表されるスルホニウムカチオンとヘキサフルオロホスフェートイオン、ヘキサフルオロアンチモンイオン、テトラキス(ペンタフルオロフェニル)ボレートイオン等のスルホニウム塩 (C) Sulfonium cations represented by Group I or Group II below and sulfonium salts such as hexafluorophosphate ion, hexafluoroantimonion ion, and tetrakis (pentafluorophenyl) borate ion.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
 また、その他の光酸発生剤としては、(η5-2,4-シクロペンタジエン-1-イル)〔(1,2,3,4,5,6-η)-(1-メチルエチル)ベンゼン〕-アイアン-ヘキサフルオロホスフェート等の鉄-アレーン錯体や、トリス(アセチルアセトナト)アルミニウム、トリス(エチルアセトナトアセタト)アルミニウム、トリス(サリチルアルデヒダト)アルミニウム等のアルミニウム錯体とトリフェニルシラノール等のシラノール類との混合物等も挙げられる。 Other photoacid generators include (η5-2,4-cyclopentadiene-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene]. -Iron-iron-arene complex such as hexafluorophosphate, aluminum complex such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salitylaldehidato) aluminum and silanol such as triphenylsilanol. A mixture with the like and the like can also be mentioned.
 また、その他の光酸発生剤としては、(η5-2,4-シクロペンタジエン-1-イル)〔(1,2,3,4,5,6-η)-(1-メチルエチル)ベンゼン〕-アイアン-ヘキサフルオロホスフェート等の鉄-アレーン錯体や、トリス(アセチルアセトナト)アルミニウム、トリス(エチルアセトナトアセタト)アルミニウム、トリス(サリチルアルデヒダト)アルミニウム等のアルミニウム錯体とトリフェニルシラノール等のシラノール類との混合物等も挙げられる。 Other photoacid generators include (η5-2,4-cyclopentadiene-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene]. -Iron-iron-arene complex such as hexafluorophosphate, aluminum complex such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salitylaldehidato) aluminum and silanol such as triphenylsilanol. A mixture with the like and the like can also be mentioned.
 これらの中でも、実用面と光感度の観点から、光酸発生剤としては、芳香族ヨードニウム塩、芳香族スルホニウム塩及び鉄-アレーン錯体が好ましく、中でも、芳香族スルホニウム塩であることが好ましく、特に、硫黄原子(S)に芳香族環が3つ結合した構造を有するトリアリールスルホニウム塩であることが好ましく、中でも特に、下記一般式(6)で表されるトリアリールスルホニウム塩であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなるからである。 Among these, from the viewpoint of practical use and photosensitivity, the photoacid generator is preferably an aromatic iodonium salt, an aromatic sulfonium salt and an iron-alene complex, and among them, an aromatic sulfonium salt is particularly preferable. , A triarylsulfonium salt having a structure in which three aromatic rings are bonded to a sulfur atom (S) is preferable, and a triarylsulfonium salt represented by the following general formula (6) is particularly preferable. .. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
(式中、R21、R22、R23、R24、R25、R26、R27、R28、R29及びR30は、それぞれ独立に、水素原子、ハロゲン原子、置換若しくは無置換の炭素原子数1~10のアルキル基、置換若しくは無置換の炭素原子数1~10のアルコキシ基又は置換若しくは無置換の炭素原子数2~10のエステル基を表すか、或いは、これらの基中のメチレン基が下記群2から選ばれる二価の基で置換された基を表し、R31、R32、R33及びR34は、それぞれ独立に、水素原子、ハロゲン原子、置換若しくは無置換の炭素原子数1~10のアルキル基又は該アルキル基中のメチレン基が下記群2から選ばれる二価の基で置換された基を表し、R35は、水素原子、ハロゲン原子、置換若しくは無置換の炭素原子数1~10のアルキル基、該アルキル基中のメチレン基が下記群2から選ばれる二価の基で置換された基又は下記化学式(6a)~(6c)より選択されるいずれかの置換基を表し、Anq-はq価の陰イオンを表し、pは電荷を中性にする係数を表す。
群2:-O-、-S-、-NR’’-、-NR’’-(C=O)-O-、-CO-、-(C=O)-O-、-O-(C=O)-、-O-(C=O)-O-、-SiR’’2
 R’’は水素原子又は炭素原子数1~10のアルキル基を表す。)
(In the formula, R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 and R 30 are independently hydrogen atom, halogen atom, substituted or unsubstituted, respectively. Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 substituted or unsubstituted carbon atoms, or an ester group having 2 to 10 substituted or unsubstituted carbon atoms, or among these groups. The methylene group represents a group substituted with a divalent group selected from the following group 2, and R 31 , R 32 , R 33 and R 34 are independently hydrogen atom, halogen atom, substituted or unsubstituted carbon. An alkyl group having 1 to 10 atoms or a methylene group in the alkyl group is represented by a divalent group selected from the following group 2, and R 35 is a hydrogen atom, a halogen atom, a substituted or unsubstituted group. An alkyl group having 1 to 10 carbon atoms, a group in which the methylene group in the alkyl group is substituted with a divalent group selected from the following group 2, or one selected from the following chemical formulas (6a) to (6c). It represents a substituent, An q- represents a q-valent anion, and p represents a coefficient for neutralizing the charge.
Group 2: -O-, -S-, -NR "-, -NR"-(C = O) -O-, -CO-,-(C = O) -O-, -O- (C) = O)-, -O- (C = O) -O-, -SiR'' 2-
R'' represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. )
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
(式中、R121、R122、R123、R124、R125、R126、R127、R128、R129、R130、R131、R132、R133、R134、R136、R137、R138、R139、R145、R146、R147、R148及びR149は、それぞれ独立に、水素原子、ハロゲン原子、置換若しくは無置換の炭素原子数1~10のアルキル基、置換若しくは無置換の炭素原子数1~10のアルコキシ基又は置換若しくは無置換の炭素原子数2~10のエステル基を表すか、或いは、これらの基中のメチレン基が上記群2から選ばれる二価の基で置換された基を表し、R140、R141、R142、R143及びR144は、それぞれ独立に、水素原子、ハロゲン原子、置換若しくは無置換の炭素原子数1~10のアルキル基該アルキル基中のメチレン基が上記群2から選ばれる二価の基で置換された基を表し、
*は、式(6)中のSとの結合位置を表す。)
(In the formula, R 121 , R 122 , R 123 , R 124 , R 125 , R 126 , R 127 , R 128 , R 129 , R 130 , R 131 , R 132 , R 133 , R 134 , R 136 , R. 137 , R 138 , R 139 , R 145 , R 146 , R 147 , R 148 and R 149 are each independently hydrogen atom, halogen atom, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted. Alternatively, it represents an unsubstituted or unsubstituted alkoxy group having 1 to 10 carbon atoms or an substituted or unsubstituted ester group having 2 to 10 carbon atoms, or the methylene group in these groups is a divalent selected from the above group 2. Represents a group substituted with a group of, and R 140 , R 141 , R 142 , R 143 and R 144 are independently alkyl groups having 1 to 10 carbon atoms of hydrogen atom, halogen atom, substituted or unsubstituted. Represents a group in which the methylene group in the alkyl group is substituted with a divalent group selected from the above group 2.
* Represents the connection position with S in the equation (6). )
 上記一般式(6)及び一般式(6a)~(6c)中で用いられるハロゲン原子としては、フッ素、塩素、臭素、ヨウ素等が挙げられる。 Examples of the halogen atom used in the general formula (6) and the general formulas (6a) to (6c) include fluorine, chlorine, bromine, iodine and the like.
 上記一般式(6)及び一般式(6a)~(6c)中で用いられる、置換若しくは無置換の炭素原子数1~10のアルキル基としては、炭素原子数1~10の直鎖又は分岐のアルキル基、及び該アルキル基中の水素原子が置換された基が挙げられる。
 上記炭素原子数1~10の直鎖又は分岐のアルキル基としては、例えば、上記「1.環状エーテル成分」の項に記載のアルキル基のうち、所定の炭素原子数のものを用いることができる。
 上記アルキル基中の水素原子の1つ以上を置換する基としては、ハロゲン原子等が挙げられる。
The substituted or unsubstituted alkyl group having 1 to 10 carbon atoms used in the general formula (6) and the general formulas (6a) to (6c) is a linear or branched alkyl group having 1 to 10 carbon atoms. Examples thereof include an alkyl group and a group in which a hydrogen atom in the alkyl group is substituted.
As the linear or branched alkyl group having 1 to 10 carbon atoms, for example, among the alkyl groups described in the above section "1. Cyclic ether component", those having a predetermined carbon atom number can be used. ..
Examples of the group that substitutes one or more of the hydrogen atoms in the alkyl group include a halogen atom and the like.
 上記一般式(6)及び一般式(6a)~(6c)中で用いられる、置換若しくは無置換の炭素原子数1~10のアルコキシ基としては、アルキル基の結合箇所側末端のメチレン基に-O-が結合した基が挙げられる。上記アルコキシ基を構成するアルキル基やその水素原子を置換する場合がある置換基としては、上記一般式(6)及び一般式(6a)~(6c)中で用いられる、置換若しくは無置換のアルキル基と同様とすることができる。 As the substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms used in the above general formulas (6) and (6a) to (6c), the methylene group at the end of the alkyl group on the bond site side is-. Examples include groups to which O- is bound. Substituents that may replace the alkyl group constituting the alkoxy group or its hydrogen atom include the substituted or unsubstituted alkyl used in the general formulas (6) and the general formulas (6a) to (6c). It can be the same as the group.
 上記一般式(6)及び一般式(6a)~(6c)中で用いられる炭素原子数2~10のエステル基としては、結合箇所側末端にエステル結合(-CO-O-又は-O-CO-)を有する基であればよく、アルキル基の結合箇所側末端のメチレン基にエステル結合が結合した基が挙げられる。上記エステル基を構成するアルキル基やその水素原子を置換する場合がある置換基は、上記一般式(6)及び一般式(6a)~(6c)R21中で用いられる、置換若しくは無置換のアルキル基と同様とすることができる。 As the ester group having 2 to 10 carbon atoms used in the general formula (6) and the general formulas (6a) to (6c), an ester bond (-CO-O- or -O-CO) is formed at the end on the bonding site side. Any group having-) may be used, and examples thereof include a group in which an ester bond is bonded to a methylene group at the end on the bonding site side of the alkyl group. The alkyl group constituting the ester group and the substituent that may replace the hydrogen atom thereof are substituted or unsubstituted groups used in the general formulas (6) and (6a) to (6c) R 21 . It can be similar to an alkyl group.
 上記一般式(6)及び一般式(6a)~(6c)中で用いられるアルキル基、アルコキシ基又はエステル基中のメチレン基が上記群2から選ばれる二価の基で置換された基において、上記二価の基同士は隣り合わないものとする。 In the group in which the methylene group in the alkyl group, alkoxy group or ester group used in the general formula (6) and the general formulas (6a) to (6c) is replaced with a divalent group selected from the above group 2. The above divalent groups shall not be adjacent to each other.
 一般式(6)中のpAnq-で表されるq価のアニオンとしては、上述の陰イオン[B]m-として挙げたもののうち、所定の価数のアニオンが挙げられる。
 pAnq-で表されるq価のアニオンとしては、例えば、テトラキス(ペンタフルオロフェニル)ボレート[(C654B]-、テトラフルオロボレート(BF4-、ヘキサフルオロホスフェート(PF6-、ヘキサフルオロアンチモネート(SbF6-、ヘキサフルオロアルセネート(AsF6-、ヘキサクロロアンチモネート(SbCl6-、トリス(ペンタフルオロメチル)トリフルオロリン酸イオン(FAPアニオン)、過塩素酸イオン(ClO4-、トリフルオロメチル亜硫酸イオン(CF3SO3-、フルオロスルホン酸イオン(FSO3-、トルエンスルホン酸陰イオン、トリニトロベンゼンスルホン酸陰イオン、カンファースルフォネート、ノナフロロブタンスルフォネート、ヘキサデカフロロオクタンスルフォネート、テトラアリールボレート、テトラキス(ペンタフルオロフェニル)ボレート等が挙げられる。
Examples of the q-valent anion represented by pAn q- in the general formula (6) include anions having a predetermined valence among those listed as the above-mentioned anions [B] m-.
Examples of the q-valent anion represented by pAn q- include tetrakis (pentafluorophenyl) borate [(C 6 F 5 ) 4 B] - , tetrafluoroborate (BF 4 ) - , and hexafluorophosphate (PF 6). ) - , Hexafluoroantimonate (SbF 6 ) - , Hexafluoroarsenate (AsF 6 ) - , Hexachloroantimonate (SbCl 6 ) - , Tris (pentafluoromethyl) trifluorophosphate ion (FAP anion), perchloric acid Ions (ClO 4 ) - , Trifluoromethyl sulfite ion (CF 3 SO 3 ) - , Fluorosulfonic acid ion (FSO 3 ) - , Toluene sulfonic acid anion, Trinitrobenzene sulfonic acid anion, Camphasulfonate, Nonafluoro Examples thereof include butane sulfonate, hexadecafluorooctanesulfonate, tetraarylborate, and tetrakis (pentafluorophenyl) borate.
 本開示においては、R35が、化学式(6a)~(6c)より選択されるものであることが好ましく、化学式(6b)であることがより好ましい。R35が上述の構造を有することにより、上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなるからである。 In the present disclosure, R 35 is preferably selected from the chemical formulas (6a) to (6c), and more preferably the chemical formula (6b). This is because the R 35 has the above-mentioned structure, so that the above-mentioned composition is excellent in the balance of dimensional stability, adhesive strength and deep curability.
 R21、R22、R23、R24、R25、R26、R27、R28、R29、R30、R31、R32、R33及びR34は、水素原子、ハロゲン原子、炭素原子数1~10のアルキル基、炭素原子数1~10のアルコキシ基又は炭素原子数2~10のエステル基であるが、水素原子、ハロゲン原子、炭素原子数1~10のアルキル基、炭素原子数1~10のアルコキシ基であることが好ましく、特に、水素原子又はハロゲン原子であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなるからである。 R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 and R 34 are hydrogen atom, halogen atom, carbon. An alkyl group having 1 to 10 atoms, an alkoxy group having 1 to 10 carbon atoms, or an ester group having 2 to 10 carbon atoms, but a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and a carbon atom. It is preferably an alkoxy group having a number of 1 to 10, and particularly preferably a hydrogen atom or a halogen atom. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability.
 R121、R122、R123、R124、R125、R126、R127、R128、R129、R130、R131、R132、R133、R134、R136、R137、R138、R139、R140、R141、R142、R143、R144、R145、R146、R147、R148及びR149は、水素原子、ハロゲン原子、炭素原子数1~10のアルキル基又は炭素原子数1~10のアルコキシ基であることが好ましく、特に、水素原子又はハロゲン原子であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなるからである。 R 121 , R 122 , R 123 , R 124 , R 125 , R 126 , R 127 , R 128 , R 129 , R 130 , R 131 , R 132 , R 133 , R 134 , R 136 , R 137 , R 138 , R 139 , R 140 , R 141 , R 142 , R 143 , R 144 , R 145 , R 146 , R 147 , R 148 and R 149 are hydrogen atoms, halogen atoms, and alkyl groups having 1 to 10 carbon atoms. Alternatively, it is preferably an alkoxy group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or a halogen atom. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability.
 上記光酸発生剤の含有量は、所望の寸法安定性、接着力及び深部硬化性が得られるものであればよいが、環状エーテル成分及び水酸基含有成分の合計100質量部に対して、0.1質量部以上10質量部以下であることが好ましく、0.5質量部以上7質量部以下であることがより好ましく、特に1質量部以上5質量部以下であることが好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、接着力及び深部硬化性に優れたものとなるからである。
 なお、光酸発生剤の市販品では、光酸発生剤を溶剤中に分散又は溶解した形態のものがある。本開示において、光酸発生剤の含有量の計算をする場合には、溶剤を除いた光酸発生剤の固形分の含有量をいうものである。
The content of the photoacid generator may be as long as it can obtain the desired dimensional stability, adhesive strength and deep curability, but it is 0. It is preferably 1 part by mass or more and 10 parts by mass or less, more preferably 0.5 part by mass or more and 7 parts by mass or less, and particularly preferably 1 part by mass or more and 5 parts by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability, and in particular, is excellent in adhesive strength and deep curability.
In addition, there is a commercially available product of the photoacid generator in a form in which the photoacid generator is dispersed or dissolved in a solvent. In the present disclosure, when the content of the photoacid generator is calculated, it means the content of the solid content of the photoacid generator excluding the solvent.
 光酸発生剤の含有量としては、上記組成物100質量部中に、0.01質量部以上4質量部以下であることが好ましく、0.05質量部以上3質量部以下であることがより好ましく、0.1質量部以上1.5質量部以下であることが特に好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなるからである。 The content of the photoacid generator is preferably 0.01 parts by mass or more and 4 parts by mass or less, and more preferably 0.05 parts by mass or more and 3 parts by mass or less in 100 parts by mass of the composition. It is preferably 0.1 part by mass or more and 1.5 part by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability.
 光酸発生剤の含有量としては、上記組成物の固形分100質量部中に、0.01質量部以上4質量部以下であることが好ましく、0.05質量部以上3質量部以下であることがより好ましく、0.1質量部以上1.5質量部以下であることが特に好ましい。上記組成物は、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなるからである。 The content of the photoacid generator is preferably 0.01 parts by mass or more and 4 parts by mass or less, and 0.05 parts by mass or more and 3 parts by mass or less in 100 parts by mass of the solid content of the above composition. It is more preferable, and it is particularly preferable that it is 0.1 part by mass or more and 1.5 part by mass or less. This is because the composition is excellent in balance of dimensional stability, adhesive strength and deep curability.
5.溶剤
 本開示の組成物は、必要に応じて、上記各成分を溶解又は分散可能な溶剤を含んでもよい。溶剤としては、25℃、大気圧下で液状であり、組成物の各成分を分散又は溶解可能なものである。また、溶剤は、環状エーテル成分、水酸基含有成分、充填剤、光酸発生剤等の上記各成分と反応しないものである。
 従って、例えば、環状エーテル成分、水酸基含有成分に分類されるものは、25℃、大気圧下で液状であっても、溶剤に該当しないものである。
5. Solvent The composition of the present disclosure may contain a solvent capable of dissolving or dispersing each of the above components, if necessary. The solvent is liquid at 25 ° C. and under atmospheric pressure, and can disperse or dissolve each component of the composition. Further, the solvent does not react with each of the above components such as a cyclic ether component, a hydroxyl group-containing component, a filler, and a photoacid generator.
Therefore, for example, those classified into a cyclic ether component and a hydroxyl group-containing component do not correspond to a solvent even if they are liquid at 25 ° C. under atmospheric pressure.
 このような溶剤としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルセロソルブ、エチルセロソルブ、クロロホルム、塩化メチレン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、ベンゼン、トルエン、キシレン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、酢酸エチル、メタノール、エタノール及びイソプロパノール等を挙げることができる。 Examples of such a solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, propylene glycol monomethyl ether, and propylene glycol monomethyl. Examples thereof include ether acetate, ethyl acetate, methanol, ethanol and isopropanol.
 溶剤の含有量としては、所望の寸法安定性、接着力及び深部硬化性が得られるものであればよいが、本開示の組成物を接着剤として使用容易とする観点からは、上記組成物100質量部中、10質量部以下が好ましく、5質量部以下がより好ましく、1質量部以下が更に好ましい。 The content of the solvent may be any as long as it can obtain desired dimensional stability, adhesive strength and deep curability, but from the viewpoint of facilitating the use of the composition of the present disclosure as an adhesive, the above composition 100 Of the parts by mass, 10 parts by mass or less is preferable, 5 parts by mass or less is more preferable, and 1 part by mass or less is further preferable.
6.シランカップリング剤
 上記組成物は、シランカップリング剤を含むことが好ましい。上記組成物は、接着力により優れたものとなるからである。
6. Silane Coupling Agent The composition preferably contains a silane coupling agent. This is because the above composition is superior in adhesive strength.
 シランカップリング剤としては、アルコキシシリル基を有する化合物を用いることができ、具体的には上記「3.充填剤」に記載のシランカップリング剤が挙げられる。 As the silane coupling agent, a compound having an alkoxysilyl group can be used, and specific examples thereof include the silane coupling agent described in "3. Filler" above.
 本開示においては、アルキル基、フェニル基等の芳香族環基、ビニル基、スチリル基、エポキシ基、メタクリル基、アクリル基、アミノ基、メルカプト基、イソシアネート基等の官能基を有するものを用いることができ、中でも、ビニル基、エポキシ基、メタクリル基、アクリル基等を有するものであることが好ましく、特に、エポキシ基を有するものであることが好ましい。上記組成物は、分散性、寸法安定性、接着力及び深部硬化性のバランスにより優れたものとなり、特に、保存安定性、接着力に優れたものとなるからである。 In the present disclosure, those having a functional group such as an aromatic ring group such as an alkyl group and a phenyl group, a vinyl group, a styryl group, an epoxy group, a methacrylic group, an acrylic group, an amino group, a mercapto group and an isocyanate group shall be used. Of these, those having a vinyl group, an epoxy group, a methacrylic group, an acrylic group and the like are preferable, and those having an epoxy group are particularly preferable. This is because the composition is excellent in balance of dispersibility, dimensional stability, adhesive strength and deep curability, and in particular, is excellent in storage stability and adhesive strength.
 シランカップリング剤の含有量としては、環状エーテル成分及び水酸基含有成分の合計100質量部に対して、0.1質量部以上15質量部以下であることが好ましく、0.5質量部以上10質量部以下であることがより好ましく、特に0.8質量部以上8質量部以下であることが好ましい。上記組成物は、接着力により優れたものとなるからである。 The content of the silane coupling agent is preferably 0.1 part by mass or more and 15 parts by mass or less, and 0.5 parts by mass or more and 10 parts by mass with respect to 100 parts by mass in total of the cyclic ether component and the hydroxyl group-containing component. It is more preferably 0 parts by mass or less, and particularly preferably 0.8 parts by mass or more and 8 parts by mass or less. This is because the above composition is superior in adhesive strength.
 シランカップリング剤の含有量としては、上記組成物100質量部中に、0.01質量部以上5質量部以下であることが好ましく、0.05質量部以上3質量部以下であることがより好ましく、特に0.1質量部以上2質量部以下であることが好ましい。上記組成物は、接着力により優れたものとなるからである。 The content of the silane coupling agent is preferably 0.01 parts by mass or more and 5 parts by mass or less, and more preferably 0.05 parts by mass or more and 3 parts by mass or less in 100 parts by mass of the composition. It is preferable, and it is particularly preferable that it is 0.1 part by mass or more and 2 parts by mass or less. This is because the above composition is superior in adhesive strength.
 シランカップリング剤の含有量としては、上記組成物の固形分100質量部中に、0.01質量部以上5質量部以下であることが好ましく、0.05質量部以上3質量部以下であることがより好ましく、特に0.1質量部以上2質量部以下であることが好ましい。上記組成物は、接着力により優れたものとなるからである。 The content of the silane coupling agent is preferably 0.01 parts by mass or more and 5 parts by mass or less, and 0.05 parts by mass or more and 3 parts by mass or less in 100 parts by mass of the solid content of the above composition. It is more preferable, and particularly preferably 0.1 part by mass or more and 2 parts by mass or less. This is because the above composition is superior in adhesive strength.
 なお充填剤がシランカップリング剤による表面処理がなされている場合、当該表面処理に用いられるシランカップリング剤の量は上記のシランカップリングの量に含まないものとする。 If the filler is surface-treated with a silane coupling agent, the amount of the silane coupling agent used for the surface treatment shall not be included in the above-mentioned silane coupling amount.
7.添加剤
 上記組成物は、環状エーテル成分、水酸基含有成分、充填剤及び光酸発生剤を含み、更に溶剤を含むことができるものであるが、必要に応じてその他の成分を含むことができる。
 このような、その他の成分としては、顔料、染料等の着色剤、光増感剤、消泡剤、増粘剤、チクソ剤、界面活性剤、レベリング剤、難燃剤、可塑剤、安定剤、重合禁止剤、紫外線吸収剤、酸化防止剤、静電防止剤、流動調整剤及び接着促進剤等の各種樹脂添加物等を含むことができる。
7. Additives The above composition contains a cyclic ether component, a hydroxyl group-containing component, a filler and a photoacid generator, and can further contain a solvent, but can also contain other components if necessary.
Such other components include colorants such as pigments and dyes, photosensitizers, defoamers, thickeners, tinctures, surfactants, leveling agents, flame retardants, plasticizers, stabilizers, etc. It can contain various resin additives such as polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow modifiers and adhesion promoters.
 また、紫外線吸収剤及び酸化防止剤としては、フェノール性水酸基が保護基で保護され、加熱等により保護基を脱離することで、紫外線吸収剤又は酸化防止剤としての機能が発現する潜在性添加剤も用いることができる。このような潜在性添加剤としては、例えば、国際公報WO2017/170465号に記載の潜在性添加剤を挙げることができる。 Further, as an ultraviolet absorber and an antioxidant, a latent addition in which a phenolic hydroxyl group is protected by a protecting group and a function as an ultraviolet absorber or an antioxidant is exhibited by removing the protecting group by heating or the like. Agents can also be used. Examples of such latent additives include the latent additives described in International Publication No. WO2017 / 170465.
 これらのその他の成分の合計の含有量は、本開示の組成物の固形分100質量部中に30質量部以下とすることができる。 The total content of these other components can be 30 parts by mass or less in 100 parts by mass of the solid content of the composition of the present disclosure.
8.用途
 本開示の組成物の用途としては、寸法安定性、接着力及び深部硬化性が要求されるものであることが好ましく、接着剤であることが好ましい。
 接着剤の用途としては、地震計、作業用ロボット、ヘルスモニタリング装置、無人運転装置、パーソナルコンピューター(例えば、モバイル型パーソナルコンピューター、ラップトップ型パーソナルコンピューター、タブレット型パーソナルコンピューター)、携帯電話機などの移動体端末、ディジタルカメラ、インクジェットプリンター等のインクジェット式吐出装置、ルーターやスイッチ等のストレージエリアネットワーク機器、ローカルエリアネットワーク機器、移動体端末基地局用機器、テレビ、ビデオカメラ、ビデオレコーダー、カーナビゲーション装置、ページャー、電子手帳、電子辞書、電卓、電子ゲーム機器、ゲーム用コントローラー、ワードプロセッサー、ワークステーション、テレビ電話、防犯用テレビモニター、電子双眼鏡、POS(point of sale)端末、医療機器(例えば電子体温計、血圧計、血糖計、心電図計測装置、超音波診断装置、電子内視鏡)、魚群探知機、各種測定機器、計器・センサ類(例えば、車両、航空機、船舶の計器・センサ類)、フライトシミュレーター、ヘッドマウントディスプレイ、モーショントレース、モーショントラッキング、モーションコントローラー、PDR(歩行者位置方位計測)等に用いられる、電子部品、光学部品の接着用であることが好ましく、中でも、光学部品の接着用であることが好ましい。上記組成物の、寸法安定性、接着力及び深部硬化性に優れるとの効果をより効果的に発揮できるからである。
 光学部品としては、光を透過する部品が挙げられ、ディスプレイ、センサ等に用いられる、レンズ、フィルム、光導波路、プリズム、プリズムシート等が挙げられる。
 電子部品としては、半導体素子、配線を含む導体材料等が挙げられる。
8. Applications The compositions of the present disclosure are preferably those that require dimensional stability, adhesive strength, and deep curability, and are preferably adhesives.
The adhesive is used for moving objects such as seismometers, work robots, health monitoring devices, unmanned driving devices, personal computers (for example, mobile personal computers, laptop personal computers, tablet personal computers), and mobile phones. Inkjet ejection devices such as terminals, digital cameras and inkjet printers, storage area network devices such as routers and switches, local area network devices, mobile terminal base station devices, televisions, video cameras, video recorders, car navigation devices, pagers. , Electronic notebooks, electronic dictionaries, calculators, electronic game devices, game controllers, word processors, workstations, videophones, security TV monitors, electronic binoculars, POS (point of sale) terminals, medical devices (eg electronic thermometers, blood pressure monitors) , Blood glucose meter, electrocardiogram measuring device, ultrasonic diagnostic device, electronic endoscope), fish finder, various measuring devices, instruments / sensors (for example, vehicles, aircraft, marine instruments / sensors), flight simulator, head It is preferably for bonding electronic parts and optical parts used in mount displays, motion traces, motion tracking, motion controllers, PDRs (pedestrian position and orientation measurement), etc., and above all, for bonding optical parts. preferable. This is because the above composition can more effectively exert the effect of being excellent in dimensional stability, adhesive strength and deep curability.
Examples of the optical component include a component that transmits light, and examples thereof include a lens, a film, an optical waveguide, a prism, a prism sheet, and the like used for a display, a sensor, and the like.
Examples of electronic components include semiconductor elements, conductor materials including wiring, and the like.
 上記組成物の用途は、厚みの大きい硬化物の形成用であることが好ましい。上記組成物の、寸法安定性、接着力及び深部硬化性に優れるとの効果をより効果的に発揮できるからである。
 上記硬化物の厚みとしては、例えば、1μm以上100mm以下とすることができるが、50μm以上であることが好ましく、中でも、200μm以上であることが好ましく、特に、500μm以上であることが好ましく、中でも特に、1mm以上であることが好ましく、中でも特に2mm以上であることが好ましい。上記組成物の、寸法安定性、接着力及び深部硬化性に優れるとの効果をより効果的に発揮できるからである。
 また、上記硬化物の厚みとしては、10mm以下であることが好ましく、中でも、5mm以下であることが好ましく、中でも特に3mm以下であることが好ましい。上記組成物の、寸法安定性、接着力及び深部硬化性に優れるとの効果をより効果的に発揮できるからである。
The composition is preferably used for forming a cured product having a large thickness. This is because the above composition can more effectively exert the effect of being excellent in dimensional stability, adhesive strength and deep curability.
The thickness of the cured product can be, for example, 1 μm or more and 100 mm or less, but is preferably 50 μm or more, particularly preferably 200 μm or more, particularly preferably 500 μm or more, and particularly preferably 500 μm or more. In particular, it is preferably 1 mm or more, and particularly preferably 2 mm or more. This is because the above composition can more effectively exert the effect of being excellent in dimensional stability, adhesive strength and deep curability.
The thickness of the cured product is preferably 10 mm or less, more preferably 5 mm or less, and particularly preferably 3 mm or less. This is because the above composition can more effectively exert the effect of being excellent in dimensional stability, adhesive strength and deep curability.
B.硬化物
 次に、本開示の硬化物について説明する。
 本開示の硬化物は、上述の組成物の硬化物である。
B. Cured product Next, the cured product of the present disclosure will be described.
The cured product of the present disclosure is a cured product of the above-mentioned composition.
 本開示によれば、上述の組成物を用いて形成されたものであるため、寸法安定性、接着力に優れ、厚みが厚い場合でも優れた接着力の硬化物を容易に形成可能となる。 According to the present disclosure, since it is formed by using the above-mentioned composition, it is possible to easily form a cured product having excellent dimensional stability and adhesive strength and having excellent adhesive strength even when the thickness is thick.
 本開示の硬化物は、上述の組成物を用いるものである。
 上記組成物の内容については、上記「A.組成物」の項に記載の内容と同様とすることができるため、ここでの説明は省略する。
 また、硬化物としては、環状エーテル成分同士及び/又は環状エーテル成分と水酸基含有成分とが反応した高分子量体を含むものであればよい。
The cured product of the present disclosure uses the above-mentioned composition.
Since the contents of the above composition can be the same as the contents described in the above-mentioned "A. Composition" section, the description thereof is omitted here.
The cured product may contain a high molecular weight substance obtained by reacting the cyclic ether components with each other and / or the cyclic ether component with the hydroxyl group-containing component.
 上記硬化物の平面視形状については、上記硬化物の用途等に応じて適宜設定することができ、例えば、ドット状、ライン状等のパターン状であってもよい。
 上記硬化物の厚みについては、上記硬化物の用途等に応じて設定されるものであり、例えば、1μm以上100mm以下とすることができるが、好ましくは、上記「A.組成物」の項に記載の、硬化物の好ましい厚みと同様とすることができる。
The plan view shape of the cured product can be appropriately set according to the intended use of the cured product, and may be, for example, a pattern shape such as a dot shape or a line shape.
The thickness of the cured product is set according to the intended use of the cured product, and may be, for example, 1 μm or more and 100 mm or less, but is preferably in the section of “A. Composition”. It can be the same as the above-mentioned preferable thickness of the cured product.
 上記硬化物の用途等については、上記「A.組成物」の項に記載の内容と同様とすることができる。 The uses and the like of the cured product can be the same as those described in the section of "A. Composition" above.
 上記硬化物の製造方法としては、上記組成物の硬化物を所望の形状となるように形成できる方法であれば特に限定されるものではない。
 このような製造方法としては、例えば、後述する「C.硬化物の製造方法」の項に記載の製造方法を用いることができる。
The method for producing the cured product is not particularly limited as long as it can form the cured product of the composition into a desired shape.
As such a manufacturing method, for example, the manufacturing method described in the section "C. Manufacturing method of cured product" described later can be used.
C.硬化物の製造方法
 次に、本開示の硬化物の製造方法について説明する。
 本開示の硬化物の製造方法は、上述の組成物に光照射する光照射工程を有するものである。
 以下、本開示の製造方法の各工程について詳細に説明する。
C. Method for producing a cured product Next, a method for producing a cured product of the present disclosure will be described.
The method for producing a cured product of the present disclosure includes a light irradiation step of irradiating the above-mentioned composition with light.
Hereinafter, each step of the manufacturing method of the present disclosure will be described in detail.
1.光照射工程
 本工程は、上記組成物に光照射する工程である。
 組成物に照射される光としては、波長300nm~450nmの光を含むものとすることができる。
 上記光照射の光源としては、例えば、超高圧水銀、水銀蒸気アーク、カーボンアーク、キセノンアーク、発光ダイオード(LED)等を挙げることができる。
 上記照射される光としては、レーザー光を用いてもよい。レーザー光としては、波長340~430nmの光を含むものを用いることができる。
 レーザー光の光源としては、アルゴンイオンレーザー、ヘリウムネオンレーザー、YAGレーザー、及び半導体レーザー等の可視から赤外領域の光を発するものも用いることができる。
 なお、これらのレーザーを使用する場合には、上記組成物は、可視から赤外の当該領域を吸収する増感色素を含むことができる。
1. 1. Light Irradiation Step This step is a step of irradiating the above composition with light.
The light irradiated to the composition may include light having a wavelength of 300 nm to 450 nm.
Examples of the light source for light irradiation include ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, light emitting diode (LED), and the like.
Laser light may be used as the light to be irradiated. As the laser light, a light having a wavelength of 340 to 430 nm can be used.
As the light source of the laser light, a light source in the visible to infrared region such as an argon ion laser, a helium neon laser, a YAG laser, and a semiconductor laser can also be used.
When these lasers are used, the composition can contain a sensitizing dye that absorbs the region from visible to infrared.
2.その他の工程
 上記硬化物の製造方法は、上記光照射工程以外に、必要に応じてその他の工程を含むものであってもよい。
 上記その他の工程としては、上記光照射工程後に、組成物の塗膜中の未重合部分を除去してパターン状硬化物を得る現像工程、上記光照射工程後に、硬化物を加熱処理するポストベーク工程、上記光照射工程前に、組成物を加熱処理して上記組成物中の溶剤を除去するプリベーク工程、上記光照射工程前に、上記組成物の塗膜を形成する工程等を挙げることができる。
2. 2. Other Steps The method for producing the cured product may include other steps, if necessary, in addition to the light irradiation step.
Other steps include a development step of removing unpolymerized portions in the coating film of the composition to obtain a patterned cured product after the light irradiation step, and a post-baking process in which the cured product is heat-treated after the light irradiation step. Examples thereof include a step, a prebaking step of heat-treating the composition to remove the solvent in the composition before the light irradiation step, a step of forming a coating film of the composition before the light irradiation step, and the like. can.
 上記現像工程における未重合部分を除去する方法としては、例えば、有機溶剤を未重合部分に塗布する方法を挙げることができる。
 上記有機溶剤としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルセロソルブ、エチルセロソルブ、クロロホルム、塩化メチレン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、ベンゼン、トルエン、キシレン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、酢酸エチル、メタノール、エタノール及びイソプロパノール等の有機溶剤現像液として一般的に使用されているものを用いることができる。
 上記現像工程の実施タイミングとしては、上記硬化工程後であればよい。
 上記ポストベーク工程における加熱条件としては、硬化工程により得られた硬化物の強度等を向上できるものであればよく、例えば、100℃以上250℃以下で10分間~90分間とすることができる。
 上記プリベーク工程における加熱条件としては、組成物中の溶剤を除去できるものであればよく、例えば、70℃以上150℃以下で30秒~300秒間とすることができる。
 上記塗膜を形成する工程で、組成物を塗布する方法としては、ディスペンサー、スピンコーター、ロールコーター、バーコーター、ダイコーター、カーテンコーター、各種の印刷、浸漬等の公知の方法を用いることができる。
 上記塗膜は、基材上に形成することができる。
 上記基材としては、硬化物の用途等に応じて適宜設定することができ、ソーダガラス、石英ガラス、半導体基板、配線基板、金属、紙、プラスチック等を含むものを挙げることができる。
 また、上記硬化物は、基材上で形成された後、基材から剥離して用いても、基材から他の被接着体に転写して用いてもよい。
As a method for removing the unpolymerized portion in the development step, for example, a method of applying an organic solvent to the unpolymerized portion can be mentioned.
Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like. Those generally used as organic solvent developing solutions such as ethyl acetate, methanol, ethanol and isopropanol can be used.
The timing of carrying out the development step may be after the curing step.
The heating conditions in the post-baking step may be any as long as they can improve the strength of the cured product obtained in the curing step, and can be, for example, 10 to 90 minutes at 100 ° C. or higher and 250 ° C. or lower.
The heating conditions in the prebaking step may be any one that can remove the solvent in the composition, and can be, for example, 70 ° C. or higher and 150 ° C. or lower for 30 seconds to 300 seconds.
As a method for applying the composition in the step of forming the coating film, known methods such as a dispenser, a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, and dipping can be used. ..
The coating film can be formed on a substrate.
The base material can be appropriately set according to the intended use of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, wiring substrates, metals, paper, plastics, and the like.
Further, the cured product may be formed on a base material and then peeled off from the base material and used, or may be transferred from the base material to another adherend and used.
3.その他
 上記製造方法により製造される硬化物及びその用途等については、上記「A.組成物」の項に記載の内容と同様とすることができる。
3. 3. Others The cured product produced by the above-mentioned production method, its use, and the like can be the same as those described in the above-mentioned "A. Composition" section.
 本開示は、上記実施形態に限定されるものではない。上記実施形態は、例示であり、本開示の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本開示の技術的範囲に包含される。 The present disclosure is not limited to the above embodiment. The above embodiment is an example, and any one having substantially the same structure as the technical idea described in the claims of the present disclosure and having the same effect and effect is the present invention. Included in the technical scope of the disclosure.
 以下、実施例及び比較例を挙げて本開示を更に詳細に説明するが、本開示はこれらの実施例等に限定されるものではない。 Hereinafter, the present disclosure will be described in more detail with reference to Examples and Comparative Examples, but the present disclosure is not limited to these Examples and the like.
[実施例及び比較例]
 下記表1~表5に記載の配合に従って、環状エーテル成分、水酸基含有成分、充填剤、光酸発生剤を混合し、25℃で1時間攪拌して各実施例及び比較例の組成物を得た。また、各成分は以下の材料を用いた。なお、表中の配合量は、各成分の質量部を表すものである。
[Examples and Comparative Examples]
According to the formulations shown in Tables 1 to 5 below, the cyclic ether component, the hydroxyl group-containing component, the filler, and the photoacid generator are mixed and stirred at 25 ° C. for 1 hour to obtain the compositions of each Example and Comparative Example. rice field. In addition, the following materials were used for each component. The blending amount in the table represents the mass part of each component.
(環状エーテル成分)
A1:脂環式エポキシ化合物(下記式A1で表される化合物、ダイセル社製セロキサイド2021P)
A2:脂環式エポキシ化合物(下記式A2で表される化合物、ユニオンカーバイト社製UVR6128)
A3:脂環式エポキシ化合物(下記式A3で表される化合物、JXTGエネルギー社製THI-DE)
A4:芳香族エポキシ化合物(下記式A4で表される化合物、ビスフェノールA型液状エポキシ化合物、DIC社製エピクロン850S、エポキシ当量185g/eq)
A5:脂肪族エポキシ化合物(下記式A5で表される化合物、2,2-ビス(ヒドロキシメチル)-1-ブタノールの1,2-エポキシ-4-(2-オキシラニル)シクロヘキサン付加物、ダイセル社製EHPE-3150、重量平均分子量Mw2400、エポキシ当量177g/eq)
A6:脂肪族エポキシ化合物(下記式A6で表される化合物)
(Cyclic ether component)
A1: Alicyclic epoxy compound (compound represented by the following formula A1, celloxide 2021P manufactured by Daicel Corporation)
A2: Alicyclic epoxy compound (compound represented by the following formula A2, UVR6128 manufactured by Union Carbide)
A3: Alicyclic epoxy compound (compound represented by the following formula A3, THI-DE manufactured by JXTG Energy Co., Ltd.)
A4: Aromatic epoxy compound (compound represented by the following formula A4, bisphenol A type liquid epoxy compound, Epicron 850S manufactured by DIC, epoxy equivalent 185 g / eq)
A5: Aliphatic epoxy compound (compound represented by the following formula A5, 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, manufactured by Daicel Co., Ltd. EHPE-3150, weight average molecular weight Mw2400, epoxy equivalent 177 g / eq)
A6: Aliphatic epoxy compound (compound represented by the following formula A6)
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
(水酸基含有成分)
B1:脂肪族化合物(下記式B1で表される化合物(l、m、nの合計は1以上)、アルコール性水酸基、3官能、ポリエステルポリオール、ダイセル社製プラクセル303(ポリカプロラクトントリオール)、水酸基価530~550mgKOH/g、分子量300、隣接する水酸基間の炭素原子数は6以上)
B2:脂肪族化合物(下記式B2で表される化合物、アルコール性水酸基、3官能、ポリオール単量体、トリメチロールプロパン、分子量134、隣接する水酸基間の炭素原子数は3)
B3:芳香族化合物(下記式B3で表される化合物(m、nの合計は1以上)、プロピレンオキサイド変性ビスフェノールA、アルコール性水酸基、2官能、ポリエーテルポリオール、隣接する水酸基間の炭素原子数は6以上)
B4:脂肪族化合物(下記式B4で表される化合物(nは平均で8)、ポリエチレングリコール、アルコール性水酸基、2官能、ポリエーテルポリオール、東邦化学工業製トーホーポリエチレングリコール400、重量平均分子量Mw400)
B5:脂肪族化合物(下記式B5で表される化合物(分子中の全てのm及びnの合計は45以上)、アルコール性水酸基、3官能、ポリエーテルポリオール、隣接する水酸基間の炭素原子数は6以上)
(Hydroxy group-containing component)
B1: Aliphatic compound (compound represented by the following formula B1 (total of l, m, n is 1 or more), alcoholic hydroxyl group, trifunctional, polyester polyol, Praxel 303 (polycaprolactone triol) manufactured by Daicel Co., Ltd., hydroxyl value 530-550 mgKOH / g, molecular weight 300, number of carbon atoms between adjacent hydroxyl groups is 6 or more)
B2: Aliphatic compound (compound represented by the following formula B2, alcoholic hydroxyl group, trifunctional, polyol monomer, trimethylolpropane, molecular weight 134, number of carbon atoms between adjacent hydroxyl groups is 3)
B3: Aromatic compound (compound represented by the following formula B3 (total of m and n is 1 or more), propylene oxide-modified bisphenol A, alcoholic hydroxyl group, bifunctional, polyether polyol, number of carbon atoms between adjacent hydroxyl groups Is 6 or more)
B4: An aliphatic compound (compound represented by the following formula B4 (n is 8 on average), polyethylene glycol, alcoholic hydroxyl group, bifunctional, polyether polyol, Toho Polyethylene Glycol 400 manufactured by Toho Chemical Industry Co., Ltd., weight average molecular weight Mw400)
B5: Aliphatic compound (compound represented by the following formula B5 (total of all m and n in the molecule is 45 or more), alcoholic hydroxyl group, trifunctional, polyether polyol, number of carbon atoms between adjacent hydroxyl groups 6 or more)
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
(充填剤)
C1:無機粒子(シリカ、アドマテックス社製アドマフューズ(登録商標)、平均粒径10μm、エポキシ基を含む表面処理層あり)
C2:無機粒子(シリカ、アドマテックス社製アドマフューズ、平均粒径20μm、エポキシ基を含む表面処理層あり)
C3:無機粒子(シリカ、アドマテックス社製アドマフューズ、平均粒径10μm、メタクリル基を含む表面処理層あり)
C4:無機粒子(シリカ、アドマテックス社製アドマフューズ、平均粒径10μm、表面処理なし)
C5:無機粒子(シリカ、日本アエロジル社製VP-NKC―130、平均粒径16nm、ヘキサデシル基を含む表面処理層あり)
 C1~C3、C5それぞれにおける表面処理層は、各充填剤の項に記載の官能基を有するシランカップリング剤によるものであった。
(filler)
C1: Inorganic particles (silica, Admafuse (registered trademark) manufactured by Admatex, average particle size 10 μm, with surface treatment layer containing epoxy group)
C2: Inorganic particles (silica, Admafuse manufactured by Admatex, average particle size 20 μm, with surface treatment layer containing epoxy group)
C3: Inorganic particles (silica, Admafuse manufactured by Admatex, average particle size 10 μm, with surface treatment layer containing methacrylic group)
C4: Inorganic particles (silica, Admafuse manufactured by Admatex, average particle size 10 μm, no surface treatment)
C5: Inorganic particles (silica, VP-NKC-130 manufactured by Aerosil Japan, average particle size 16 nm, with surface treatment layer containing hexadecyl group)
The surface-treated layers in each of C1 to C3 and C5 were made of a silane coupling agent having a functional group described in the section of each filler.
(光酸発生剤)
D1:下記式(D1)で表される化合物の炭酸プロピレン50質量%溶液
(Photoacid generator)
D1: A 50% by mass solution of propylene carbonate of the compound represented by the following formula (D1).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
(カップリング剤)
E1:信越シリコーン社、KBM-403
(Coupling agent)
E1: Shinetsu Silicone Co., Ltd., KBM-403
[評価]
 実施例及び比較例で調製した組成物について、寸法安定性、接着力、深部硬化性及び分散性について評価を行った。
[evaluation]
The compositions prepared in Examples and Comparative Examples were evaluated for dimensional stability, adhesive strength, deep curability and dispersibility.
1.寸法安定性
 実施例及び比較例で得られた組成物をガラス基材上に塗布し、塗膜に対して365nmLED(300nm~500nmの範囲内で365nmにピークトップを有するLEDランプ、(株)アイテックシステム製)で5000mJ/cm(波長365nmの積算光量)照射し、膜厚150μmの硬化物を得た。
 次いで、硬化物をガラス基材から剥離し、測定用サンプル(膜厚150μm×幅4mm×長さ30mm)を得た。
 得られた測定用サンプルについて、HITACHIハイテク製TMA7100を用い、以下の条件で熱線膨張率を測定し、以下の基準で評価した。結果を下記表1~表5に示す。
(測定条件)
測定温度:-20℃~250℃
昇温速度:5℃/分
(評価基準)
+++:30ppm未満
++:30ppm以上50ppm未満
+:50ppm以上80ppm未満
-:80ppm以上
 なお、熱線膨張率が小さいほど、寸法安定性に優れると判断できる。
1. 1. Dimensional stability The compositions obtained in Examples and Comparative Examples are applied onto a glass substrate, and a 365 nm LED (LED lamp having a peak top at 365 nm within the range of 300 nm to 500 nm) with respect to the coating film, Aitec Co., Ltd. Irradiation was performed at 5000 mJ / cm 2 (integrated light intensity at a wavelength of 365 nm) with (manufactured by System) to obtain a cured product having a film thickness of 150 μm.
Next, the cured product was peeled off from the glass substrate to obtain a measurement sample (film thickness 150 μm × width 4 mm × length 30 mm).
The obtained measurement sample was measured for heat ray expansion rate under the following conditions using TMA7100 manufactured by Hitachi High-Tech, and evaluated according to the following criteria. The results are shown in Tables 1 to 5 below.
(Measurement condition)
Measurement temperature: -20 ° C to 250 ° C
Temperature rise rate: 5 ° C / min (evaluation standard)
+++: Less than 30 ppm ++: 30 ppm or more and less than 50 ppm +: 50 ppm or more and less than 80 ppm −: 80 ppm or more It can be judged that the smaller the coefficient of linear thermal expansion, the better the dimensional stability.
2.接着力
 図1に示すサンプルを以下の手順で得た。25mm×50mmのアルミ基板1の上に実施例及び比較例で得られた組成物を直径3mm程度の円形に塗布した。
 次いで、組成物の両端に1mm厚のシリコンシートをスペーサ4として置き、アルミ基板1と同形状のガラス基板3を上から被せ、しっかりとクリップ等で固定した。ガラス基板側から365nmLED(300nm~500nmの範囲内で365nmにピークトップを有するLEDランプ、(株)アイテックシステム製)で5,000mJ/cm2(波長365nmの積算光量)照射し、アルミ基板1と、組成物の硬化物2及びスペーサ4と、ガラス基板3と、がこの順で積層した評価用サンプルを得た。
 次いで、万能試験機(島津社製AGS-X)で、アルミ基板の硬化物形成面が鉛直方向と平行となるように、評価用サンプル10を固定した。
 次いで、図1に示すように、アルミ基板1と、組成物の硬化物2及びスペーサ4と、ガラス基板3と、がこの順で積層した評価用サンプル10に対して、アルミ基板1の硬化物形成面と平行に鉛直方向上方から鉛直方向下方に、試験速度5.0mm/分でガラス基板3を押込む圧縮試験を行い、JIS K7181(1994)に従い、圧縮降伏応力を測定し、得られた圧縮降伏応力を硬化物2とアルミ基板3との接着面の面積で除して、圧縮せん断強度(MPa)を計算し、下記基準で評価した。結果を表1~表5に示す。なお図1におけるXは、鉛直方向下方への押込み力を示す。
(評価基準)
+++:3MPa以上
++:2MPa以上3MPa未満
+:1MPa以上2MPa未満
-:1MPa未満
 圧縮せん断強度が大きいほど、接着力に優れると判断できる。
2. 2. Adhesive strength The sample shown in FIG. 1 was obtained by the following procedure. The compositions obtained in Examples and Comparative Examples were applied onto an aluminum substrate 1 having a diameter of 25 mm × 50 mm in a circular shape having a diameter of about 3 mm.
Next, a silicon sheet having a thickness of 1 mm was placed on both ends of the composition as spacers 4, a glass substrate 3 having the same shape as the aluminum substrate 1 was covered from above, and the glass substrate 3 was firmly fixed with a clip or the like. From the glass substrate side, irradiate 5,000 mJ / cm 2 (integrated light intensity with a wavelength of 365 nm) with a 365 nm LED (LED lamp having a peak top at 365 nm in the range of 300 nm to 500 nm, manufactured by Aitec System Co., Ltd.) with the aluminum substrate 1. , The cured product 2 and the spacer 4 of the composition, and the glass substrate 3 were laminated in this order to obtain an evaluation sample.
Next, the evaluation sample 10 was fixed with a universal testing machine (AGS-X manufactured by Shimadzu Corporation) so that the cured product-forming surface of the aluminum substrate was parallel to the vertical direction.
Next, as shown in FIG. 1, the cured product of the aluminum substrate 1 is subjected to the evaluation sample 10 in which the aluminum substrate 1, the cured product 2 and the spacer 4 of the composition, and the glass substrate 3 are laminated in this order. A compression test was conducted in which the glass substrate 3 was pushed in from above in the vertical direction to below in the vertical direction in parallel with the forming surface at a test speed of 5.0 mm / min, and the compressive yield stress was measured according to JIS K7181 (1994). The compressive yield stress was divided by the area of the adhesive surface between the cured product 2 and the aluminum substrate 3, and the compressive shear strength (MPa) was calculated and evaluated according to the following criteria. The results are shown in Tables 1 to 5. Note that X in FIG. 1 indicates a pushing force downward in the vertical direction.
(Evaluation criteria)
+++: 3 MPa or more ++: 2 MPa or more and less than 3 MPa +: 1 MPa or more and less than 2 MPa −: less than 1 MPa It can be judged that the larger the compressive shear strength, the better the adhesive strength.
3.深部硬化性
 実施例及び比較例で得られた組成物を、内側を離型処理した円筒形のガラス容器(直径10mm)に任意の高さになるように流し込んだ。
 次いで、ガラス容器の上面から365nmLED(300nm~500nmの範囲内で365nmにピークトップを有するLEDランプ、(株)アイテックシステム製)で5000mJ/cm2(波長365nmの積算光量)照射した。
 次いで、ガラス容器から、光照射後の組成物を取り出し、光照射してない方(裏面)を触診してタックの有無を調べた。裏面にタックが出る直前の高さをその組成物の深部硬化度とし、下記基準で評価した。なお、高さ1mm未満を評価する場合には、離型フィルム(東洋紡社製TN-100)上に任意の膜厚で組成物を塗布し、上記の条件で硬化させ、離型フィルム側を触診し、評価した。結果を表1~表5に示す。
(評価基準)
+++:2mm以上
++:1mm以上2mm未満
+:0.05mm以上1mm未満
-:0.05mm未満
 なお、硬化物の高さが高いほど、深部まで硬化が進行しており、深部硬化性に優れると判断できる。
3. 3. Deep Curability The compositions obtained in Examples and Comparative Examples were poured into a cylindrical glass container (diameter 10 mm) having a mold release treatment on the inside so as to have an arbitrary height.
Next, the upper surface of the glass container was irradiated with a 365 nm LED (LED lamp having a peak top at 365 nm in the range of 300 nm to 500 nm, manufactured by Aitec System Co., Ltd.) at 5000 mJ / cm 2 (integrated light intensity at a wavelength of 365 nm).
Next, the composition after light irradiation was taken out from the glass container, and the one not irradiated with light (back surface) was palpated to check for tack. The height immediately before the tack appeared on the back surface was defined as the degree of deep curing of the composition, and was evaluated according to the following criteria. When evaluating a height of less than 1 mm, the composition is applied on a release film (TN-100 manufactured by Toyobo Co., Ltd.) with an arbitrary film thickness, cured under the above conditions, and the release film side is palpated. And evaluated. The results are shown in Tables 1 to 5.
(Evaluation criteria)
++++: 2 mm or more ++: 1 mm or more and less than 2 mm +: 0.05 mm or more and less than 1 mm-: less than 0.05 mm The higher the height of the cured product, the deeper the curing progresses, and the better the deep curing property. I can judge.
4.分散性
 実施例及び比較例で得られた組成物の液性状を目視で観察し、下記基準で評価を行った。
++:均一に分散し、流動性が高い(粘性が低い)。
+:均一に分散しているが、流動性が低い(粘性が高い)。
-:凝集物や充填剤の分離(粉状)、沈殿が見られる。
4. Dispersibility The liquid properties of the compositions obtained in Examples and Comparative Examples were visually observed and evaluated according to the following criteria.
++: Disperses uniformly and has high fluidity (low viscosity).
+: It is uniformly dispersed, but its fluidity is low (high viscosity).
-: Aggregates and fillers are separated (powdered) and settled.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
 表1~表5より、実施例の組成物は、寸法安定性、接着力及び深部硬化性が良好であることが確認できた。また、実施例の組成物は、露光後に加熱処理を行わない場合であっても優れた接着力及び深部硬化性を発揮することが確認できた。
 また、実施例の組成物は、分散性も良好であることが確認できた。
From Tables 1 to 5, it was confirmed that the compositions of Examples had good dimensional stability, adhesive strength and deep curability. Further, it was confirmed that the composition of the example exhibited excellent adhesive strength and deep curability even when the heat treatment was not performed after the exposure.
It was also confirmed that the composition of the example had good dispersibility.
 1・・・アルミ基板
 2・・・硬化物
 3・・・ガラス基板
 4・・・スペーサ
 10・・評価用サンプル
 X・・・押込み力
1 ... Aluminum substrate 2 ... Cured product 3 ... Glass substrate 4 ... Spacer 10 ... Evaluation sample X ... Pushing force

Claims (10)

  1.  環状エーテル成分と、
     水酸基含有成分と、
     充填剤と、
     光酸発生剤と、
    を含む組成物であって、
     前記環状エーテル成分は、脂環式エポキシ化合物を含み、
     前記脂環式エポキシ化合物の含有量が、前記環状エーテル成分100質量部中に80質量部以上であり、
     前記充填剤の含有量が、前記環状エーテル成分及び前記水酸基含有成分の合計100質量部に対して、40質量部以上である組成物。
    Cyclic ether component and
    Hydroxy group-containing components and
    Filler and
    With a photoacid generator
    It is a composition containing
    The cyclic ether component contains an alicyclic epoxy compound.
    The content of the alicyclic epoxy compound is 80 parts by mass or more in 100 parts by mass of the cyclic ether component.
    A composition in which the content of the filler is 40 parts by mass or more with respect to 100 parts by mass in total of the cyclic ether component and the hydroxyl group-containing component.
  2.  前記充填剤の平均粒径が、1μm以上100μm以下である請求項1に記載の組成物。 The composition according to claim 1, wherein the average particle size of the filler is 1 μm or more and 100 μm or less.
  3.  前記充填剤が、表面処理層により被覆された粒子を含む請求項1又は請求項2に記載の組成物。 The composition according to claim 1 or 2, wherein the filler contains particles coated with a surface treatment layer.
  4.  前記水酸基含有成分が、水酸基の数が3個以上の化合物を含む請求項1から請求項3までのいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 3, wherein the hydroxyl group-containing component contains a compound having 3 or more hydroxyl groups.
  5.  前記水酸基含有成分が、脂肪族アルコール化合物を含む請求項1から請求項4までのいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 4, wherein the hydroxyl group-containing component contains an aliphatic alcohol compound.
  6.  前記水酸基含有成分の含有量が、前記環状エーテル成分及び前記水酸基含有成分の合計100質量部中に、5質量部以上50質量部以下である請求項1から請求項5までのいずれか一項に記載の組成物。 The item according to any one of claims 1 to 5, wherein the content of the hydroxyl group-containing component is 5 parts by mass or more and 50 parts by mass or less in a total of 100 parts by mass of the cyclic ether component and the hydroxyl group-containing component. The composition described.
  7.  前記脂環式エポキシ化合物が、シクロアルケンオキサイド構造を2個以上有する化合物を含む請求項1から請求項6までのいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 6, wherein the alicyclic epoxy compound contains a compound having two or more cycloalkene oxide structures.
  8.  接着剤として用いられる請求項1から請求項7までのいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 7, which is used as an adhesive.
  9.  請求項1から請求項8までのいずれか一項に記載の組成物の硬化物。 A cured product of the composition according to any one of claims 1 to 8.
  10.  請求項1から請求項8までのいずれか一項に記載の組成物に光照射する光照射工程を有する硬化物の製造方法。 A method for producing a cured product, which comprises a light irradiation step of irradiating the composition according to any one of claims 1 to 8.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6121126A (en) * 1984-07-11 1986-01-29 Suriibondo:Kk Ultraviolet-curable resin composition
JPH08283388A (en) * 1995-04-06 1996-10-29 Mitsubishi Rayon Co Ltd Active energy radiation curing composition
JPH11199681A (en) * 1997-11-14 1999-07-27 Asahi Denka Kogyo Kk Photopolymerizable composition and formation of curable coating film
JP2018159911A (en) * 2017-01-27 2018-10-11 住友化学株式会社 Polarizing plate and image display device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6121126A (en) * 1984-07-11 1986-01-29 Suriibondo:Kk Ultraviolet-curable resin composition
JPH08283388A (en) * 1995-04-06 1996-10-29 Mitsubishi Rayon Co Ltd Active energy radiation curing composition
JPH11199681A (en) * 1997-11-14 1999-07-27 Asahi Denka Kogyo Kk Photopolymerizable composition and formation of curable coating film
JP2018159911A (en) * 2017-01-27 2018-10-11 住友化学株式会社 Polarizing plate and image display device

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