WO2022014552A1 - Composition, produit durci et procédé de production d'un produit durci - Google Patents

Composition, produit durci et procédé de production d'un produit durci 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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English (en)
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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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the present 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.

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Abstract

L'objectif principal de la présente divulgation est de fournir une composition présentant une excellente stabilité dimensionnelle, une excellente force d'adhérence et une excellente aptitude au durcissement en profondeur. La présente divulgation permet d'atteindre l'objectif ci-dessus en fournissant une composition contenant un composant éther cyclique, un composant contenant un groupe hydroxyle, une charge et un générateur de photoacide, le composant éther cyclique contenant un composé époxy alicyclique, la teneur en composé époxy alicyclique étant au moins égale à 80 parties en masse pour 100 parties en masse du composant éther cyclique, et la teneur en charge étant au moins égale à 40 parties en masse pour 100 parties en masse au total du composant éther cyclique et du composant contenant un groupe hydroxyle.
PCT/JP2021/026214 2020-07-16 2021-07-13 Composition, produit durci et procédé de production d'un produit durci WO2022014552A1 (fr)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
JPS6121126A (ja) * 1984-07-11 1986-01-29 Suriibondo:Kk 紫外線硬化性樹脂組成物
JPH08283388A (ja) * 1995-04-06 1996-10-29 Mitsubishi Rayon Co Ltd 活性エネルギー線硬化性組成物
JPH11199681A (ja) * 1997-11-14 1999-07-27 Asahi Denka Kogyo Kk 光重合性組成物および硬化塗膜形成方法
JP2018159911A (ja) * 2017-01-27 2018-10-11 住友化学株式会社 偏光板及び画像表示装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6121126A (ja) * 1984-07-11 1986-01-29 Suriibondo:Kk 紫外線硬化性樹脂組成物
JPH08283388A (ja) * 1995-04-06 1996-10-29 Mitsubishi Rayon Co Ltd 活性エネルギー線硬化性組成物
JPH11199681A (ja) * 1997-11-14 1999-07-27 Asahi Denka Kogyo Kk 光重合性組成物および硬化塗膜形成方法
JP2018159911A (ja) * 2017-01-27 2018-10-11 住友化学株式会社 偏光板及び画像表示装置

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