WO2020045358A1 - Composition, adhesive including same, cured object obtained therefrom, and production method therefor - Google Patents

Composition, adhesive including same, cured object obtained therefrom, and production method therefor Download PDF

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Publication number
WO2020045358A1
WO2020045358A1 PCT/JP2019/033348 JP2019033348W WO2020045358A1 WO 2020045358 A1 WO2020045358 A1 WO 2020045358A1 JP 2019033348 W JP2019033348 W JP 2019033348W WO 2020045358 A1 WO2020045358 A1 WO 2020045358A1
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WIPO (PCT)
Prior art keywords
compound
composition
mass
parts
component
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PCT/JP2019/033348
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French (fr)
Japanese (ja)
Inventor
和幸 板野
智志 渡辺
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株式会社Adeka
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Application filed by 株式会社Adeka filed Critical 株式会社Adeka
Priority to CN201980046766.4A priority Critical patent/CN112399978A/en
Priority to JP2020539448A priority patent/JP7437306B2/en
Priority to KR1020217005076A priority patent/KR20210053885A/en
Publication of WO2020045358A1 publication Critical patent/WO2020045358A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

  • the present invention relates to a composition, an adhesive containing the same, a cured product thereof, and a method for producing the same.
  • the composition is excellent in curing speed and water resistance, and a cured product excellent in adhesive strength is obtained.
  • the present invention relates to an adhesive, a cured product thereof, and a method for producing the same.
  • Cation curable compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members and the like. Various reports have been made on the improvement of such a curable composition.
  • Patent Literature 1 proposes an active energy ray-curable adhesive composition for a plastic film or the like, which has a low viscosity, is excellent in curability, and has excellent adhesive strength to various plastic films or sheets and excellent colorless transparency.
  • Patent Document 2 discloses an activity for a plastic film having low viscosity, excellent curability, excellent adhesion to various plastic films even when the atmospheric humidity during coating and curing is high, and excellent colorless transparency.
  • Energy ray-curable adhesive compositions have been proposed.
  • Patent Document 3 even if the humidity of the coating environment is high, the curability is excellent, the adhesive strength after a certain period of time, the durability, the adhesive strength after the end of the moist heat resistance test, and the low viscosity.
  • Photocurable adhesives have been proposed. Furthermore, in Patent Document 4, a curable resin composition layer is formed by applying a light and thermosetting resin composition having diacrylate having a dicyclopentadiene skeleton and diglycidyl ether having a dicyclopentadiene skeleton. There has been proposed a method for producing a laminate having a step and a step of irradiating the curable resin composition layer with an active energy ray.
  • the cationically curable compositions proposed in Patent Literatures 1 to 4 have a problem in that sufficient curability cannot be obtained, and the obtained cured product has insufficient water resistance.
  • the curing speed may be insufficient or sufficient adhesive strength and water resistance may not be obtained.
  • an object of the present invention is to provide a composition that is excellent in curing speed and water resistance, and that can obtain a cured product having excellent adhesive strength, To provide an adhesive, a cured product thereof, and a production method thereof.
  • the composition of the present invention is a composition containing a radically polymerizable component (A) and a cationically polymerizable component (B), wherein the radically polymerizable component (A) is a radically polymerizable compound having a crosslinked condensed ring. 70 to 100 parts by mass of (A1) per 100 parts by mass of the radically polymerizable component (A),
  • the cationically polymerizable component (B) contains 10 to 50 parts by mass of a cationically polymerizable compound (B1) having a crosslinked condensed ring per 100 parts by mass of the cationically polymerizable component (B). .
  • the composition of the present invention further contains a radically polymerizable initiator (C) and a cationically polymerizable initiator (D),
  • the radical polymerizable component (A), the cationic polymerizable component (B), the radical polymerizable initiator (C) and the cationic polymerizable initiator (D) in a total amount of 100 parts by mass contain the radical polymerizable component.
  • Such a composition has excellent initial curability.
  • the crosslinked condensed ring contained in the radically polymerizable compound (A1) and the cationically polymerizable compound (B1) has a structure represented by the following formula (I). It is preferred that In such a composition, the obtained cured product has excellent water resistance.
  • composition of the present invention contains, as the cationic polymerizable component (B), a cationic polymerizable compound (B2) having no crosslinked condensed ring and having a weight average molecular weight of 1,000 or more and less than 30,000. Is preferred. From such a composition, a cured product having excellent water resistance can be obtained.
  • the cationically polymerizable component (B) may contain a cationically polymerizable compound (B3) having a weight average molecular weight of not less than 200 and less than 1,000 having no crosslinked condensed ring. preferable. From such a composition, a cured product having excellent coatability and water resistance can be obtained.
  • the cationically polymerizable compound (B3) preferably contains a compound having an oxetanyl group. From such a composition, a cured product having excellent water resistance can be obtained.
  • composition of the present invention contains, as the radically polymerizable component (A), a radically polymerizable compound (A2) having a cationically polymerizable group and not having an isocyanurate ring or a crosslinked condensed ring. Is preferred. Such a composition is excellent in coatability and initial adhesiveness.
  • the radical polymerizable component (A) contains a radical polymerizable compound (A3) containing an isocyanurate ring and having no cross-linked condensed ring. From such a composition, a cured product having excellent water resistance can be obtained.
  • the adhesive of the present invention is characterized by containing the composition of the present invention.
  • an adhesive can be obtained which is excellent in curing speed and can obtain a cured product excellent in adhesive strength and water resistance.
  • the cured product of the present invention is a cured product of the composition of the present invention.
  • a cured product having excellent adhesive strength and water resistance is obtained.
  • the method for producing a cured product of the present invention includes a step of irradiating or heating an active energy ray to the composition of the present invention. Since the composition of the present invention contains the above components, a cured product excellent in adhesive strength and water resistance can be easily obtained.
  • the present invention it is possible to provide a composition capable of obtaining a cured product having excellent curing speed and water resistance and excellent adhesive strength, an adhesive containing the composition, a cured product thereof, and a method for producing the same.
  • composition of the present invention an adhesive containing the same, a cured product thereof, and a method for producing the same will be described in detail.
  • the composition of the present invention comprises a radical polymerizable component (A) (hereinafter, also referred to as “component (A)”) and a cationically polymerizable component (B) (hereinafter, also referred to as “component (B)”). Things.
  • component (A) a radical polymerizable component
  • component (B) a cationically polymerizable component
  • Things 70 to 100 parts by mass of the radically polymerizable compound (A1) having a crosslinked condensed ring (hereinafter, also referred to as “compound (A1)”) is contained in 100 parts by mass of the component (A).
  • a cationically polymerizable compound (B1) having a crosslinked condensed ring (hereinafter, also referred to as “compound (B1)”) per 100 parts by mass of component (B).
  • a radically polymerizable initiator (C) hereinafter, also referred to as “component (C)”
  • component (D) a cationically polymerizable initiator
  • Preferred proportions of component (A), component (B), component (C) and component (D) in the composition of the present invention are component (A), component (B), component (C) and component (D).
  • the ratio of the component (A) to the component (B) is preferably 50 to 130 parts by mass with respect to 100 parts by mass of the component (A).
  • a cured product having excellent adhesive strength and water resistance is preferably obtained.
  • Component (A) is a compound having a radical polymerizable group.
  • the radical polymerizable group means a group that can be polymerized in the presence of a radical, and includes, for example, an acryl group, a methacryl group, a vinyl group, and a thiol group.
  • Component (A) is compound (A1), a radically polymerizable compound (A2) having a cationically polymerizable group and not having an isocyanurate ring or a cross-linked condensed ring (hereinafter, also referred to as “compound (A2)”), Radical polymerizable compound (A3) having an isocyanurate ring and no cross-linked condensed ring (hereinafter also referred to as “compound (A3)”) and other radical polymerization not belonging to compounds (A1) to (A3) It is composed of a sex compound.
  • these compounds can be used alone or in combination of two or more.
  • the component (A) preferably contains a low molecular weight compound from the viewpoint of ease of application and curing speed of the composition of the present invention. Further, the low molecular weight compound is excellent in dispersibility or solubility in the composition and the like, so that a cured product excellent in transparency can be obtained.
  • the radical polymerizable compound preferably contains a high molecular weight compound from the viewpoint of the adhesive strength of the composition of the present invention. It is preferable that the radically polymerizable compound contains both a low molecular weight compound and a high molecular weight compound from the viewpoint of the balance between the ease of application of the composition, the curing speed, and the adhesive strength. Further, when the high molecular weight compound is used together with the low molecular weight compound, the dispersion or solubility in the composition of the present invention can be improved, and a cured product having excellent transparency can be obtained.
  • the molecular weight of the low molecular weight compound is not particularly limited as long as desired coatability and the like can be obtained.
  • the molecular weight can be 1,000 or less, preferably 50 to 500, and more preferably 50 to 300.
  • the following is preferred.
  • the molecular weight of the high molecular weight compound is not particularly limited as long as desired adhesion easiness and the like can be obtained.
  • the molecular weight can be larger than 1,000, and is preferably 1,000 or more and 50,000 or less, Especially, it is preferable that it is 5,000 or more and 20,000 or less.
  • the molecular weight indicates the weight average molecular weight (Mw) when the compound is a polymer.
  • the weight average molecular weight can be determined as a standard polystyrene conversion value by gel permeation chromatography (GPC).
  • the weight average molecular weight Mw is determined, for example, by using GPC (LC-2000plus series) manufactured by JASCO Corporation, eluting solvent as tetrahydrofuran, and polystyrene standard for calibration curve as Mw 1,110,000, 707,000, 397,000. , 189,000, 98,900, 37,200, 13,700, 9,490, 5,430, 3,120, 1,010,589 (Tosoh Corp. TSKgel standard polystyrene), and the measurement column was used.
  • the measurement temperature can be 40 ° C.
  • the flow rate can be 1.0 mL / min.
  • the content of the component (A) contained in the composition of the present invention is preferably from 40 to 60 parts by mass, and particularly preferably from 45 to 55 parts by mass, since water resistance is excellent with respect to 100 parts by mass of the composition. It is.
  • Compound (A1) is a radically polymerizable compound having a crosslinked condensed ring.
  • the bridged condensed ring of the compound (A1) means a condensed ring having three or more carbon atoms, and preferably contains a crosslinked condensed ring having a structure represented by the general formula (I). .
  • Examples of the crosslinked condensed ring having such a structure include the following crosslinked condensed rings.
  • crosslinked condensed ring No. 6 no. 7 and No. 7
  • An adhesive containing the compound (A1) having 8 is preferable because it has high adhesive strength and water resistance.
  • Bridged condensed ring No. 6 is particularly preferable because of its stable structure and high productivity.
  • the compound (A1) having 1 to 4 radically polymerizable groups is preferable because it has a good balance between adhesion and coatability, and the compound (A1) having 1 to 3 radically polymerizable groups is preferred. Is particularly preferred.
  • Examples of the compound (A1) include tricyclodecane dimethanol di (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dimethylol dicyclopentanedi (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, adamantane (meth) acrylate, 2-isopropyl-2-adamantyl (meth) acrylate and the like.
  • ⁇ ⁇ As the compound (A1), a commercially available product can also be used. Commercial products include, for example, Kayarad R-684 (all manufactured by Nippon Kayaku); A-DCP and DCP (all manufactured by Shin-Nakamura Chemical); FA-511AS, FA-512AS, FA-513AS, FA-512M. , FA-512MT and FA-513M (all manufactured by Hitachi Chemical).
  • the compound (A2) is not particularly limited as long as it is a radical polymerizable compound having a cationic polymerizable group and not having an isocyanurate ring or a cross-linked condensed ring.
  • the cationically polymerizable group means a group that can be polymerized in the presence of an acid, and includes, for example, a hydroxyl group, an epoxy group, an alicyclic epoxy group, an oxetanyl group, and a vinyl ether group.
  • a hydroxyl group is preferable from the viewpoint of substrate adhesion.
  • Epoxy groups are preferred from the viewpoints of initial curability and adhesive strength.
  • Examples of the compound (A2) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxy Hydroxyl-containing acrylates such as propyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dipentaerythritol penta (meth) acrylate and pentaerythritol tri (meth) acrylate; N-2-hydroxyethyl (meth) acrylamide; Hydroxy group-containing acrylamides such as N-vinylformamide; vinyl alcohols such as vinyl phenol, allyl alcohol and crotyl alcohol; Epoxy (meth) acrylate of ethylene glycol diglycidyl ether, mono (meth) acrylate of diethylene glycol diglycidyl ether, mono (meth) acrylate of triethylene glyco
  • the radical polymerizable group of the compound (A2) is preferably an acrylic group. Further, from the viewpoint of low viscosity and excellent coatability, it is preferable to have one or two radically polymerizable groups.
  • the preferable content of the radically polymerizable compound (A2) is excellent in adhesiveness, water resistance and fluidity.
  • the amount is preferably from 0 to 20 parts by mass, particularly preferably from 5 to 10 parts by mass, per 100 parts by mass of the component (A).
  • the compound (A3) is not particularly limited as long as it is a radical polymerizable compound containing an isocyanurate ring and not having a crosslinked condensed ring.
  • Examples of the compound (A3) include ⁇ -caprolactone-modified tris [2- (meth) acryloxyethyl] isocyanurate, tri [(meth) acryloylethyl] isocyanurate, and tris [3- (meth) acryloxypropyl] isocyanate Tris [(meth) acryloxyalkyl] isocyanurate and di [(meth) acryloylethyl] -2-hydroxyethyl isocyanurate, monoallyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate and the following compound (A3 ) No. 1 and the like.
  • a commercially available product can also be used.
  • Commercially available products include, for example, Aronix M-215, M-315 (above, Toagosei); NK esters A-9300, A-9300-1CL, A-9300-3CL (above, manufactured by Shin-Nakamura Chemical Co., Ltd.); (Mitsubishi Chemical).
  • an acryl group is preferable from the viewpoint of excellent curability. Further, from the viewpoint of excellent curability, it preferably has a plurality of radically polymerizable groups, and particularly preferably has two or three radically polymerizable groups.
  • the preferable content of the radically polymerizable compound (A3) is such that the radically polymerizable component (A) is excellent in water resistance and fluidity.
  • the amount is preferably from 0 to 20 parts by mass, particularly preferably from 5 to 10 parts by mass, per 100 parts by mass.
  • radically polymerizable compounds include, for example, unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid, ⁇ -chloro Acrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, mono [2- (meth) acryloyl succinate Roxyethyl], mono [2- (meth) acryloyloxyethyl phthalate], ⁇ -carboxypolycaprolactone mono (meth) acrylate, etc., a polymer mono (meth) acrylate having a carboxy
  • Acid anhydrides of unsaturated polybasic acids Amides of unsaturated monobasic acids and polyamines such as (meth) acrylamide, methylenebis- (meth) acrylamide, diethylenetriaminetris (meth) acrylamide, xylylenebis (meth) acrylamide and ⁇ -chloroacrylamide; unsaturated aldehydes such as acrolein; Unsaturated nitriles such as (meth) acrylonitrile, ⁇ -chloroacrylonitrile, vinylidene cyanide and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, Unsaturated aromatic compounds such as divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl
  • radical polymerizable compounds commercially available products can also be used.
  • Commercially available products include, for example, Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (all manufactured by Nippon Kayaku); NK ester A-DOD-N, A-DPH, A- TMPC, A-HD-N, TMPT, NPG and HD-N (all manufactured by Shin-Nakamura Chemical Co., Ltd.); SPC-1000, SPC-3000 (all manufactured by Showa Denko); NK Oligo @ U-4HA, U-4H, U-6HA, U-15HA, U-108A, U-1084A, U-200AX, U-122A, U-340A, U-324A, UA-53H, UA-100, AH-600 (Shin-Nakamura Chemical Co., Ltd.) UA-306H, AI-600, UA-101T, UA-101I, UA-306T
  • the cationically polymerizable component (B) contained in the composition of the present invention is a compound having a cationically polymerizable group and not having a radically polymerizable group.
  • the component (B) is a compound (B1), a cationically polymerizable compound (B2) having a cationically polymerizable group and having no crosslinked condensed ring and having a weight average molecular weight of 1,000 or more and less than 30,000 (hereinafter referred to as “compound”).
  • compound (B2) a cationically polymerizable compound (B3) having no crosslinked condensed ring and having a weight average molecular weight of 200 or more and less than 1,000 (hereinafter also referred to as “compound (B3)”) and compounds (B1) to It is composed of other cationically polymerizable compounds not belonging to compound (B3).
  • compound (B3) a cationically polymerizable compound having no crosslinked condensed ring and having a weight average molecular weight of 200 or more and less than 1,000
  • compound (B3) a cationically polymerizable compound (B3) having no crosslinked condensed ring and having a weight average molecular weight of 200 or more and less than 1,000
  • compound (B3) a cationically polymerizable compound (B3) having no crosslinked condensed ring and having a weight average molecular weight of 200 or more and less than 1,000
  • compound (B3) a cationically polymerizable compound having no crosslinked condensed ring and
  • the content of the component (B) contained in the composition of the present invention is preferably from 30 to 50 parts by mass, particularly preferably from 40 to 50 parts by mass, since water resistance is excellent with respect to 100 parts by mass of the composition. is there.
  • Component (B) preferably contains a low molecular weight compound from the viewpoint of ease of application and curing speed of the composition of the present invention. Further, the low molecular weight compound is excellent in dispersibility or solubility in the composition and the like, so that a cured product excellent in transparency can be obtained.
  • the cationically polymerizable compound preferably contains a high molecular weight compound from the viewpoint of the adhesive strength of the composition of the present invention and the like. Further, the cationically polymerizable compound preferably contains both a low molecular weight compound and a high molecular weight compound from the viewpoint of the balance between the ease of application of the composition, the curing speed, and the adhesive strength. Also, when the high molecular weight compound is used together with the low molecular weight compound, the dispersion or solubility in the composition of the present invention can be improved, and a cured product excellent in transparency can be obtained.
  • the content of the high molecular weight compound is not particularly limited as long as a desired curing rate and adhesive strength can be obtained.
  • the content is appropriately adjusted from the viewpoint of a balance between adhesive strength and transparency. is there.
  • the content of the high molecular weight compound can be 0 to 20 parts by mass in 100 parts by mass of the solid content of the composition of the present invention, and can be 2 to 15 parts by mass. It is particularly preferable that the amount is 3 parts by mass or more and 10 parts by mass or less.
  • the composition of the present invention becomes excellent in curing speed and adhesive strength, and it is possible to form a cured product excellent in transparency and particularly excellent in adhesive strength. Because it becomes.
  • Compound (B1) is a cationically polymerizable compound having a crosslinked condensed ring.
  • a crosslinked condensed ring having a structure represented by the above general formula (I) is preferable because of its excellent water resistance. 6
  • An adhesive containing the compound (B1) having 8 has a high adhesive strength and water resistance, and is therefore preferred.
  • Bridged condensed ring No. 6 is particularly preferable because of its stable structure and high productivity.
  • the compound (B1) for example, the following compound (B1) No. 1 to No. 22 and the like.
  • ⁇ ⁇ As the compound (B1), a commercial product can also be used.
  • Commercially available products include, for example, Adeka Resin EP-4088L, 4088S (above, manufactured by ADEKA); XD-1000 (manufactured by Nippon Kayaku), HP-7200 (manufactured by DIC).
  • the cationically polymerizable group of the compound (B1) an epoxy group is preferable, and a glycidyl ether group is particularly preferable from the viewpoint of high curability and excellent adhesive strength. Further, from the viewpoint of excellent curability, it preferably has a plurality of cationically polymerizable groups, and particularly preferably has two or three cationically polymerizable groups.
  • the compound (B2) is not particularly limited as long as it is a cationic polymerizable compound having a weight average molecular weight of 1,000 or more and less than 30,000 having no crosslinked condensed ring.
  • the weight average molecular weight can be measured by the above-mentioned measuring method.
  • the composition containing the compound (B2) is preferable because the water resistance is improved.
  • Examples of the compound (B2) include a glycidyl methacrylate polymer and a glycidyl methacrylate copolymer such as a glycidyl methacrylate and methyl methacrylate copolymer, and a partially modified glycidyl methacrylate.
  • a glycidyl methacrylate polymer and a glycidyl methacrylate copolymer such as a glycidyl methacrylate and methyl methacrylate copolymer
  • a partially modified glycidyl methacrylate such as a glycidyl methacrylate and methyl methacrylate copolymer
  • a partially modified glycidyl methacrylate such as a glycidyl methacrylate and methyl methacrylate copolymer
  • a partially modified glycidyl methacrylate such as a glycidyl methacrylate and methyl
  • polymers such as novolak type epoxy resins, 2-hydroxyethyl vinyl ether, triethylene glycol vinyl monoether, tetraethylene glycol divinyl ether, and trimethylolpropane trivinyl ether, and copolymers thereof, and the like are also included. .
  • ⁇ ⁇ As the compound (B2), a commercial product can also be used.
  • Commercially available products include, for example, G-0130M (both manufactured by NOF) and EOCN-104S (manufactured by Nippon Kayaku).
  • the compound (B2) having an epoxy equivalent of 1,000 or less is preferable because of excellent curability, and the epoxy equivalent is particularly preferably 200 to 600.
  • an epoxy group is preferable, and a glycidyl ether group is particularly preferable, since a composition having high curability and high adhesive force can be obtained.
  • the preferable content of the cationically polymerizable compound (B2) which may be contained in the cationically polymerizable component (B) is 0 to 100 parts by mass of the cationically polymerizable component (B) because of its excellent water resistance and fluidity.
  • the amount is 30 parts by mass, particularly preferably 5 to 20 parts by mass.
  • the compound (B3) is not particularly limited as long as it is a cationically polymerizable compound having a weight average molecular weight of 200 or more and less than 1,000 without a crosslinked condensed ring.
  • the composition containing the compound (B3) is preferable because it can achieve both adhesive strength and applicability.
  • Examples of the compound (B3) include an aromatic epoxy compound, an alicyclic epoxy compound, an aliphatic epoxy compound, an oxetane compound, and the like. However, compounds having an epoxy group and an oxetanyl group in the same molecule are classified as oxetane compounds.
  • a composition containing a compound (B3) having an epoxy equivalent of 500 or less is preferable because of excellent curability, and a composition containing a compound (B3) having an epoxy equivalent of 200 or less is particularly preferable.
  • an epoxy group is preferable, and a glycidyl ether group is particularly preferable, since a composition having high curability and high adhesive strength can be obtained.
  • a compound having an oxetanyl group is also preferable, since a composition having excellent water resistance can be obtained.
  • the content is preferably from 0 to 90 per 100 parts by mass of the cationically polymerizable component (B) because of its excellent water resistance and fluidity.
  • the parts by mass are preferable, and particularly preferably 35 to 80 parts by mass.
  • composition containing the compound (B3) containing 1 to 3 cationically polymerizable groups is preferable because both the adhesive strength and the applicability can be achieved, and the compound (B3) containing 1 to 2 cationically polymerizable groups is particularly preferable. .
  • the alicyclic epoxy compound as the compound (B3) is a cation having an alicyclic epoxy group (3,4-epoxycyclohexyl group) and not having a crosslinked condensed ring and having a weight average molecular weight of 200 or more and less than 1,000. It means a polymerizable compound. It is preferable to use an alicyclic epoxy compound as the compound (B3) because the initial curability is improved.
  • Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 3,4-epoxy- 1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3 -Methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclo Hexylmethyl) adipate, 3,4-epoxy-6-methylcyclo
  • Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate and 2,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate is preferred from the viewpoint of improving adhesive strength.
  • alicyclic epoxy compound Commercially available products can be used as the alicyclic epoxy compound, and examples thereof include Celloxide 2021P, Celloxide 2081, Celloxide 2000, Celloxide 3000, Cyclomer M100 (manufactured by Daicel); CYRACURE @ UVR-6128 (manufactured by Dow Chemical Company). Manufactured).
  • the content of the alicyclic epoxy compound may be any as long as a desired curing rate and adhesive strength can be obtained.
  • the content can be 0 to 50 parts by mass in 100 parts by mass of the compound (B). However, it is preferably from 1 part by mass to 20 parts by mass. When the content is in such a range, the composition of the present invention has excellent curing speed and adhesive strength.
  • the aliphatic epoxy compound as the compound (B3) refers to a cationic polymerizable compound having a weight average molecular weight of 200 or more and less than 1,000 having no crosslinked condensed ring that is not classified as an alicyclic epoxy compound or an aromatic epoxy compound described below. Refers to those that do not contain aliphatic and aromatic rings.
  • the aliphatic epoxy compound examples include a glycidyl ether compound of an aliphatic alcohol, a monofunctional epoxy compound such as a glycidyl ester of an alkyl carboxylic acid, a polyglycidyl ether compound of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof, and a fatty acid.
  • polyfunctional epoxy compounds such as polyglycidyl esters of long-chain polybasic acids.
  • aliphatic epoxy compounds include 1,4-butanediol diglycidylate, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, and 1,4-butanediol.
  • Further examples include monoglycidyl ethers of aliphatic higher alcohols and glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, epoxidized soybean oil, and epoxidized polybutadiene.
  • a glycidyl etherified product of an aliphatic alcohol or a polyglycidyl etherified product of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof is preferable because viscosity, coating property and reactivity are improved.
  • Glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether or 1,6-hexanediol diglycidyl ether is preferred.
  • aliphatic epoxy compound commercially available products can be used.
  • the content of the aliphatic epoxy compound may be any as long as the desired curing rate and adhesive strength can be obtained.
  • the content can be 0 to 90 parts by mass in 100 parts by mass of the compound (B). , 30 parts by mass or more and 80 parts by mass or less.
  • the composition of the present invention has excellent curing speed and adhesive strength.
  • the aromatic epoxy compound as the compound (B3) means an epoxy compound containing an aromatic ring having a weight average molecular weight of 200 or more and less than 1,000, which is not classified as an alicyclic epoxy compound and has no crosslinked condensed ring.
  • the aromatic epoxy compound include a monohydric phenol having at least one aromatic ring such as phenol, cresol and butyl phenol, or a mono / polyglycidyl etherified product of an alkylene oxide adduct thereof, for example, bisphenol A, bisphenol F Or a glycidyl etherified compound of a compound to which an alkylene oxide is further added, or a phenol novolak type epoxy compound; a glycidyl ether of an aromatic compound having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol; benzene dimethanol or benzene Polyglycidyl etherified aromatic compounds having two or more alcoholic hydroxyl groups such as diethanol and benzenedibutanol; phthalic acid, terephthalic acid, trimellitic acid, etc.
  • a monohydric phenol having at least one aromatic ring such as phenol, cresol and butyl phenol
  • polyglycidyl ethers of phenols polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups
  • polyglycidyl ethers of polyhydric phenols polyglycidyl esters of benzoic acids
  • polyglycidyl esters of polybasic acids It is preferable to contain at least one selected from the group from the viewpoint of reducing the viscosity of the composition of the present invention.
  • aromatic epoxy compound a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol E type epoxy compound, and a phenol novolak type epoxy compound are preferable because of their excellent adhesive strength.
  • aromatic epoxy compound commercially available ones can be used.
  • the content of the aromatic epoxy compound may be any as long as the desired curing rate and adhesive strength can be obtained.
  • the content can be 0 to 90 parts by mass per 100 parts by mass of the compound (B). It is preferably from 10 parts by mass to 50 parts by mass.
  • the composition of the present invention has excellent curing speed and adhesive strength.
  • the oxetane compound as the compound (B3) means an oxetane compound having an oxetanyl group and having no crosslinked condensed ring and having a weight average molecular weight of 200 or more and less than 1,000.
  • Oxetane compounds containing 1 to 3 oxetanyl groups are preferred, and oxetane compounds containing two oxetanyl groups are particularly preferred because of their excellent balance between curability and coatability.
  • oxetane compound examples include 3,3 ′-[oxybis (methylene)] bis (3-ethyloxetane), (3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3 -Ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] Propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1 , 4-bis (3-ethyl-3-oxetanylmethoxy
  • oxetane compound a commercially available product containing a cationic polymerizable monomer as a main component can be used.
  • a commercially available product containing a cationic polymerizable monomer as a main component can be used.
  • Alonoxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212, OXT-221 manufactured by Toagosei Co., Ltd.
  • etanacol OXBP, OXTP manufactured by Ube Industries
  • the content of the oxetane compound is not particularly limited as long as the desired curing rate and adhesive strength can be obtained.
  • the content of the oxetane compound can be 0 to 50 parts by mass in 100 parts by mass of the compound (B). However, it is preferably from 5 parts by mass to 30 parts by mass. When the content is within such a range, the composition of the present invention has excellent coatability and curing speed.
  • ⁇ Radical polymerizable initiator (C)> As the component (C) used in the composition of the present invention, a conventionally known radically polymerizable initiator can be used.
  • Component (C) is a photoradical polymerizable initiator and a thermal radical polymerizable initiator.
  • the photo-radical polymerization initiator is more preferable because of its high reactivity.
  • the component (C) is not particularly limited as long as it generates a radical by light irradiation, and a conventionally known compound can be used.
  • a conventionally known compound can be used.
  • an acetophenone-based compound, a benzyl-based compound, a benzophenone-based compound, and a thioxanthone-based compound can be used.
  • Compounds and oxime ester compounds can be exemplified as preferred ones.
  • acetophenone-based compound examples include benzoin, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, ⁇ -hydroxyacetophenone-based compounds such as -hydroxymethyl-2-methylpropiophenone and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one; ⁇ -alkoxyacetates such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether diethoxyacetophenone and 2,2-dimethoxy-1,2-diphenylethan-1-one Phenone compounds; p-dimethylaminoacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino
  • an acetophenone-based compound is preferable, and an ⁇ -hydroxyacetophenone-based compound is particularly preferable because the obtained cured product has excellent transparency.
  • Benzyl compounds include benzyl and the like.
  • benzophenone-based compound examples include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide. .
  • Thioxanthones include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone and the like.
  • the oxime ester-based compound means a compound having an oxime ester group, and is preferable since it has good sensitivity among photo-radical polymerization initiators.
  • ⁇ Preferred oxime ester-based compounds include, for example, Compound No. C1 to No. C14.
  • radically polymerizable initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyr- 1-yl)] titanocene compounds such as titanium.
  • radical initiators include ADEKA OPTOMER N-1414, N-1717, N-1919, ADEKA ARKULS NCI-831 and NCI-930 (all manufactured by ADEKA); 01, IRGACURE OXE 02, IRGACURE 784 (all manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (all manufactured by Tronly).
  • the heat radical polymerizable initiator is not particularly limited as long as it generates a radical by heating, and a conventionally known compound can be used.
  • a conventionally known compound can be used.
  • examples include an azo compound, a peroxide, and a persulfate. It can be exemplified as a preferable one.
  • azo compound examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'- Azobis (1-acetoxy-1-phenylethane) and the like.
  • peroxide examples include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butylperoxypivalate, di (4-t-butylcyclohexyl) peroxydicarbonate, and the like.
  • persulfate examples include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.
  • the component (C) can be used singly or as a mixture of two or more.
  • the content of the component (C) is not particularly limited, but is preferably 1 to 10 parts by mass in a total of 100 parts by mass of the components (A) to (D).
  • the amount is preferably from 1 to 10 parts by mass, more preferably from 3 to 8 parts by mass, because the curability is good with respect to 100 parts by mass of the component (A).
  • the content of the component (C) is within the above range, a curable composition having good curability and excellent storage stability without precipitation of a polymerizable initiator is obtained, which is preferable.
  • ⁇ Cationically polymerizable initiator (D)> The component (D) used in the composition of the present invention generates an acid upon irradiation with an active energy ray (hereinafter, also simply referred to as “active energy ray”) such as visible light, ultraviolet light, X-ray, electron beam, or high frequency.
  • active energy ray such as visible light, ultraviolet light, X-ray, electron beam, or high frequency.
  • Compound hereinafter, also referred to as "photo-cationic polymerizable initiator” or a compound capable of generating an acid by heating (hereinafter, also referred to as "thermal-cationic polymerizable initiator”). is there.
  • the component (D) has an aromatic ring and the number of aromatic rings is 3 or more.
  • the aromatic ring forms a ring structure such as an aromatic hydrocarbon ring, a furan ring, a benzofuran ring, a dibenzofuran ring, and a thiophene ring in which all atoms forming the ring structure such as a benzene ring, a naphthalene ring, and an anthracene ring are carbon atoms.
  • any of a cationic photopolymerizable initiator and a thermal cationic polymerizable initiator can be used. It is preferably an agent.
  • a double salt or a derivative thereof which is an onium salt, or 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 benzoin tosylate compound,
  • An iron arene complex, an acetophenone derivative compound, or the like can be used, and these can be used alone or as a mixture of two or more.
  • the photocationically polymerizable initiator is an onium salt double salt or a derivative thereof. This is because the composition of the present invention is excellent in curing speed and adhesive force by being such a photocationic polymerizable initiator.
  • examples of the compound having three or more aromatic rings include cation and anion salts represented by the following general formula (1).
  • the cation [A] m + is preferably onium, and its structure can be represented by, for example, the following general formula (2).
  • R 10 is an organic group having 1 to 60 carbon atoms and which may contain any number of atoms other than carbon atoms.
  • a is an integer of 1 to 5.
  • a number of R 10 are each independently, it may be the same or different.
  • At least one R 10 is the above-mentioned organic group having an aromatic ring, and the number of aromatic rings contained in the a R 10 is 3 or more.
  • the anion [B] m- is preferably a halide complex, and its structure can be represented by, for example, the following general formula (3).
  • L is a metal or metalloid (Metalloid) which is the central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V , Cr, Mn, Co and the like.
  • X is a halogen atom.
  • anion [LX b ] m- in the general formula (3) examples include tetrakis (pentafluorophenyl) borate [(C 6 F 5 ) 4 B] ⁇ , tetrafluoroborate (BF 4 ) ⁇ , and hexafluoro Phosphate (PF 6 ) ⁇ , hexafluoroantimonate (SbF 6 ) ⁇ , hexafluoroarsenate (AsF 6 ) ⁇ , hexachloroantimonate (SbCl 6 ) ⁇ , tris (pentafluoromethyl) trifluorophosphate ion (FAP anion) And the like.
  • anion [B] m- those having a structure represented by the following general formula (4) can also be preferably used.
  • L, X and b are the same as above.
  • Other usable anions include perchlorate ion (ClO 4 ) ⁇ , trifluoromethyl sulfite ion (CF 3 SO 3 ) ⁇ , fluorosulfonic acid ion (FSO 3 ) ⁇ , and toluenesulfonic acid anion , Trinitrobenzenesulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.
  • composition of the present invention among such onium salts, a sulfonium cation represented by the following Group I or Group II and a sulfonium salt such as hexafluoroantimony ion or tetrakis (pentafluorophenyl) borate ion may be used. Especially effective. Among these, one kind can be used alone, or two or more kinds can be used in combination.
  • Aromatic sulfonium salts are more preferred in terms of sensitivity.
  • the composition of the present invention becomes excellent in curing speed and adhesive strength.
  • R 121 , R 122 , R 123 , R 124 , R 125 , R 126 , R 127 , R 128 , R 129 and R 130 each independently represent a hydrogen atom or a halogen atom
  • R 131 , R 132 , R 133 and R 134 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 135 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or any substituent selected from the following chemical formulas (A) to (C)
  • An q- is a q-valent anion.
  • p represents a coefficient for neutralizing the charge.
  • R 221 , R 222 , R 223 , R 224 , R 225 , R 226 , R 227 , R 228 , R 229 , R 230 , R 231 , R 232 , R 233 , R 234 , R 236 , R 237 , R 238 , R 239 , R 245 , R 246 , R 247 , R 248 and R 249 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, Represents an alkoxy group having 1 to 10 carbon atoms or an ester group having 2 to 10 carbon atoms, R 240 , R 241 , R 242 , R 243 and R 244 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms, and * represents S in the general formula (5). Represents the bonding
  • the halogen atom represented by 236 , R237 , R238 , R239 , R240 , R241 , R242 , R243 , R244 , R245 , R246 , R247 , R248 and R249 is fluorine. , Chlorine, bromine, iodine and the like.
  • Examples of the alkyl group having 1 to 10 carbon atoms represented by 240 , R 241 , R 242 , R 243 , R 244 , R 245 , R 246 , R 247 , R 248 and R 249 include methyl, ethyl, propyl, Isopropyl, butyl, s-
  • alkoxy group having 1 to 10 carbon atoms examples include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, s-butyloxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, Cyclohexyloxy, cyclohexylmethyloxy , Tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethyloxy, 3-methoxypropyloxy, 4-methoxybutyloxy, 2-butoxyethyloxy, methoxyethoxyethyloxy, methoxyethoxyethoxyethyloxy, 3-methoxybutyloxy , 2-methylthioethyloxy, trifluoromethyloxy and the like.
  • ester group having 2 to 10 carbon atoms examples include methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy, propionyloxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy , T -Butylcarbonyloxy, methoxyacetyloxy, benzoyloxy and the like.
  • an anion having a predetermined valence can be used among the above-mentioned anions [B] m- .
  • R 135 is preferably selected from the chemical formulas (A) to (C), and particularly preferably selected from the chemical formulas (A) or (C). Is preferred. This is because when R 135 has the above-mentioned structure, the dispersion stability of the component (D) and the balance between the curing speed and the adhesive strength are excellent.
  • R 135 is a compound represented by the chemical formula (C).
  • R 135 is a compound represented by the chemical formula (A).
  • R 135 of the component (D) is represented by the chemical formula (A) from the viewpoint of achieving an excellent balance between the dispersion stability of the component (D), the curing speed, and the adhesive strength. It is preferable to include both the compound represented by the formula (C)
  • Component (D), if it contains both as R 135 is as a chemical formula (A), Formula (C), the content of those R 135 is a chemical formula (A), formula (C) It can be 10 parts by mass or more and 200 parts by mass or less, preferably 50 parts by mass or more and 200 parts by mass or less, and preferably 80 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass. It is preferred that When the content is in such a range, the dispersion stability of the component (D), the curing speed, and the balance between the adhesive strength are excellent.
  • 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 and R 134 are a hydrogen atom, a halogen atom, a carbon atom
  • composition of the present invention has an excellent balance between the dispersion stability of the component (D), the curing speed, and the adhesive strength due to the above-mentioned functional group. Also, the above-mentioned cationically polymerizable initiator can be easily synthesized.
  • R 221 , R 222 , R 223 , R 224 , R 225 , R 226 , R 227 , R 228 , R 229 , R 230 , R 231 , R 232 , R 233 , R 234 , R 236 , R 237 , R 238 , R 239 , R 240 , R 241 , R 242 , R 243 , R 244 , R 245 , R 246 , R 247 , R 248 and R 249 are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, It is preferably an alkoxy group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom.
  • composition of the present invention has an excellent balance between the dispersion stability of the component (D), the curing speed, and the adhesive strength due to the above-mentioned functional group. Also, the above-mentioned cationically polymerizable initiator can be easily synthesized.
  • the content of the component (D) is not particularly limited as long as a desired curing rate and adhesive strength can be obtained.
  • the content of the component (D) is not particularly limited as long as a desired curing rate and adhesive strength can be obtained.
  • the solid content of 100 parts by mass of the composition of the present invention It is preferably from 0.1 to 10 parts by mass, more preferably from 0.5 to 8 parts by mass, and particularly preferably from 1.0 to 7 parts by mass. And more preferably 1.5 to 6 parts by mass, and particularly preferably 2.0 to 5 parts by mass.
  • the composition of the present invention has an excellent balance between the dispersion stability of the component (D), the curing speed, and the adhesive strength.
  • the solid content of the composition of the present invention includes all components other than the solvent.
  • cationically polymerizable initiator (D) examples include, for example, “CPI-100P” and “CPI-101A” (manufactured by San-Apro Co., Ltd.); “IRGACURE 250” (manufactured by BASF SE), “ADEKA “Optomer SP-172”, “ADEKA OPTOMER SP-170”, “ADEKA OPTOMER SP-152”, “ADEKA OPTOMER SP-150” (all manufactured by ADEKA CORPORATION); “SAN AID @ SI-60L”; “Sun-Aid SI-80L”, “Sun-Aid SI-100L”, “Sun-Aid SI-150L” (all manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.
  • the composition of the present invention has a component (D) content of 1 to 10 parts by mass in a total of 100 parts by mass of the components (A) to (D) from the viewpoint of excellent curing speed and adhesive strength.
  • a component (D) content of 1 to 10 parts by mass in a total of 100 parts by mass of the components (A) to (D) from the viewpoint of excellent curing speed and adhesive strength.
  • it is particularly preferably from 2.0 parts by mass to 6 parts by mass, and particularly preferably from 3.0 parts by mass to 5 parts by mass.
  • a solvent may be used in the composition of the present invention.
  • the solvent is a compound capable of dispersing or dissolving each component in the composition, and is a liquid compound at normal temperature and normal pressure.
  • a solvent that does not include a compound having an acryl group, a methacryl group, a vinyl group, an epoxy group, or an oxetane group can be used.
  • Either water or an organic solvent can be used as such a solvent, but an organic solvent can be preferably used.
  • the content of the organic solvent is not particularly limited as long as a desired curing rate and adhesive strength can be obtained, and is preferably 80 parts by mass or more, more preferably 90 parts by mass or more in 100 parts by mass of the solvent, Among them, the amount is preferably 95 parts by mass or more, particularly preferably 100 parts by mass, that is, it is preferable to contain only an organic solvent as a solvent.
  • the composition of the present invention becomes excellent in the balance between the dispersion stability of the component (C) and the component (D), the curing speed, and the adhesive strength.
  • organic solvent examples include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate and diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and 2-heptanone; ethylene glycol, ethylene Polyhydric alcohols such as glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol and dipropylene glycol monoacetate, such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether and monophenyl ether And derivatives thereof; cyclic ethers such as dioxane Ters: ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruv
  • the composition of the present invention has an excellent balance between the dispersion stability of the component (C) and the component (D) and the curing speed and adhesive strength.
  • the molecular weight of the organic solvent is preferably 50 or more and 300 or less from the viewpoint of achieving an excellent balance between the solubility or dispersion stability of the components (A) to (D) and the curing speed and adhesive strength.
  • it is preferably 80 or more and 200 or less, and more preferably 90 or more and 150 or less.
  • the boiling point of the organic solvent is preferably from 100 ° C. to 350 ° C., and more preferably from 130 ° C. to 300 ° C., particularly from the viewpoint of reducing the volatilization from the cured product.
  • the temperature is preferably from 200 ° C to 300 ° C, particularly preferably from 200 ° C to 250 ° C.
  • the boiling point indicates a value under the atmospheric pressure.
  • the composition of the present invention can contain other components as required in addition to the above components.
  • Other components include inorganic fillers, organic fillers, pigments, silane coupling agents, coloring agents such as dyes, photosensitizers, defoamers, thickeners, thixotropic agents, surfactants, and leveling.
  • the total content of other components is preferably 30% by mass or less in the solid content of the composition of the present invention.
  • the method for producing the composition of the present invention is not particularly limited as long as the above components can be uniformly mixed.
  • the components (C) and (B) may be added to the components (A) and (B).
  • Component (D) and a solvent may be added to the components (A) and (B).
  • a mixing method a method using a known mixing device can be adopted, and for example, a method using a three-roll, sand mill, ball mill, or the like can be used.
  • the method of curing the composition of the present invention is appropriately set according to the types of the components (C) and (D).
  • the curing method when the component (C) and the component (D) are a photoradical polymerization initiator and a photocationic polymerization initiator, the active energy of irradiating the composition of the present invention with an active energy ray is used.
  • a method of performing a line irradiation treatment can be used.
  • the active energy ray includes visible light, ultraviolet light, electron beam, X-ray, radiation, high frequency and the like, and ultraviolet light is most economically preferable.
  • the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.
  • the composition of the present invention can be cured by irradiation with an LED light source.
  • the active energy rays from the LED light source include ultraviolet rays.
  • the wavelength of the active energy ray from the LED light source may be 350 nm to 405 nm.
  • the composition of the present invention is usually brought into a dry state to the touch or a solvent-insoluble state after 0.1 seconds to several minutes by irradiation with active energy rays. Can be cured.
  • the active energy ray and the exposure time to the active energy ray can be the same as those described in WO 2013/172145 or the like.
  • the composition of the present invention when the component (C) is a thermal radically polymerizable initiator, or when the component (D) is a thermocationically polymerizable initiator, the composition of the present invention
  • a method of performing a heat treatment can be used.
  • the conditions for curing the composition of the present invention by heating may be from 70 ° C. to 250 ° C. for 1 to 100 minutes. After pre-baking (PAB; Pre-applied bake), pressure may be applied to perform post-baking (PEB; Post-exposure bake), or baking may be performed at several different temperatures.
  • the heating conditions vary depending on the type and mixing ratio of each component. For example, the heating temperature may be 70 ° C.
  • a cured film is obtained by heating at 180 ° C. to 250 ° C., preferably 200 ° C. to 250 ° C. for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate to cure the coating film.
  • 180 ° C. to 250 ° C. preferably 200 ° C. to 250 ° C. for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate to cure the coating film.
  • composition of the present invention is not particularly limited as long as it is used to form and use a cured product.
  • Passivation films for solar cells interlayer insulating films, protective films, protective films for color filters, spacers, DNA separation chips, microreactors, nanobio devices, Used for hard disk recording materials, solid-state imaging devices, light-emitting diodes, organic light-emitting devices, luminescent films, fluorescent films, actuators, holograms, plasmon devices, polarizing plates, polarizing films, retardation films, and backlights for liquid crystal displays Prism lens sheets, Fresnel lens sheets used for screens of projection televisions, etc., lens parts of lens sheets such as lenticular lens sheets, or backlights using such sheets, optical lenses such as microlenses, optical elements, Examples include an optical connector, an optical waveguide, and a casting agent for optical modeling.
  • the composition of the present invention is preferably used for an adhesive from the viewpoint of more effectively exhibiting the effects of excellent curing speed and adhesive strength.
  • Specific applications of the adhesive include optical materials such as glasses and imaging lenses, electronic materials such as laminates and printed boards, in-vehicle devices such as head-up displays and car navigation systems, and organic materials. It can be used for various applications such as display panels represented by EL and liquid crystal. Above all, it is preferably used for applications requiring transparency, and particularly preferably used for applications such as optical materials, in-vehicle equipment, and display panels.
  • an adherend adhered by the adhesive of the present invention may be an inorganic material or an organic material.
  • organic material examples include cellulose esters such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, and nitrocellulose; polyamides; polyimides; polyurethanes; epoxy compounds; polycarbonates; Polyesters such as naphthalate, polybutylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate; polystyrene; polyethylene, polypropylene, Polyolefins such as polymethylpentene, polytetrafluoroethylene and cycloolefin polymers; Vinyl compounds such as alcohol, polyvinyl acetate, polyvinyl chloride and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylate; polycarbonate; polysulfone
  • the adhesive of the present invention contains the composition of the present invention.
  • the adhesive of the present invention is excellent in curing speed, adhesive strength and water resistance.
  • the adhesive of the present invention can be produced using the composition of the present invention.
  • the adhesive of the present invention may be composed of only the composition of the present invention, and the composition of the present invention and various additives known to be used when manufacturing the adhesive. It can be manufactured by mixing using a known mixing device.
  • the use of the composition and the adhesive of the present invention can be the same as those described in the section of the composition, and thus the description thereof is omitted.
  • the thickness after curing of the adhesive of the present invention is appropriately set according to the use of the adhesive of the present invention.
  • the thickness can be set to 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the cured product of the present invention is a cured product of the composition of the present invention.
  • the cured product of the present invention can be used, for example, as an adhesive layer having excellent curing speed and adhesive strength. Note that the composition of the present invention can be the same as the content described in the section of “composition”, and the description is omitted here.
  • the cured product of the present invention is a cured product of the composition of the present invention, and includes a polymer of the composition of the present invention. That is, the cured product of the present invention has a crosslinked condensed ring.
  • plan view shape, thickness, and the like of the cured product of the present invention can be appropriately set according to the use of the cured product.
  • the cured product of the present invention is obtained by forming the composition of the present invention into a desired shape and curing the composition, and the production method is not particularly limited.
  • a production method can be, for example, the same as the content described in the section of the method for producing a cured product described below, and thus the description thereof is omitted here.
  • the method for producing a cured product of the present invention has a curing step of curing the composition of the present invention. According to the method for producing a cured product of the present invention, since the curing step uses the composition of the present invention, a cured product having a curing speed and adhesive strength can be obtained.
  • each step of the method for producing a cured product of the present invention will be described in detail.
  • the curing step is a step of curing the composition of the present invention, and includes a step of irradiating or heating with active energy rays. Such a curing method can be the same as that described in the section “A. Composition”.
  • the method for producing a cured product of the present invention may have other steps as necessary.
  • Examples of such a step include a step of applying the composition of the present invention before the step of curing the composition of the present invention.
  • a method of applying the composition of the present invention known methods such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing and dipping can be used.
  • the composition of the present invention can be applied on a substrate.
  • the base material can be appropriately set according to the use of the cured product and the like, and examples include those containing soda glass, quartz glass, semiconductor substrates, metal, paper, plastic, and the like. Further, after the cured product is formed on the base material, the cured product may be peeled off from the base material or used by transferring from the base material to another adherend.
  • the cured product produced by the production method of the present invention, its use, and the like can be the same as those described in the section of the cured product.
  • composition of the present invention is not limited to the above embodiments.
  • the above embodiment is an exemplification, and has substantially the same configuration as the technical idea described in the scope of the claims of the present invention. It is included in the technical scope of the invention.
  • Examples 1 to 28 and Comparative Examples 1 to 7 According to the formulations shown in Tables 1 to 5, the components were blended to obtain compositions. The following materials were used for each component. In addition, the compounding amount in a table
  • surface represents the mass part of each component.
  • A1-1 Tricyclodecane dimethanol diacrylate
  • A1-2 Dicyclopentanyl acrylate
  • A2-1 4-n-hydroxybutyl acrylate
  • A2-2 Compound (A2) No. 1
  • A3-1 Tri (acryloylethyl) isocyanurate
  • A3-2 ⁇ -caprolactone-modified tris (2-acryloxyethyl) Isocyanurate
  • A4-1 1,6-hexanediol diacrylate
  • A4-2 1,10-decanediol diacrylate
  • Component (B) B1-1 Compound (B1) No. 1 B1-2: Compound (B1) No. 2 B2-1: Copolymer of glycidyl methacrylate and methyl methacrylate (weight average molecular weight 8,000, epoxy equivalent 500-600 g / eq. )
  • B2-2 Copolymer of glycidyl methacrylate and methyl methacrylate (weight average molecular weight 15,000, epoxy equivalent 500-600 g / eq.
  • B3-1 1,4-butanediol diglycidylate
  • B3-2 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate
  • B3-3 trimethylolpropane triglycidyl ether
  • B3-4 3,3 '-[Oxybis (methylene)] bis (3-ethyloxetane)
  • B3-5 Diglycidyl ether of bisphenol A
  • Component (C) C-1 1-hydroxycyclohexyl phenyl ketone
  • Component (D) D-1 CPI-100P (manufactured by San Apro)
  • Additive E-1 Leveling agent (SH-29PA manufactured by Dow Corning Toray)
  • the viscosity of each of the obtained compositions was measured at 25 ° C. using an E-type viscometer.
  • a composition having a viscosity of 30 to 80 mPa ⁇ s is preferable because of excellent coating properties, and a composition having a viscosity of 40 to 70 mPa ⁇ s is particularly preferable.
  • A Adhesive force of 0.6 N / 20 mm or more
  • B Adhesive force of 0.4 N / 20 mm or more, less than 0.6 N / 20 mm
  • C Adhesive force of less than 0.4 N / 20 mm
  • Adhesive strength The obtained evaluation sample was cut out to a width of 2.0 cm 12 hours after exposure under conditions of 30 ° C., 50% RH and atmospheric pressure to obtain a sample for evaluation of adhesive strength. The obtained sample was subjected to a 90 ° peel test under the above conditions to measure the adhesive strength, and evaluated according to the following criteria.
  • the adhesive force is 2.5 N / 20 mm or more
  • B The adhesive force is 1.5 N / 20 mm or more and less than 2.5 N / 20 mm
  • C The adhesive force is 1.0 N / 20 mm or more and less than 1.5 N / 20 mm
  • D The adhesive force is An adhesive having an adhesive strength of A or B of less than 1.0 N / 20 mm can be used as an adhesive, and an adhesive of A is particularly preferable. Adhesives having C and D are not preferable as an adhesive.
  • the water resistance was evaluated by the adhesive strength after warm water.
  • the obtained evaluation sample was immersed in warm water of 60 ° C. for 48 hours after exposure at 30 ° C., 50% RH and atmospheric pressure for 12 hours, taken out of the warm water and dried, and then reduced to 2.0 cm width. After cutting out, a sample for evaluation of adhesive strength after warm water was obtained. The obtained sample was subjected to a 90 ° peel test by the above-described method, and the adhesive strength after warm water was measured, and evaluated according to the following criteria.
  • Adhesion after warm water is 2.5 N / 20 mm or more
  • B Adhesion after warm water is 1.5 N / 20 mm or more and less than 2.5 N / 20 mm
  • C Adhesion after warm water is 1.0 N / 20 mm or more and 1.5 N / 20 mm
  • D Adhesive strength after warm water is less than 1.0 N / 20 mm.
  • Those having an adhesive strength after warm water of A, B or C can be used as an adhesive having excellent water resistance. Is preferred. Those having an adhesive strength after warm water of D are not preferred as adhesives for applications requiring water resistance.
  • compositions of Examples were excellent in coating properties, initial curing properties, adhesive strength and water resistance. Therefore, the composition of the present invention is useful as an adhesive.

Abstract

Provided is a composition excellent in terms of curing rate and water resistance and capable of giving cured objects having excellent adhesive strength. Also provided are an adhesive including the composition, a cured object obtained therefrom, and a production method therefor. The composition comprises a radical-polymerizable ingredient (A) and a cationically polymerizable ingredient (B). The radical-polymerizable ingredient (A) includes a radical-polymerizable compound (A1) having a bridged fused ring, in an amount of 70-100 parts by mass per 100 parts by mass of the radical-polymerizable ingredient (A). The cationically polymerizable ingredient (B) includes a cationically polymerizable compound (B1) having a bridged fused ring, in an amount of 10-50 parts by mass per 100 parts by mass of the cationically polymerizable ingredient (B).

Description

組成物、これを含有する接着剤、その硬化物およびその製造方法Composition, adhesive containing the same, cured product thereof, and method for producing the same
　本発明は、組成物、これを含有する接着剤、その硬化物およびその製造方法に関し、詳しくは、硬化速度および耐水性に優れ、かつ、接着力に優れた硬化物が得られる組成物、これを含有する接着剤、その硬化物およびその製造方法に関する。 The present invention relates to a composition, an adhesive containing the same, a cured product thereof, and a method for producing the same.Specifically, the composition is excellent in curing speed and water resistance, and a cured product excellent in adhesive strength is obtained. The present invention relates to an adhesive, a cured product thereof, and a method for producing the same.
　カチオン硬化性組成物は、インキ、塗料、各種コーティング剤、接着剤、光学部材等の分野において用いられている。このような、硬化性組成物の改良に関して、種々の報告がなされている。 Cation curable compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members and the like. Various reports have been made on the improvement of such a curable composition.
　例えば、特許文献１では、低粘度で、硬化性に優れ、各種プラスチックフィルムまたはシートへの接着力および無色透明性にも優れたプラスチックフィルム等用活性エネルギー線硬化型接着剤組成物が提案されている。また、特許文献２では、低粘度で、硬化性に優れ、塗工・硬化時の雰囲気湿度が高くとも各種プラスチックフィルム等への接着力に優れ、無色透明性にも優れたプラスチックフィルム等用活性エネルギー線硬化型接着剤組成物が提案されている。さらに、特許文献３では、塗工環境の湿度が高くても、硬化性に優れ、一定時間経過後の接着力、耐久性および耐湿熱試験終了後の接着力が良好であり、低粘度である光硬化性接着剤が提案されている。さらにまた、特許文献４では、ジシクロペンタジエン骨格を有するジアクリレートとジシクロペンタジエン骨格を有するジグリシジルエーテルを有する光および熱硬化性樹脂組成物を適用して、硬化性樹脂組成物層を形成する工程と、さらに硬化性樹脂組成物層に活性エネルギー線を照射する工程を有する積層体の製造方法が提案されている。 For example, Patent Literature 1 proposes an active energy ray-curable adhesive composition for a plastic film or the like, which has a low viscosity, is excellent in curability, and has excellent adhesive strength to various plastic films or sheets and excellent colorless transparency. I have. Patent Document 2 discloses an activity for a plastic film having low viscosity, excellent curability, excellent adhesion to various plastic films even when the atmospheric humidity during coating and curing is high, and excellent colorless transparency. Energy ray-curable adhesive compositions have been proposed. Furthermore, in Patent Document 3, even if the humidity of the coating environment is high, the curability is excellent, the adhesive strength after a certain period of time, the durability, the adhesive strength after the end of the moist heat resistance test, and the low viscosity. Photocurable adhesives have been proposed. Furthermore, in Patent Document 4, a curable resin composition layer is formed by applying a light and thermosetting resin composition having diacrylate having a dicyclopentadiene skeleton and diglycidyl ether having a dicyclopentadiene skeleton. There has been proposed a method for producing a laminate having a step and a step of irradiating the curable resin composition layer with an active energy ray.
特開２０１５－０３４１８８号公報JP-A-2015-034188 特開２０１５－０５７４６７号公報JP-A-2005-057467 特開２０１５－１４３３５２号公報JP-A-2015-143352 特開２０１７－１４９１３５号公報JP-A-2017-149135
　しかしながら、特許文献１～４で提案されているカチオン硬化性組成物では、十分な硬化性が得られず、得られる硬化物の耐水性が十分ではないという問題がある。例えば、接着剤として用いた場合に、硬化速度が不十分な場合や、十分な接着力および耐水性が得られない場合がある。 However, the cationically curable compositions proposed in Patent Literatures 1 to 4 have a problem in that sufficient curability cannot be obtained, and the obtained cured product has insufficient water resistance. For example, when used as an adhesive, the curing speed may be insufficient or sufficient adhesive strength and water resistance may not be obtained.
　そこで、本発明は、上記問題点に鑑みてなされたものであり、本発明の目的は、硬化速度および耐水性に優れ、かつ、接着力に優れた硬化物が得られる組成物、これを含有する接着剤、その硬化物およびその製造方法を提供することにある。 Therefore, the present invention has been made in view of the above problems, and an object of the present invention is to provide a composition that is excellent in curing speed and water resistance, and that can obtain a cured product having excellent adhesive strength, To provide an adhesive, a cured product thereof, and a production method thereof.
　本発明者等は、上記課題を解消するために鋭意検討した結果、上記の目的を達成したものである。以下に、本発明について、詳細に説明する。 The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have achieved the above object. Hereinafter, the present invention will be described in detail.
　すなわち、本発明の組成物は、ラジカル重合性成分（Ａ）およびカチオン重合性成分（Ｂ）を含有する組成物において、　前記ラジカル重合性成分（Ａ）が、架橋縮合環を有するラジカル重合性化合物（Ａ１）をラジカル重合性成分（Ａ）１００質量部中に７０～１００質量部含有し、
　前記カチオン重合性成分（Ｂ）が、架橋縮合環を有するカチオン重合性化合物（Ｂ１）をカチオン重合性成分（Ｂ）１００質量部中に１０～５０質量部含有することを特徴とするものである。 That is, the composition of the present invention is a composition containing a radically polymerizable component (A) and a cationically polymerizable component (B), wherein the radically polymerizable component (A) is a radically polymerizable compound having a crosslinked condensed ring. 70 to 100 parts by mass of (A1) per 100 parts by mass of the radically polymerizable component (A),
The cationically polymerizable component (B) contains 10 to 50 parts by mass of a cationically polymerizable compound (B1) having a crosslinked condensed ring per 100 parts by mass of the cationically polymerizable component (B). .
　本発明の組成物においては、さらに、ラジカル重合性開始剤（Ｃ）およびカチオン重合性開始剤（Ｄ）を含有し、
　前記ラジカル重合性成分（Ａ）、前記カチオン重合性成分（Ｂ）、前記ラジカル重合性開始剤（Ｃ）および前記カチオン重合性開始剤（Ｄ）の総量１００質量部中に、前記ラジカル重合性成分（Ａ）４０～６０質量部、前記カチオン重合性成分（Ｂ）３０～５０質量部、前記ラジカル重合性開始剤（Ｃ）１～１０質量部および前記カチオン重合性開始剤（Ｄ）１～１０質量部を含有することが好ましい。かかる組成物は、初期硬化性に優れている。 The composition of the present invention further contains a radically polymerizable initiator (C) and a cationically polymerizable initiator (D),
The radical polymerizable component (A), the cationic polymerizable component (B), the radical polymerizable initiator (C) and the cationic polymerizable initiator (D) in a total amount of 100 parts by mass contain the radical polymerizable component. (A) 40 to 60 parts by mass, the cationically polymerizable component (B) 30 to 50 parts by mass, the radically polymerizable initiator (C) 1 to 10 parts by mass, and the cationically polymerizable initiator (D) 1 to 10 It is preferable to contain parts by mass. Such a composition has excellent initial curability.
　また、本発明の組成物においては、前記ラジカル重合性化合物（Ａ１）および前記カチオン重合性化合物（Ｂ１）に含まれる架橋縮合環が、下記式（Ｉ）で表される構造を有する架橋縮合環であることが好ましい。かかる組成物は、得られる硬化物が耐水性に優れている。　
Figure JPOXMLDOC01-appb-I000002
In the composition of the present invention, the crosslinked condensed ring contained in the radically polymerizable compound (A1) and the cationically polymerizable compound (B1) has a structure represented by the following formula (I). It is preferred that In such a composition, the obtained cured product has excellent water resistance.
Figure JPOXMLDOC01-appb-I000002
　さらに、本発明の組成物においては、前記カチオン重合性成分（Ｂ）として、架橋縮合環を有さない重量平均分子量１，０００以上３０，０００未満のカチオン重合性化合物（Ｂ２）を含有することが好ましい。かかる組成物からは、耐水性に優れる硬化物が得られる。 Further, the composition of the present invention contains, as the cationic polymerizable component (B), a cationic polymerizable compound (B2) having no crosslinked condensed ring and having a weight average molecular weight of 1,000 or more and less than 30,000. Is preferred. From such a composition, a cured product having excellent water resistance can be obtained.
　さらにまた、本発明の組成物においては、前記カチオン重合性成分（Ｂ）として、架橋縮合環を有さない重量平均分子量２００以上１，０００未満のカチオン重合性化合物（Ｂ３）を含有することが好ましい。かかる組成物からは、塗工性および耐水性に優れる硬化物が得られる。 Furthermore, in the composition of the present invention, the cationically polymerizable component (B) may contain a cationically polymerizable compound (B3) having a weight average molecular weight of not less than 200 and less than 1,000 having no crosslinked condensed ring. preferable. From such a composition, a cured product having excellent coatability and water resistance can be obtained.
　また、本発明の組成物においては、前記カチオン重合性化合物（Ｂ３）が、オキセタニル基を有する化合物を含むことが好ましい。かかる組成物からは、耐水性に優れる硬化物が得られる。 In the composition of the present invention, the cationically polymerizable compound (B3) preferably contains a compound having an oxetanyl group. From such a composition, a cured product having excellent water resistance can be obtained.
　さらに、本発明の組成物においては、前記ラジカル重合性成分（Ａ）として、カチオン重合性基を有し、イソシアヌレート環および架橋縮合環を有さないラジカル重合性化合物（Ａ２）を含有することが好ましい。かかる組成物は、塗工性および初期接着性に優れている。 Further, the composition of the present invention contains, as the radically polymerizable component (A), a radically polymerizable compound (A2) having a cationically polymerizable group and not having an isocyanurate ring or a crosslinked condensed ring. Is preferred. Such a composition is excellent in coatability and initial adhesiveness.
　さらにまた、本発明の組成物においては、前記ラジカル重合性成分（Ａ）として、イソシアヌレート環を含有し、架橋縮合環を有さないラジカル重合性化合物（Ａ３）を含有することが好ましい。かかる組成物からは、耐水性に優れる硬化物が得られる。 Furthermore, in the composition of the present invention, it is preferable that the radical polymerizable component (A) contains a radical polymerizable compound (A3) containing an isocyanurate ring and having no cross-linked condensed ring. From such a composition, a cured product having excellent water resistance can be obtained.
　本発明の接着剤は、本発明の組成物を含むことを特徴とするものである。本発明の組成物を含有することで、硬化速度に優れ、かつ、接着力および耐水性に優れた硬化物が得られる接着剤となる。 接着 The adhesive of the present invention is characterized by containing the composition of the present invention. By containing the composition of the present invention, an adhesive can be obtained which is excellent in curing speed and can obtain a cured product excellent in adhesive strength and water resistance.
　本発明の硬化物は、本発明の組成物の硬化物であることを特徴とするものである。本発明の組成物を用いることで接着力および耐水性に優れた硬化物となる。 硬化 The cured product of the present invention is a cured product of the composition of the present invention. By using the composition of the present invention, a cured product having excellent adhesive strength and water resistance is obtained.
　本発明の硬化物の製造方法は、本発明の組成物に対して、活性エネルギー線を照射または加熱する工程を含むことを特徴とするものである。本発明の組成物は、上記成分を含むものであるため、接着力および耐水性に優れた硬化物を容易に得ることができる。 方法 The method for producing a cured product of the present invention includes a step of irradiating or heating an active energy ray to the composition of the present invention. Since the composition of the present invention contains the above components, a cured product excellent in adhesive strength and water resistance can be easily obtained.
　本発明によれば、硬化速度および耐水性に優れ、かつ、接着力に優れた硬化物が得られる組成物、これを含有する接着剤、その硬化物およびその製造方法を提供することができる。 According to the present invention, it is possible to provide a composition capable of obtaining a cured product having excellent curing speed and water resistance and excellent adhesive strength, an adhesive containing the composition, a cured product thereof, and a method for producing the same.
　以下、本発明の組成物、これを含有する接着剤、その硬化物およびその製造方法について、詳細に説明する。 Hereinafter, the composition of the present invention, an adhesive containing the same, a cured product thereof, and a method for producing the same will be described in detail.
＜組成物＞
　まず、本発明の組成物について説明する。本発明の組成物は、ラジカル重合性成分（Ａ）（以下、「成分（Ａ）」とも称す）およびカチオン重合性成分（Ｂ）（以下、「成分（Ｂ）」とも称す）を含有する組成物である。本発明の組成物においては、架橋縮合環を有するラジカル重合性化合物（Ａ１）（以下、「化合物（Ａ１）」とも称す」を、成分（Ａ）１００質量部中に７０～１００質量部含有し、架橋縮合環を有するカチオン重合性化合物（Ｂ１）（以下、「化合物（Ｂ１）」とも称す）を、成分（Ｂ）１００質量部中に１０～５０部含有する。すなわち、化合物（Ａ１）と化合物（Ｂ１）を上記の通り適切な割合で含有することにより、硬化速度に優れ、かつ、接着力および耐水性に優れた硬化物が得られる。 <Composition>
First, the composition of the present invention will be described. The composition of the present invention comprises a radical polymerizable component (A) (hereinafter, also referred to as “component (A)”) and a cationically polymerizable component (B) (hereinafter, also referred to as “component (B)”). Things. In the composition of the present invention, 70 to 100 parts by mass of the radically polymerizable compound (A1) having a crosslinked condensed ring (hereinafter, also referred to as “compound (A1)”) is contained in 100 parts by mass of the component (A). And 10 to 50 parts of a cationically polymerizable compound (B1) having a crosslinked condensed ring (hereinafter, also referred to as “compound (B1)”) per 100 parts by mass of component (B). By containing the compound (B1) in an appropriate ratio as described above, a cured product having an excellent curing speed and excellent adhesive strength and water resistance can be obtained.
　本発明の組成物においては、化合物（Ａ１）、化合物（Ｂ１）に加えてラジカル重合性開始剤（Ｃ）（以下、「成分（Ｃ）」とも称す）およびカチオン重合性開始剤（Ｄ）（以下、「成分（Ｄ）」とも称す）を含有すると、硬化性が高い組成物が得られることから好ましい。本発明の組成物中の成分（Ａ）、成分（Ｂ）、成分（Ｃ）および成分（Ｄ）の好ましい割合は、成分（Ａ）、成分（Ｂ）、成分（Ｃ）および成分（Ｄ）の総量１００質量部中に、それぞれ成分（Ａ）４０～６０質量部、成分（Ｂ）３０～５０質量部、成分（Ｃ）１～１０質量部および成分（Ｄ）１～１０質量部である。かかる割合とすることで、硬化速度に優れ、かつ、接着力および耐水性に優れた硬化物が得られる組成物を得ることできる。 In the composition of the present invention, in addition to the compound (A1) and the compound (B1), a radically polymerizable initiator (C) (hereinafter, also referred to as “component (C)”) and a cationically polymerizable initiator (D) ( Hereinafter, it is also preferable to include "component (D)") since a composition having high curability can be obtained. Preferred proportions of component (A), component (B), component (C) and component (D) in the composition of the present invention are component (A), component (B), component (C) and component (D). Is 40 to 60 parts by mass of the component (A), 30 to 50 parts by mass of the component (B), 1 to 10 parts by mass of the component (C), and 1 to 10 parts by mass of the component (D) in the total amount of 100 parts by mass. . With such a ratio, it is possible to obtain a composition that is excellent in curing speed and that can obtain a cured product excellent in adhesive strength and water resistance.
　また、本発明の組成物において、成分（Ａ）と成分（Ｂ）の割合としては、成分（Ａ）１００質量部に対して成分（Ｂ）が５０～１３０質量部の場合が好ましい。成分（Ａ）と成分（Ｂ）の割合が上記の範囲である場合、接着力と耐水性に優れた硬化物が得られることから好ましい。以下、各成分について、詳細に説明する。 In the composition of the present invention, the ratio of the component (A) to the component (B) is preferably 50 to 130 parts by mass with respect to 100 parts by mass of the component (A). When the ratio of the component (A) to the component (B) is within the above range, a cured product having excellent adhesive strength and water resistance is preferably obtained. Hereinafter, each component will be described in detail.
＜ラジカル重合性成分（Ａ）＞
　成分（Ａ）は、ラジカル重合性基を有する化合物である。このラジカル重合性基とは、ラジカルの存在下で重合が可能な基を意味し、例えば、アクリル基、メタクリル基、ビニル基およびチオール基等が挙げられる。成分（Ａ）は、化合物（Ａ１）、カチオン重合性基を有し、イソシアヌレート環および架橋縮合環を有さないラジカル重合性化合物（Ａ２）（以下、「化合物（Ａ２）」とも称す）、イソシアヌレート環を有し、架橋縮合環を有さないラジカル重合性化合物（Ａ３）（以下、「化合物（Ａ３）」とも称す）および化合物（Ａ１）～化合物（Ａ３）に属さないその他のラジカル重合性化合物から構成される。なお、単独または２種以上の、これらの化合物を混合して使用することができる。 <Radical polymerizable component (A)>
Component (A) is a compound having a radical polymerizable group. The radical polymerizable group means a group that can be polymerized in the presence of a radical, and includes, for example, an acryl group, a methacryl group, a vinyl group, and a thiol group. Component (A) is compound (A1), a radically polymerizable compound (A2) having a cationically polymerizable group and not having an isocyanurate ring or a cross-linked condensed ring (hereinafter, also referred to as “compound (A2)”), Radical polymerizable compound (A3) having an isocyanurate ring and no cross-linked condensed ring (hereinafter also referred to as “compound (A3)”) and other radical polymerization not belonging to compounds (A1) to (A3) It is composed of a sex compound. In addition, these compounds can be used alone or in combination of two or more.
　成分（Ａ）は、本発明の組成物の塗工容易性、硬化速度等の観点からは、低分子量化合物を含むことが好ましい。また、低分子量化合物は、組成物中への分散性または溶解性等に優れるため、透明性に優れた硬化物を得ることができるからである。一方、ラジカル重合性化合物は、本発明の組成物の接着力等の観点からは、高分子量化合物を含むことが好ましい。組成物の塗工容易性、硬化速度、接着力のバランスの観点から、ラジカル重合性化合物は、低分子量化合物および高分子量化合物の両者を含むことが好ましい。さらに、高分子量化合物は、低分子量化合物と共に用いられることで、本発明の組成物中への分散または溶解性を向上でき、透明性に優れた硬化物を得ることができる。 The component (A) preferably contains a low molecular weight compound from the viewpoint of ease of application and curing speed of the composition of the present invention. Further, the low molecular weight compound is excellent in dispersibility or solubility in the composition and the like, so that a cured product excellent in transparency can be obtained. On the other hand, the radical polymerizable compound preferably contains a high molecular weight compound from the viewpoint of the adhesive strength of the composition of the present invention. It is preferable that the radically polymerizable compound contains both a low molecular weight compound and a high molecular weight compound from the viewpoint of the balance between the ease of application of the composition, the curing speed, and the adhesive strength. Further, when the high molecular weight compound is used together with the low molecular weight compound, the dispersion or solubility in the composition of the present invention can be improved, and a cured product having excellent transparency can be obtained.
　低分子量化合物の分子量としては、所望の塗工性等が得られるものであればよく、例えば、１，０００以下とすることができ、５０以上５００以下であることが好ましく、なかでも５０以上３００以下であることが好ましい。高分子量化合物の分子量は、所望の接着容易性等が得られるものであればよく、例えば、１，０００より大きいものとすることができ、１，０００以上５０，０００以下であることが好ましく、なかでも、５，０００以上２０，０００以下であることが好ましい。なお、以下、分子量は、化合物が重合体である場合には、重量平均分子量（Ｍｗ）を示すものである。 The molecular weight of the low molecular weight compound is not particularly limited as long as desired coatability and the like can be obtained. For example, the molecular weight can be 1,000 or less, preferably 50 to 500, and more preferably 50 to 300. The following is preferred. The molecular weight of the high molecular weight compound is not particularly limited as long as desired adhesion easiness and the like can be obtained. For example, the molecular weight can be larger than 1,000, and is preferably 1,000 or more and 50,000 or less, Especially, it is preferable that it is 5,000 or more and 20,000 or less. Hereinafter, the molecular weight indicates the weight average molecular weight (Mw) when the compound is a polymer.
　ここで、重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）により、標準ポリスチレン換算値として求めることができる。重量平均分子量Ｍｗは、例えば、日本分光（株）製のＧＰＣ（ＬＣ－２０００ｐｌｕｓシリーズ）を用い、溶出溶剤をテトラヒドロフランとし、校正曲線用ポリスチレンスタンダードをＭｗ１，１１０，０００、７０７，０００、３９７，０００、１８９，０００、９８，９００、３７，２００、１３，７００、９，４９０、５，４３０、３，１２０、１，０１０、５８９（東ソー（株）社製　ＴＳＫｇｅｌ標準ポリスチレン）とし、測定カラムをＫＦ－８０４、ＫＦ－８０３、ＫＦ－８０２（昭和電工（株）製）として測定して得ることができる。また、測定温度は４０℃とすることができ、流速は１．０ｍＬ／分とすることができる。 Here, the weight average molecular weight can be determined as a standard polystyrene conversion value by gel permeation chromatography (GPC). The weight average molecular weight Mw is determined, for example, by using GPC (LC-2000plus series) manufactured by JASCO Corporation, eluting solvent as tetrahydrofuran, and polystyrene standard for calibration curve as Mw 1,110,000, 707,000, 397,000. , 189,000, 98,900, 37,200, 13,700, 9,490, 5,430, 3,120, 1,010,589 (Tosoh Corp. TSKgel standard polystyrene), and the measurement column was used. It can be obtained by measuring as KF-804, KF-803, and KF-802 (manufactured by Showa Denko KK). Also, the measurement temperature can be 40 ° C., and the flow rate can be 1.0 mL / min.
　本発明の組成物に含有される成分（Ａ）の含有量は、組成物１００質量部に対して耐水性に優れることから、４０～６０質量部が好ましく、特に好ましくは、４５～５５質量部である。 The content of the component (A) contained in the composition of the present invention is preferably from 40 to 60 parts by mass, and particularly preferably from 45 to 55 parts by mass, since water resistance is excellent with respect to 100 parts by mass of the composition. It is.
＜化合物（Ａ１）＞
　化合物（Ａ１）は、架橋縮合環を有するラジカル重合性化合物である。化合物（Ａ１）が有する架橋縮合環とは、３個以上の炭素原子を共有する縮合環を意味し、一般式（Ｉ）で表される構造を有する架橋縮合環が含まれていることが好ましい。 <Compound (A1)>
Compound (A1) is a radically polymerizable compound having a crosslinked condensed ring. The bridged condensed ring of the compound (A1) means a condensed ring having three or more carbon atoms, and preferably contains a crosslinked condensed ring having a structure represented by the general formula (I). .
Figure JPOXMLDOC01-appb-I000003
Figure JPOXMLDOC01-appb-I000003
　このような構造の架橋縮合環としては、例えば下記に示す架橋縮合環が挙げられる。  架橋 Examples of the crosslinked condensed ring having such a structure include the following crosslinked condensed rings.
Figure JPOXMLDOC01-appb-I000004
Figure JPOXMLDOC01-appb-I000004
　例示した架橋縮合環の中でも、架橋縮合環Ｎｏ．６、Ｎｏ．７およびＮｏ．８を有する化合物（Ａ１）を含有する接着剤は、高い接着力および耐水性を有することから、好ましい。架橋縮合環Ｎｏ．６は、構造が安定で生産性が高いことから特に好ましい。 中 で も Among the exemplified crosslinked condensed rings, crosslinked condensed ring No. 6, no. 7 and No. 7 An adhesive containing the compound (A1) having 8 is preferable because it has high adhesive strength and water resistance. Bridged condensed ring No. 6 is particularly preferable because of its stable structure and high productivity.
　ラジカル重合性基の数が、１～４個の化合物（Ａ１）は、接着力と塗工性のバランスが良いことから好ましく、ラジカル重合性基の数が、１～３個の化合物（Ａ１）は、特に好ましい。 The compound (A1) having 1 to 4 radically polymerizable groups is preferable because it has a good balance between adhesion and coatability, and the compound (A1) having 1 to 3 radically polymerizable groups is preferred. Is particularly preferred.
　化合物（Ａ１）としては、例えば、トリシクロデカンジメタノールジ（メタ）アクリレート、ジシクロペンタニルオキシエチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレ－ト、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、ジメチロールジシクロペンタンジ（メタ）アクリレート、ジメチロール－トリシクロデカンジ（メタ）アクリレート、アダマンタン（メタ）アクリレート、２－イソプロピル－２－アダマンチル（メタ）アクリレート等が挙げられる。 Examples of the compound (A1) include tricyclodecane dimethanol di (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dimethylol dicyclopentanedi (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, adamantane (meth) acrylate, 2-isopropyl-2-adamantyl (meth) acrylate and the like.
　化合物（Ａ１）としては、市販品を用いることもできる。市販品としては、例えば、カヤラッドＲ－６８４（以上、日本化薬製）；Ａ－ＤＣＰおよびＤＣＰ（以上、新中村化学工業製）；ＦＡ－５１１ＡＳ、ＦＡ－５１２ＡＳ、ＦＡ－５１３ＡＳ、ＦＡ－５１２Ｍ、ＦＡ－５１２ＭＴ、ＦＡ－５１３Ｍ（以上、日立化成製）が挙げられる。 市 販 As the compound (A1), a commercially available product can also be used. Commercial products include, for example, Kayarad R-684 (all manufactured by Nippon Kayaku); A-DCP and DCP (all manufactured by Shin-Nakamura Chemical); FA-511AS, FA-512AS, FA-513AS, FA-512M. , FA-512MT and FA-513M (all manufactured by Hitachi Chemical).
＜化合物（Ａ２）＞
　化合物（Ａ２）としては、カチオン重合性基を有し、イソシアヌレート環および架橋縮合環を有さないラジカル重合性化合物であればよく、特に制限されない。 <Compound (A2)>
The compound (A2) is not particularly limited as long as it is a radical polymerizable compound having a cationic polymerizable group and not having an isocyanurate ring or a cross-linked condensed ring.
　カチオン重合性基とは、酸の存在下で重合が可能な基を意味し、例えば、水酸基、エポキシ基、脂環式エポキシ基、オキセタニル基およびビニルエーテル基等が挙げられる。化合物（Ａ２）の有するカチオン重合性基としては、基材密着性の観点からは水酸基が好ましい。初期硬化性および接着力の観点からは、エポキシ基が好ましい。 The cationically polymerizable group means a group that can be polymerized in the presence of an acid, and includes, for example, a hydroxyl group, an epoxy group, an alicyclic epoxy group, an oxetanyl group, and a vinyl ether group. As the cationically polymerizable group of the compound (A2), a hydroxyl group is preferable from the viewpoint of substrate adhesion. Epoxy groups are preferred from the viewpoints of initial curability and adhesive strength.
　化合物（Ａ２）としては、例えば、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシ－３－アクリロイロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート等の水酸基含有アクリル酸エステル；Ｎ－２－ヒドロキシエチル（メタ）アクリルアミド、Ｎ－ビニルホルムアミド等の水酸基含有アクリルアミド；ビニルフェノール、アリルアルコール、クロチルアルコール等のビニルアルコール；、水酸基含有ビニルモノマー、エポキシ化合物に（メタ）アクリル酸を反応させた、エチレングリコールジグリシジルエーテルのエポキシ（メタ）アクリレート、ジエチレングリコールジグリシジルエーテルのモノ（メタ）アクリレート、トリエチレングリコールジグリシジルエーテルのモノ（メタ）アクリレート、ポリエチレングリコールジグリシジルエーテルのモノ（メタ）アクリレート、プロピレングリコールジグリシジルエーテルのモノ（メタ）アクリレート、トリプロピレングリコールジグリシジルエーテルのモノ（メタ）アクリレート、ポリプロピレングリコールジグリシジルエーテルのモノ（メタ）アクリレート、ネオペンチルグリコールジグリシジルエーテルのモノ（メタ）アクリレート等のエポキシ（メタ）アクリレート；、（メタ）アクリル酸グリシジル、および下記化合物（Ａ２）Ｎｏ．１～Ｎｏ．４、（３－エチルオキセタン－３－イル）メチルアクリレート等が挙げられる。 Examples of the compound (A2) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxy Hydroxyl-containing acrylates such as propyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dipentaerythritol penta (meth) acrylate and pentaerythritol tri (meth) acrylate; N-2-hydroxyethyl (meth) acrylamide; Hydroxy group-containing acrylamides such as N-vinylformamide; vinyl alcohols such as vinyl phenol, allyl alcohol and crotyl alcohol; Epoxy (meth) acrylate of ethylene glycol diglycidyl ether, mono (meth) acrylate of diethylene glycol diglycidyl ether, mono (meth) acrylate of triethylene glycol diglycidyl ether, mono (polyethylene glycol diglycidyl ether) (Meth) acrylate, mono (meth) acrylate of propylene glycol diglycidyl ether, mono (meth) acrylate of tripropylene glycol diglycidyl ether, mono (meth) acrylate of polypropylene glycol diglycidyl ether, mono (neopentyl glycol diglycidyl ether) Epoxy (meth) acrylates such as (meth) acrylate; glycidyl (meth) acrylate, and the following compound (A2 No. 1 to No. 4, (3-ethyloxetane-3-yl) methyl acrylate, and the like.
Figure JPOXMLDOC01-appb-I000005
Figure JPOXMLDOC01-appb-I000005
Figure JPOXMLDOC01-appb-I000006
Figure JPOXMLDOC01-appb-I000006
Figure JPOXMLDOC01-appb-I000007
Figure JPOXMLDOC01-appb-I000007
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000008
　化合物（Ａ２）のラジカル重合性基としては、硬化性が優れるとの観点から、ラジカル重合性基としては、アクリル基が好ましい。また、粘度が低く塗工性に優れるとの観点から、ラジカル重合性基を１つまたは２つ有することが好ましい。 ア ク リ ル From the viewpoint of excellent curability, the radical polymerizable group of the compound (A2) is preferably an acrylic group. Further, from the viewpoint of low viscosity and excellent coatability, it is preferable to have one or two radically polymerizable groups.
　ラジカル重合性化合物（Ａ２）がラジカル重合性成分（Ａ）に含有される場合、ラジカル重合性化合物（Ａ２）の好ましい含有量は、接着性、耐水性および流動性に優れることから、ラジカル重合性成分（Ａ）１００質量部中に０～２０質量部が好ましく、特に好ましくは、５～１０質量部である。 When the radically polymerizable compound (A2) is contained in the radically polymerizable component (A), the preferable content of the radically polymerizable compound (A2) is excellent in adhesiveness, water resistance and fluidity. The amount is preferably from 0 to 20 parts by mass, particularly preferably from 5 to 10 parts by mass, per 100 parts by mass of the component (A).
＜化合物（Ａ３）＞
　化合物（Ａ３）としては、イソシアヌレート環を含有し、架橋縮合環を有さないラジカル重合性化合物であればよく、特に制限されない。 <Compound (A3)>
The compound (A3) is not particularly limited as long as it is a radical polymerizable compound containing an isocyanurate ring and not having a crosslinked condensed ring.
　化合物（Ａ３）としては、例えば、ε－カプロラクトン変性トリス［２－（メタ）アクリロキシエチル］イソシアヌレート、トリ［（メタ）アクリロイルエチル］イソシアヌレート、トリス［３－（メタ）アクリロキシプロピル］イソシアヌレート等のトリス［（メタ）アクリロキシアルキル］イソシアヌレート、およびジ［（メタ）アクリロイルエチル］－２－ヒドロキシエチルイソシアヌレート、モノアリルイソシアヌレート、ジアリルイソシアヌレート、トリアリルイソシアヌレートおよび下記化合物（Ａ３）Ｎｏ．１等が挙げられる。 Examples of the compound (A3) include ε-caprolactone-modified tris [2- (meth) acryloxyethyl] isocyanurate, tri [(meth) acryloylethyl] isocyanurate, and tris [3- (meth) acryloxypropyl] isocyanate Tris [(meth) acryloxyalkyl] isocyanurate and di [(meth) acryloylethyl] -2-hydroxyethyl isocyanurate, monoallyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate and the following compound (A3 ) No. 1 and the like.
Figure JPOXMLDOC01-appb-I000009
Figure JPOXMLDOC01-appb-I000009
　化合物（Ａ３）としては、市販品を用いることもできる。市販品としては、例えば、アロニックスＭ－２１５、Ｍ－３１５（以上、東亞合成）；ＮＫエステルＡ－９３００、Ａ－９３００－１ＣＬ、Ａ－９３００－３ＣＬ（以上、新中村化学工業製）；タイク（三菱ケミカル製）等が挙げられる。 市 販 As the compound (A3), a commercially available product can also be used. Commercially available products include, for example, Aronix M-215, M-315 (above, Toagosei); NK esters A-9300, A-9300-1CL, A-9300-3CL (above, manufactured by Shin-Nakamura Chemical Co., Ltd.); (Mitsubishi Chemical).
　化合物（Ａ３）のラジカル重合性基としては、硬化性が優れるとの観点から、アクリル基が好ましい。また、硬化性が優れるとの観点から、複数のラジカル重合性基を有することが好ましく、特に２～３個が好ましい。 ア ク リ ル As the radical polymerizable group of the compound (A3), an acryl group is preferable from the viewpoint of excellent curability. Further, from the viewpoint of excellent curability, it preferably has a plurality of radically polymerizable groups, and particularly preferably has two or three radically polymerizable groups.
　ラジカル重合性化合物（Ａ３）がラジカル重合性成分（Ａ）に含有される場合、ラジカル重合性化合物（Ａ３）の好ましい含有量は、耐水性および流動性に優れることからラジカル重合性成分（Ａ）１００質量部中に０～２０質量部が好ましく、特に好ましくは、５～１０質量部である。 When the radically polymerizable compound (A3) is contained in the radically polymerizable component (A), the preferable content of the radically polymerizable compound (A3) is such that the radically polymerizable component (A) is excellent in water resistance and fluidity. The amount is preferably from 0 to 20 parts by mass, particularly preferably from 5 to 10 parts by mass, per 100 parts by mass.
＜その他のラジカル重合性化合物＞
　その他のラジカル重合性化合物としては、例えば、エチレン、プロピレン、ブチレン、イソブチレン、塩化ビニル、塩化ビニリデン、フッ化ビニリデン、テトラフルオロエチレン等の不飽和脂肪族炭化水素；（メタ）アクリル酸、α－クロルアクリル酸、イタコン酸、マレイン酸、シトラコン酸、フマル酸、ハイミック酸、クロトン酸、イソクロトン酸、ビニル酢酸、アリル酢酸、桂皮酸、ソルビン酸、メサコン酸、コハク酸モノ［２－（メタ）アクリロイロキシエチル］、フタル酸モノ［２－（メタ）アクリロイロキシエチル］、ω－カルボキシポリカプロラクトンモノ（メタ）アクリレート等の両末端にカルボキシ基と水酸基とを有するポリマーのモノ（メタ）アクリレート；１個のカルボキシル基と２個以上の（メタ）アクリロイル基とを有する多官能（メタ）アクリレート等の不飽和多塩基酸；（メタ）（メタ）アクリル酸メチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸－ｔ－ブチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸ジメチルアミノメチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸アミノプロピル、（メタ）アクリル酸ジメチルアミノプロピル、（メタ）アクリル酸エトキシエチル、（メタ）アクリル酸ポリ（エトキシ）エチル、（メタ）アクリル酸ブトキシエトキシエチル、（メタ）アクリル酸エチルヘキシル、（メタ）アクリル酸フェノキシエチル、（メタ）アクリル酸テトラヒドロフリル、（メタ）アクリル酸ビニル、（メタ）アクリル酸アリル、（メタ）アクリル酸ベンジル、１，１０－デカンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ポリエステル（メタ）アクリレートオリゴマー等の不飽和一塩基酸および多価アルコールまたは多価フェノールのエステル；（メタ）アクリル酸亜鉛、（メタ）アクリル酸マグネシウム等の不飽和多塩基酸の金属塩；マレイン酸無水物、イタコン酸無水物、シトラコン酸無水物、メチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、トリアルキルテトラヒドロ無水フタル酸、５－（２，５－ジオキソテトラヒドロフリル）－３－メチル－３－シクロヘキセン－１，２－ジカルボン酸無水物、トリアルキルテトラヒドロ無水フタル酸－無水マレイン酸付加物、ドデセニル無水コハク酸、無水メチルハイミック酸等の不飽和多塩基酸の酸無水物；（メタ）アクリルアミド、メチレンビス－（メタ）アクリルアミド、ジエチレントリアミントリス（メタ）アクリルアミド、キシリレンビス（メタ）アクリルアミド、α－クロロアクリルアミド等の不飽和一塩基酸および多価アミンのアミド；アクロレイン等の不飽和アルデヒド；（メタ）アクリロニトリル、α－クロロアクリロニトリル、シアン化ビニリデン、シアン化アリル等の不飽和ニトリル；スチレン、４－メチルスチレン、４－エチルスチレン、４－メトキシスチレン、４－ヒドロキシスチレン、４－クロロスチレン、ジビニルベンゼン、ビニルトルエン、ビニル安息香酸、ビニルスルホン酸、４－ビニルベンゼンスルホン酸、ビニルベンジルメチルエーテル、ビニルベンジルグリシジルエーテル等の不飽和芳香族化合物；メチルビニルケトン等の不飽和ケトン；ビニルアミン、アリルアミン、Ｎ－ビニルピロリドン、ビニルピペリジン等の不飽和アミン化合物；ビニルメチルエーテル、ビニルエチルエーテル、ｎ－ブチルビニルエーテル、イソブチルビニルエーテル、アリルグリシジルエーテル等のビニルエーテル；マレイミド、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド等の不飽和イミド類；インデン、１－メチルインデン等のインデン類；１，３－ブタジエン、イソプレン、クロロプレン等の脂肪族共役ジエン類；ポリスチレン、ポリメチル（メタ）アクリレート、ポリ－ｎ－ブチル（メタ）アクリレート、ポリシロキサン等の重合体分子鎖の末端にモノ（メタ）アクリロイル基を有するマクロモノマー類；ビニルクロリド、ビニリデンクロリド、ジビニルスクシナート、ジアリルフタラート、トリアリルホスファート、トリアリルイソシアヌラート、ビニルチオエーテル、ビニルイミダゾール、ビニルオキサゾリン、ビニルカルバゾール、ビニルピロリドンおよびビニルピリジンおよびポリイソシアネート化合物のビニルウレタン化合物等が挙げられる。 <Other radically polymerizable compounds>
Other radically polymerizable compounds include, for example, unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid, α-chloro Acrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, mono [2- (meth) acryloyl succinate Roxyethyl], mono [2- (meth) acryloyloxyethyl phthalate], ω-carboxypolycaprolactone mono (meth) acrylate, etc., a polymer mono (meth) acrylate having a carboxy group and a hydroxyl group at both terminals; 1 Carboxyl groups and two or more (meth) acryloyl groups Unsaturated polybasic acids such as polyfunctional (meth) acrylates having: (meth) methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, Cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxy (meth) acrylate Ethyl, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, (meth) acrylic acid Poly (ethoxy) ethyl, butoxyethoxy (meth) acrylate Ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, 1,10-decane Diol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4 -Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri (meth) acrylate, trimethylolpropanetri (meth) acrylate, dipentaerythri Esters of unsaturated monobasic acids and polyhydric alcohols or phenols, such as allyl hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate and polyester (meth) acrylate oligomers; zinc (meth) acrylate, (meth) acrylic acid Metal salts of unsaturated polybasic acids such as magnesium; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2, 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methylhymic anhydride, etc. Acid anhydrides of unsaturated polybasic acids; Amides of unsaturated monobasic acids and polyamines such as (meth) acrylamide, methylenebis- (meth) acrylamide, diethylenetriaminetris (meth) acrylamide, xylylenebis (meth) acrylamide and α-chloroacrylamide; unsaturated aldehydes such as acrolein; Unsaturated nitriles such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, Unsaturated aromatic compounds such as divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, vinylbenzyl glycidyl ether; Unsaturated ketones such as nyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidine; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; Unsaturated imides such as N-phenylmaleimide and N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl (meth) Macromonomers having a mono (meth) acryloyl group at the terminal of a polymer molecular chain, such as acrylate, poly-n-butyl (meth) acrylate, and polysiloxane; vinyl chloride, vinylidene chloride, Succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinylimidazole, vinyloxazoline, vinylcarbazole, vinyl urethane compounds such as vinyl pyrrolidone and vinyl pyridine and polyisocyanate compounds.
　その他のラジカル重合性化合物としては、市販品を用いることもできる。市販品としては、例えば、カヤラッドＤＰＨＡ、ＤＰＥＡ－１２、ＰＥＧ４００ＤＡ、ＴＨＥ－３３０、ＲＰ－１０４０、ＮＰＧＤＡ、ＰＥＴ３０（以上、日本化薬製）；ＮＫエステルＡ－ＤＯＤ－Ｎ、Ａ－ＤＰＨ、Ａ－ＴＭＰＴ、Ａ－ＨＤ－Ｎ、ＴＭＰＴ、ＮＰＧおよびＨＤ－Ｎ（以上、新中村化学工業製）；ＳＰＣ－１０００、ＳＰＣ－３０００（以上、昭和電工製）；ＮＫオリゴ　Ｕ－４ＨＡ、Ｕ－４Ｈ、Ｕ－６ＨＡ、Ｕ－１５ＨＡ、Ｕ－１０８Ａ、Ｕ－１０８４Ａ、Ｕ－２００ＡＸ、Ｕ－１２２Ａ、Ｕ－３４０Ａ、Ｕ－３２４Ａ、ＵＡ－５３Ｈ、ＵＡ－１００、ＡＨ－６００（以上、新中村化学工業（株）製）、ＵＡ－３０６Ｈ、ＡＩ－６００、ＵＡ－１０１Ｔ、ＵＡ－１０１Ｉ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ（以上、共栄社化学（株）製）、アートレジン　ＵＮ－９２００Ａ、ＵＮ－３３２０ＨＡ、ＵＮ－３３２０ＨＢ、ＵＮ－３３２０ＨＣ、ＵＮ－３３２０ＨＳ、ＳＨ－３８０Ｇ、ＳＨ－５００、ＳＨ－９８３２、ＵＮ－９０１Ｔ、ＵＮ－９０４、ＵＮ－９０５、ＵＮ－９０６、ＵＮ－９０６Ｓ、ＵＮ－９０７、ＵＮ－９５２、ＵＮ－９５３、ＵＮ－９５４、Ｈ－９１、Ｈ－１３５（以上、根上工業（株）製）、サートマー　ＣＮ９６８、ＣＮ９７５、ＣＮ９８９、ＣＮ９００１、ＣＮ９０１０、ＣＮ９０２５、ＣＮ９０２９、ＣＮ９１６５、ＣＮ２２６０（以上、サートマー社製）、ＥＢＥＣＲＹＬ　８８１０（ダイセル社製）等が挙げられる。 市 販 As other radical polymerizable compounds, commercially available products can also be used. Commercially available products include, for example, Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (all manufactured by Nippon Kayaku); NK ester A-DOD-N, A-DPH, A- TMPC, A-HD-N, TMPT, NPG and HD-N (all manufactured by Shin-Nakamura Chemical Co., Ltd.); SPC-1000, SPC-3000 (all manufactured by Showa Denko); NK Oligo @ U-4HA, U-4H, U-6HA, U-15HA, U-108A, U-1084A, U-200AX, U-122A, U-340A, U-324A, UA-53H, UA-100, AH-600 (Shin-Nakamura Chemical Co., Ltd.) UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (Kyoeisha Co., Ltd.) Co., Ltd.), Art Resin @ UN-9200A, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, SH-380G, SH-500, SH-9832, UN-901T, UN-904, UN- 905, UN-906, UN-906S, UN-907, UN-952, UN-953, UN-954, H-91, H-135 (all manufactured by Negami Industry Co., Ltd.), Sartomer CN968, CN975, CN989 , CN9001, CN9010, CN9025, CN9029, CN9165, CN2260 (manufactured by Sartomer), EBECRYL # 8810 (manufactured by Daicel), and the like.
＜カチオン重合性成分（Ｂ）＞
　本発明の組成物に含まれるカチオン重合性成分（Ｂ）は、カチオン重合性基を有し、ラジカル重合性基を有さない化合物である。成分（Ｂ）は、化合物（Ｂ１）、カチオン重合性基を有し、架橋縮合環を有さない重量平均分子量１，０００以上３０，０００未満のカチオン重合性化合物（Ｂ２）（以下、「化合物（Ｂ２）」とも称す）、架橋縮合環を有さない重量平均分子量２００以上１，０００未満のカチオン重合性化合物（Ｂ３）（以下、「化合物（Ｂ３）」とも称す）および化合物（Ｂ１）～化合物（Ｂ３）に属さないその他のカチオン重合性化合物から構成される。なお、本発明の組成物では、単独または２種以上の成分（Ｂ）を混合して使用することができる。また、分子量は、化合物が重合体である場合には、重量平均分子量（Ｍｗ）を示すものである。 <Cationically polymerizable component (B)>
The cationically polymerizable component (B) contained in the composition of the present invention is a compound having a cationically polymerizable group and not having a radically polymerizable group. The component (B) is a compound (B1), a cationically polymerizable compound (B2) having a cationically polymerizable group and having no crosslinked condensed ring and having a weight average molecular weight of 1,000 or more and less than 30,000 (hereinafter referred to as “compound”). (B2)), a cationically polymerizable compound (B3) having no crosslinked condensed ring and having a weight average molecular weight of 200 or more and less than 1,000 (hereinafter also referred to as “compound (B3)”) and compounds (B1) to It is composed of other cationically polymerizable compounds not belonging to compound (B3). In the composition of the present invention, a single component or a mixture of two or more components (B) can be used. The molecular weight indicates a weight average molecular weight (Mw) when the compound is a polymer.
　本発明の組成物に含有される成分（Ｂ）の含有量は、組成物１００質量部に対して耐水性に優れることから３０～５０質量部が好ましく、特に好ましくは、４０～５０質量部である。 The content of the component (B) contained in the composition of the present invention is preferably from 30 to 50 parts by mass, particularly preferably from 40 to 50 parts by mass, since water resistance is excellent with respect to 100 parts by mass of the composition. is there.
　成分（Ｂ）は、本発明の組成物の塗工容易性、硬化速度等の観点からは、低分子量化合物を含むことが好ましい。また、低分子量化合物は、組成物中への分散性または溶解性等に優れるため、透明性に優れた硬化物を得ることができるからである。一方、カチオン重合性化合物は、本発明の組成物の接着力等の観点からは、高分子量化合物を含むことが好ましい。また、カチオン重合性化合物は、組成物の塗工容易性、硬化速度、接着力のバランスの観点からは、低分子量化合物および高分子量化合物の両者を含むことが好ましい。また、高分子量化合物は、低分子量化合物と共に用いられることで、本発明の組成物中への分散または溶解性を向上でき、透明性に優れた硬化物を得ることができるからである。 Component (B) preferably contains a low molecular weight compound from the viewpoint of ease of application and curing speed of the composition of the present invention. Further, the low molecular weight compound is excellent in dispersibility or solubility in the composition and the like, so that a cured product excellent in transparency can be obtained. On the other hand, the cationically polymerizable compound preferably contains a high molecular weight compound from the viewpoint of the adhesive strength of the composition of the present invention and the like. Further, the cationically polymerizable compound preferably contains both a low molecular weight compound and a high molecular weight compound from the viewpoint of the balance between the ease of application of the composition, the curing speed, and the adhesive strength. Also, when the high molecular weight compound is used together with the low molecular weight compound, the dispersion or solubility in the composition of the present invention can be improved, and a cured product excellent in transparency can be obtained.
　高分子量化合物の含有量は、所望の硬化速度および接着力が得られるものであれば特に限定されるものではなく、例えば、接着力および透明性等のバランスの観点から、適宜調整されるものである。高分子量化合物の含有量は、具体的には、本発明の組成物の固形分１００質量部中に０質量部以上２０質量部以下とすることができ、２質量部以上１５質量部以下であることが好ましく、なかでも、３質量部以上１０質量部以下であることが好ましい。含有量がかかる範囲内であることで、本発明の組成物は、硬化速度および接着力に優れたものとなるからであり、特に接着力に優れると共に透明性に優れた硬化物を形成可能となるからである。 The content of the high molecular weight compound is not particularly limited as long as a desired curing rate and adhesive strength can be obtained.For example, the content is appropriately adjusted from the viewpoint of a balance between adhesive strength and transparency. is there. Specifically, the content of the high molecular weight compound can be 0 to 20 parts by mass in 100 parts by mass of the solid content of the composition of the present invention, and can be 2 to 15 parts by mass. It is particularly preferable that the amount is 3 parts by mass or more and 10 parts by mass or less. When the content is within such a range, the composition of the present invention becomes excellent in curing speed and adhesive strength, and it is possible to form a cured product excellent in transparency and particularly excellent in adhesive strength. Because it becomes.
＜化合物（Ｂ１）＞
　化合物（Ｂ１）は、架橋縮合環を有するカチオン重合性化合物である。架橋縮合環の中でも耐水性に優れることから、上記一般式（Ｉ）で表される構造を有する架橋縮合環が好ましく、特に上記架橋縮合環Ｎｏ．６、Ｎｏ．７およびＮｏ．８を有する化合物（Ｂ１）を含有する接着剤は高い接着力および耐水性を有することから、好ましい。架橋縮合環Ｎｏ．６は、構造が安定で生産性が高いことから特に好ましい。 <Compound (B1)>
Compound (B1) is a cationically polymerizable compound having a crosslinked condensed ring. Among the crosslinked condensed rings, a crosslinked condensed ring having a structure represented by the above general formula (I) is preferable because of its excellent water resistance. 6, no. 7 and No. 7 An adhesive containing the compound (B1) having 8 has a high adhesive strength and water resistance, and is therefore preferred. Bridged condensed ring No. 6 is particularly preferable because of its stable structure and high productivity.
　化合物（Ｂ１）としては、例えば、下記化合物（Ｂ１）Ｎｏ．１～Ｎｏ．２２等が挙げられる。  As the compound (B1), for example, the following compound (B1) No. 1 to No. 22 and the like.
Figure JPOXMLDOC01-appb-I000010
Figure JPOXMLDOC01-appb-I000010
　化合物（Ｂ１）としては、市販品を用いることもできる。市販品としては、例えば、アデカレジンＥＰ－４０８８Ｌ、４０８８Ｓ（以上、ＡＤＥＫＡ製）；ＸＤ－１０００（日本化薬製）ＨＰ－７２００（ＤＩＣ製）等が挙げられる。 市 販 As the compound (B1), a commercial product can also be used. Commercially available products include, for example, Adeka Resin EP-4088L, 4088S (above, manufactured by ADEKA); XD-1000 (manufactured by Nippon Kayaku), HP-7200 (manufactured by DIC).
　化合物（Ｂ１）のカチオン重合性基としては、硬化性が高く、接着力に優れるとの観点からは、エポキシ基が好ましく、特にグリシジルエーテル基が好ましい。また、硬化性が優れること観点から、複数のカチオン重合性基を有することが好ましく、特に２～３個が好ましい。 カ チ オ ン As the cationically polymerizable group of the compound (B1), an epoxy group is preferable, and a glycidyl ether group is particularly preferable from the viewpoint of high curability and excellent adhesive strength. Further, from the viewpoint of excellent curability, it preferably has a plurality of cationically polymerizable groups, and particularly preferably has two or three cationically polymerizable groups.
＜化合物（Ｂ２）＞
　化合物（Ｂ２）は、架橋縮合環を有さない重量平均分子量１，０００以上３０，０００未満のカチオン重合性化合物であればよく、特に制限されない。重量平均分子量は、上述の測定方法によって測定できる。化合物（Ｂ２）を含有する組成物は、耐水性が向上することから好ましい。 <Compound (B2)>
The compound (B2) is not particularly limited as long as it is a cationic polymerizable compound having a weight average molecular weight of 1,000 or more and less than 30,000 having no crosslinked condensed ring. The weight average molecular weight can be measured by the above-mentioned measuring method. The composition containing the compound (B2) is preferable because the water resistance is improved.
　化合物（Ｂ２）としては、例えば、グリシジルメタクリレートの重合物およびグリシジルメタクリレートとメチルメタクリレートの共重合物等のグリシジルメタクリレートの共重合物、並びにそれらの一部を変性したものが挙げられ、グリシジルメタクリレートとしては、グリシジルメタクリレート、２－メチルグリシジルメタクリレート、４－ヒドロキシブチルメタクリレート、ビスフェノールＡのジグリシジルエーテル、ビスフェノールＦのジグリシジルエーテル等を挙げることができる。また、これ以外にも、ノボラック型エポキシ樹脂、２－ヒドロキシエチルビニルエーテル、トリエチレングリコールビニルモノエーテル、テトラエチレングリコールジビニルエーテル、トリメチロールプロパントリビニルエーテル等の重合体およびこれらの共重合体等が挙げられる。 Examples of the compound (B2) include a glycidyl methacrylate polymer and a glycidyl methacrylate copolymer such as a glycidyl methacrylate and methyl methacrylate copolymer, and a partially modified glycidyl methacrylate. Glycidyl methacrylate, 2-methyl glycidyl methacrylate, 4-hydroxybutyl methacrylate, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and the like. In addition, polymers such as novolak type epoxy resins, 2-hydroxyethyl vinyl ether, triethylene glycol vinyl monoether, tetraethylene glycol divinyl ether, and trimethylolpropane trivinyl ether, and copolymers thereof, and the like are also included. .
　化合物（Ｂ２）としては、市販品を用いることもできる。市販品としては、例えば、Ｇ－０１３０Ｍ（以上、日油製）、ＥＯＣＮ－１０４Ｓ（日本化薬製）等が挙げられる。 市 販 As the compound (B2), a commercial product can also be used. Commercially available products include, for example, G-0130M (both manufactured by NOF) and EOCN-104S (manufactured by Nippon Kayaku).
　化合物（Ｂ２）としては、エポキシ当量が１，０００以下の場合、硬化性に優れることから好ましく、エポキシ当量が２００～６００が特に好ましい。 The compound (B2) having an epoxy equivalent of 1,000 or less is preferable because of excellent curability, and the epoxy equivalent is particularly preferably 200 to 600.
　また、化合物（Ｂ２）の有するカチオン重合性基としては、硬化性が高く、接着力が高い組成物が得られることから、エポキシ基が好ましく、特にグリシジルエーテル基が好ましい。 カ チ オ ン Further, as the cationically polymerizable group of the compound (B2), an epoxy group is preferable, and a glycidyl ether group is particularly preferable, since a composition having high curability and high adhesive force can be obtained.
　カチオン重合性成分（Ｂ）に含有されていてもよいカチオン重合性化合物（Ｂ２）の好ましい含有量は、耐水性および流動性に優れることからカチオン重合性成分（Ｂ）１００質量部中に０～３０質量部であり、特に好ましくは、５～２０質量部である。 The preferable content of the cationically polymerizable compound (B2) which may be contained in the cationically polymerizable component (B) is 0 to 100 parts by mass of the cationically polymerizable component (B) because of its excellent water resistance and fluidity. The amount is 30 parts by mass, particularly preferably 5 to 20 parts by mass.
＜化合物（Ｂ３）＞
　化合物（Ｂ３）は、架橋縮合環を有さない重量平均分子量２００以上１，０００未満のカチオン重合性化合物であればよく、特に限定されない。化合物（Ｂ３）を含有する組成物は、接着力と塗布性を両立できることから好ましい。化合物（Ｂ３）としては、例えば芳香族エポキシ化合物、脂環式エポキシ化合物、脂肪族エポキシ化合物、オキセタン化合物等が挙げられる。ただし、エポキシ基とオキセタニル基を同一分子内に有する化合物は、オキセタン化合物に分類される。 <Compound (B3)>
The compound (B3) is not particularly limited as long as it is a cationically polymerizable compound having a weight average molecular weight of 200 or more and less than 1,000 without a crosslinked condensed ring. The composition containing the compound (B3) is preferable because it can achieve both adhesive strength and applicability. Examples of the compound (B3) include an aromatic epoxy compound, an alicyclic epoxy compound, an aliphatic epoxy compound, an oxetane compound, and the like. However, compounds having an epoxy group and an oxetanyl group in the same molecule are classified as oxetane compounds.
　エポキシ当量が５００以下の化合物（Ｂ３）を含有する組成物は、硬化性に優れることから好ましく、エポキシ当量が２００以下の化合物（Ｂ３）を含有する組成物が、特に好ましい。 (4) A composition containing a compound (B3) having an epoxy equivalent of 500 or less is preferable because of excellent curability, and a composition containing a compound (B3) having an epoxy equivalent of 200 or less is particularly preferable.
　化合物（Ｂ３）の有するカチオン重合性基としては、硬化性が高く、接着力が高い組成物が得られることから、エポキシ基が好ましく、特にグリシジルエーテル基が好ましい。また、化合物（Ｂ３）としては、耐水性に優れた組成物が得られるため、オキセタニル基を有する化合物も好ましい。 カ チ オ ン As the cationically polymerizable group of the compound (B3), an epoxy group is preferable, and a glycidyl ether group is particularly preferable, since a composition having high curability and high adhesive strength can be obtained. As the compound (B3), a compound having an oxetanyl group is also preferable, since a composition having excellent water resistance can be obtained.
　カチオン重合性化合物（Ｂ３）がカチオン重合性成分（Ｂ）に含有される場合、好ましい含有量は、耐水性および流動性に優れることからカチオン重合性成分（Ｂ）１００質量部中に０～９０質量部が好ましく、特に好ましくは、３５～８０質量部である。 When the cationically polymerizable compound (B3) is contained in the cationically polymerizable component (B), the content is preferably from 0 to 90 per 100 parts by mass of the cationically polymerizable component (B) because of its excellent water resistance and fluidity. The parts by mass are preferable, and particularly preferably 35 to 80 parts by mass.
　カチオン重合性基を１～３つ含む化合物（Ｂ３）を含有する組成物は、接着力と塗布性を両立できることから好ましく、特にカチオン重合性基を１～２つ含む化合物（Ｂ３）が特に好ましい。 The composition containing the compound (B3) containing 1 to 3 cationically polymerizable groups is preferable because both the adhesive strength and the applicability can be achieved, and the compound (B3) containing 1 to 2 cationically polymerizable groups is particularly preferable. .
　化合物（Ｂ３）としての脂環式エポキシ化合物とは、脂環式エポキシ基（３，４－エポキシシクロヘキシル基）を有し、架橋縮合環を有さない重量平均分子量２００以上１，０００未満のカチオン重合性化合物を意味する。化合物（Ｂ３）として脂環式エポキシ化合物を用いることで、初期硬化性が向上することから好ましい。 The alicyclic epoxy compound as the compound (B3) is a cation having an alicyclic epoxy group (3,4-epoxycyclohexyl group) and not having a crosslinked condensed ring and having a weight average molecular weight of 200 or more and less than 1,000. It means a polymerizable compound. It is preferable to use an alicyclic epoxy compound as the compound (B3) because the initial curability is improved.
　脂環式エポキシ化合物としては、例えば、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキシルカルボキシレート、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシ－１－メチルシクロヘキシル－３，４－エポキシ－１－メチルヘキサンカルボキシレート、６－メチル－３，４－エポキシシクロヘキシルメチル－６－メチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシ－３－メチルシクロヘキシルメチル－３，４－エポキシ－３－メチルシクロヘキサンカルボキシレート、３，４－エポキシ－５－メチルシクロヘキシルメチル－３，４－エポキシ－５－メチルシクロヘキサンカルボキシレート、ビス（３，４－エポキシシクロヘキシルメチル）アジペート、３，４－エポキシ－６－メチルシクロヘキサンカルボキシレート、メチレンビス（３，４－エポキシシクロヘキサン）、プロパン－２，２－ジイル－ビス（３，４－エポキシシクロヘキサン）、２，２－ビス（３，４－エポキシシクロヘキシル）プロパン、ジシクロペンタジエンジエポキサイド、エチレンビス（３，４－エポキシシクロヘキサンカルボキシレート）、エポキシヘキサヒドロフタル酸ジオクチル、エポキシヘキサヒドロフタル酸ジ－２－エチルヘキシル、１－エポキシエチル－３，４－エポキシシクロヘキサン、１，２－エポキシ－２－エポキシエチルシクロヘキサン、７－オキサビシクロ［４．１．０］ヘプタン，ポリ［オキシ－（１－オキソ－１，６－ヘキサンジイル）］誘導体、ヘキサン二酸ビス［（７－オキサビシクロ［４．１．０］ヘプタン－３－イル）メチル］、α－ピネンオキシド、リモネンジオキシドが挙げられる。 Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 3,4-epoxy- 1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3 -Methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclo Hexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2- Bis (3,4-epoxycyclohexyl) propane, dicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1- Epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, 7-oxabicyclo [4.1.0] heptane, poly [oxy- (1-oxo-1,6-hexanediyl) )] Derivative, hexa Diacid bis [(7-oxabicyclo [4.1.0] heptan-3-yl) methyl], alpha-pinene oxide, and limonene dioxide.
　脂環式エポキシ化合物としては、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレートまたは３，４－エポキシ－１－メチルシクロヘキシル－３，４－エポキシ－１－メチルヘキサンカルボキシレートおよび３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキシルカルボキシレートが、接着力向上の観点から好ましい。 Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate and 2,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate is preferred from the viewpoint of improving adhesive strength.
　脂環式エポキシ化合物としては、市販品のものを用いることができ、例えば、セロキサイド２０２１Ｐ、セロキサイド２０８１、セロキサイド２０００、セロキサイド３０００、サイクロマーＭ１００（ダイセル社製）；ＣＹＲＡＣＵＲＥ　ＵＶＲ－６１２８（ダウ・ケミカル社製）等が挙げられる。 Commercially available products can be used as the alicyclic epoxy compound, and examples thereof include Celloxide 2021P, Celloxide 2081, Celloxide 2000, Celloxide 3000, Cyclomer M100 (manufactured by Daicel); CYRACURE @ UVR-6128 (manufactured by Dow Chemical Company). Manufactured).
　脂環式エポキシ化合物の含有量としては、所望の硬化速度および接着力を得られればよく、例えば、化合物（Ｂ）１００質量部中に０質量部以上５０質量部以下とすることができ、なかでも、１質量部以上２０質量部以下であることが好ましい。含有量がかかる範囲であることで、本発明の組成物は、硬化速度および接着力に優れたものとなる。 The content of the alicyclic epoxy compound may be any as long as a desired curing rate and adhesive strength can be obtained. For example, the content can be 0 to 50 parts by mass in 100 parts by mass of the compound (B). However, it is preferably from 1 part by mass to 20 parts by mass. When the content is in such a range, the composition of the present invention has excellent curing speed and adhesive strength.
　化合物（Ｂ３）としての脂肪族エポキシ化合物とは、脂環式エポキシ化合物や後述の芳香族エポキシ化合物に分類されない架橋縮合環を有さない重量平均分子量２００以上１，０００未満のカチオン重合性化合物を指し、脂肪族環および芳香族環を含まないものを意味する。 The aliphatic epoxy compound as the compound (B3) refers to a cationic polymerizable compound having a weight average molecular weight of 200 or more and less than 1,000 having no crosslinked condensed ring that is not classified as an alicyclic epoxy compound or an aromatic epoxy compound described below. Refers to those that do not contain aliphatic and aromatic rings.
　脂肪族エポキシ化合物の具体例としては、脂肪族アルコールのグリシジルエーテル化物、アルキルカルボン酸のグリシジルエステル等の単官能エポキシ化合物や、脂肪族多価アルコールまたはそのアルキレンオキサイド付加物のポリグリシジルエーテル化物、脂肪族長鎖多塩基酸のポリグリシジルエステル等の多官能エポキシ化合物が挙げられる。 Specific examples of the aliphatic epoxy compound include a glycidyl ether compound of an aliphatic alcohol, a monofunctional epoxy compound such as a glycidyl ester of an alkyl carboxylic acid, a polyglycidyl ether compound of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof, and a fatty acid. And polyfunctional epoxy compounds such as polyglycidyl esters of long-chain polybasic acids.
　脂肪族エポキシ化合物の代表的な化合物としては、１，４－ブタンジオールジグリシジレート、アリルグリシジルエーテル、ブチルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、Ｃ１２～１３混合アルキルグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、水素添加ビスフェノールＡジグリシジルエーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ソルビトールテトラグリシジルエーテル、ジペンタエリスリトールヘキサグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル等の多価アルコールのグリシジルエーテル、またプロピレングリコール、トリメチロールプロパン、グリセリン等の脂肪族多価アルコールに１種または２種以上のアルキレンオキサイドを付加することによって得られるポリエーテルポリオールのポリグリシジルエーテル化物、脂肪族長鎖二塩基酸のジグリシジルエステルが挙げられる。更に、脂肪族高級アルコールのモノグリシジルエーテルや高級脂肪酸のグリシジルエステル、エポキシ化大豆油、エポキシステアリン酸オクチル、エポキシステアリン酸ブチル、エポキシ化大豆油、エポキシ化ポリブタジエン等が挙げられる。 Representative examples of the aliphatic epoxy compounds include 1,4-butanediol diglycidylate, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, and 1,4-butanediol. Diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, polyethylene glycol diglycidyl Glycidyl ether of polyhydric alcohol such as ether, polypropylene glycol diglycidyl ether, and propylene Polyglycidyl etherified products of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as recol, trimethylolpropane and glycerin, and diglycidyl esters of aliphatic long-chain dibasic acids Is mentioned. Further examples include monoglycidyl ethers of aliphatic higher alcohols and glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, epoxidized soybean oil, and epoxidized polybutadiene.
　脂肪族エポキシ化合物としては、脂肪族アルコールのグリシジルエーテル化物あるいは脂肪族多価アルコールまたはそのアルキレンオキサイド付加物のポリグリシジルエーテル化物が、粘度、塗工性および反応性が向上するので好ましく、さらに、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテルまたは１，６－ヘキサンジオールジグリシジルエーテルが好ましい。 As the aliphatic epoxy compound, a glycidyl etherified product of an aliphatic alcohol or a polyglycidyl etherified product of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof is preferable because viscosity, coating property and reactivity are improved. Glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether or 1,6-hexanediol diglycidyl ether is preferred.
　脂肪族エポキシ化合物としては、市販品のものを用いることができ、例えば、デナコールＥＸ－１２１、デナコールＥＸ－１７１、デナコールＥＸ－１９２、デナコールＥＸ－２１１、デナコールＥＸ－２１２、デナコールＥＸ－３１３、デナコールＥＸ－３１４、デナコールＥＸ－３２１、デナコールＥＸ－４１１、デナコールＥＸ－４２１、デナコールＥＸ－５１２、デナコールＥＸ－５２１、デナコールＥＸ－６１１、デナコールＥＸ－６１２、デナコールＥＸ－６１４、デナコールＥＸ－６２２、デナコールＥＸ－８１０、デナコールＥＸ－８１１、デナコールＥＸ－８５０、デナコールＥＸ－８５１、デナコールＥＸ－８２１、デナコールＥＸ－８３０、デナコールＥＸ－８３２、デナコールＥＸ－８４１、デナコールＥＸ－８６１、デナコールＥＸ－９１１、デナコールＥＸ－９４１、デナコールＥＸ－９２０、デナコールＥＸ－９３１（以上、ナガセケムテックス製）；エポライトＭ－１２３０、エポライト４０Ｅ、エポライト１００Ｅ、エポライト２００Ｅ、エポライト４００Ｅ、エポライト７０Ｐ、エポライト２００Ｐ、エポライト４００Ｐ、エポライト１５００ＮＰ、エポライト１６００、エポライト８０ＭＦ、エポライト１００ＭＦ（以上、共栄社化学製）、アデカグリシロールＥＤ－５０３、アデカグリシロールＥＤ－５０３Ｇ、アデカグリシロールＥＤ－５０６、アデカグリシロールＥＤ－５２３Ｔ、アデカレジンＥＰ－４０８８Ｓ、ＫＲＭ－５２３Ｐ、ＫＲＭ－４０８、ＫＲＭ－１４０（以上、ＡＤＥＫＡ製）；２ＥＨ（四日市合成製）等が挙げられる。 As the aliphatic epoxy compound, commercially available products can be used. For example, denacol EX-121, denacol EX-171, denacol EX-192, denacol EX-211, denacol EX-212, denacol EX-313, denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-8 1, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (all manufactured by Nagase ChemteX); Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (all manufactured by Kyoeisha Chemical Co., Ltd.), Adekaglycylol ED-503, Adekaglycylol ED-503G, Adekaglycylol ED-506, Adekaglycylol ED -523T, Adeka Resin EP-4088S, KRM-523P, KRM-408, KRM-140 (all manufactured by ADEKA); 2EH (Yokaichi Gosei) and the like. That.
　脂肪族エポキシ化合物の含有量としては、所望の硬化速度および接着力を得られればよく、例えば、化合物（Ｂ）１００質量部中に０質量部以上９０質量部以下とすることができ、なかでも、３０質量部以上８０質量部以下であることが好ましい。含有量がかかる範囲であることで、本発明の組成物は、硬化速度および接着力に優れたものとなる。 The content of the aliphatic epoxy compound may be any as long as the desired curing rate and adhesive strength can be obtained. For example, the content can be 0 to 90 parts by mass in 100 parts by mass of the compound (B). , 30 parts by mass or more and 80 parts by mass or less. When the content is in such a range, the composition of the present invention has excellent curing speed and adhesive strength.
　化合物（Ｂ３）としての芳香族エポキシ化合物は、脂環式エポキシ化合物に分類されず架橋縮合環を有さない重量平均分子量２００以上１，０００未満の芳香環を含有するエポキシ化合物を意味する。 芳香 The aromatic epoxy compound as the compound (B3) means an epoxy compound containing an aromatic ring having a weight average molecular weight of 200 or more and less than 1,000, which is not classified as an alicyclic epoxy compound and has no crosslinked condensed ring.
　芳香族エポキシ化合物の具体例としては、フェノール、クレゾール、ブチルフェノール等、少なくとも１個の芳香族環を有する１価フェノールまたは、そのアルキレンオキサイド付加物のモノ／ポリグリシジルエーテル化物、例えばビスフェノールＡ、ビスフェノールＦ、またはこれらに更にアルキレンオキサイドを付加した化合物のグリシジルエーテル化物やフェノールノボラック型エポキシ化合物；レゾルシノールやハイドロキノン、カテコール等の２個以上のフェノール性水酸基を有する芳香族化合物のグリシジルエーテル；ベンゼンジメタノールやベンゼンジエタノール、ベンゼンジブタノール等のアルコール性水酸基を２個以上有する芳香族化合物のポリグリシジルエーテル化物；フタル酸、テレフタル酸、トリメリット酸等の２個以上のカルボン酸を有する多塩基酸芳香族化合物のポリグリシジルエステル、安息香酸やトルイル酸、ナフトエ酸等の安息香酸類のポリグリシジルエステル、安息香酸のグリシジルエステル、スチレンオキサイドまたはジビニルベンゼンのエポキシ化物等が挙げられる。中でも、フェノール類のポリグリシジルエーテル、アルコール性水酸基を２個以上有する芳香族化合物のポリグリシジルエーテル化物、多価フェノール類のポリグリシジルエーテル化物、安息香酸類のポリグリシジルエステル、多塩基酸類のポリグリシジルエステルの群から選ばれる少なくとも一種を含有することが、本発明の組成物の低粘度化の観点から好ましい。芳香族エポキシ化合物としては、ビスフェノールＡ型エポキシ化合物、ビスフェノールＦ型エポキシ化合物、ビスフェノールＥ型エポキシ化合物、フェノールノボラック型エポキシ化合物が、接着力に優れるため好ましい。 Specific examples of the aromatic epoxy compound include a monohydric phenol having at least one aromatic ring such as phenol, cresol and butyl phenol, or a mono / polyglycidyl etherified product of an alkylene oxide adduct thereof, for example, bisphenol A, bisphenol F Or a glycidyl etherified compound of a compound to which an alkylene oxide is further added, or a phenol novolak type epoxy compound; a glycidyl ether of an aromatic compound having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol; benzene dimethanol or benzene Polyglycidyl etherified aromatic compounds having two or more alcoholic hydroxyl groups such as diethanol and benzenedibutanol; phthalic acid, terephthalic acid, trimellitic acid, etc. Polyglycidyl ester of polybasic acid aromatic compound having two or more carboxylic acids, benzoic acid, toluic acid, polyglycidyl ester of benzoic acid such as naphthoic acid, glycidyl ester of benzoic acid, epoxide of styrene oxide or divinylbenzene, etc. Is mentioned. Among them, polyglycidyl ethers of phenols, polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups, polyglycidyl ethers of polyhydric phenols, polyglycidyl esters of benzoic acids, polyglycidyl esters of polybasic acids It is preferable to contain at least one selected from the group from the viewpoint of reducing the viscosity of the composition of the present invention. As the aromatic epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol E type epoxy compound, and a phenol novolak type epoxy compound are preferable because of their excellent adhesive strength.
　芳香族エポキシ化合物としては、市販品のものを用いることができ、例えば、デナコールＥＸ－１４５、デナコールＥＸ－１４６、デナコールＥＸ－１４７、デナコールＥＸ－２０１、デナコールＥＸ－２０３、デナコールＥＸ－７１１、デナコールＥＸ－７２１、オンコートＥＸ－１０２０、オンコートＥＸ－１０３０、オンコートＥＸ－１０４０、オンコートＥＸ－１０５０、オンコートＥＸ－１０５１、オンコートＥＸ－１０１０、オンコートＥＸ－１０１１、オンコート１０１２（ナガセケムテックス社製）；オグソールＰＧ－１００、オグソールＥＧ－２００、オグソールＥＧ－２１０、オグソールＥＧ－２５０（大阪ガスケミカル社製）；ＨＰ４０３２、ＨＰ４０３２Ｄ、ＨＰ４７００（ＤＩＣ社製）；ＥＳＮ－４７５Ｖ（新日鉄住金化学社製）；エピコートＹＸ８８００（三菱化学社製）；マープルーフＧ－０１０５ＳＡ、マープルーフＧ－０１３０ＳＰ（日油社製）；エピクロンＮ－６６５、エピクロンＨＰ－７２００（ＤＩＣ社製）；ＥＯＣＮ－１０２０、ＥＯＣＮ－１０２Ｓ、ＥＯＣＮ－１０３Ｓ、ＥＯＣＮ－１０４Ｓ、ＸＤ－１０００、ＮＣ－３０００、ＥＰＰＮ－５０１Ｈ、ＥＰＰＮ－５０１ＨＹ、ＥＰＰＮ－５０２Ｈ、ＮＣ－７０００Ｌ（日本化薬社製）；アデカレジンＥＰ－４０００、アデカレジンＥＰ－４００５、アデカレジンＥＰ－４１００、アデカレジンＥＰ－４９０１、アデカレジンＥＰ－３３００Ｅ、アデカレジンＥＰ－３９５０Ｓ、ＫＲＭ－４３０、ＫＲＭ－５０１（ＡＤＥＫＡ社製）；ＴＥＣＨＭＯＲＥ　ＶＧ－３１０１Ｌ（プリンテック社製）等が挙げられる。 As the aromatic epoxy compound, commercially available ones can be used. For example, Denacol EX-145, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, on-coat EX-1020, on-coat EX-1030, on-coat EX-1040, on-coat EX-1050, on-coat EX-1051, on-coat EX-1010, on-coat EX-1011, on-coat 1012 ( Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (Osaka Gas Chemical); HP4032, HP4032D, HP4700 (DIC); ESN-475V (New) Epicoat YX8800 (manufactured by Mitsubishi Chemical); Marproof G-0105SA, Marproof G-0130SP (manufactured by NOF Corporation); Epicron N-665, Epicron HP-7200 (manufactured by DIC); EOCN -1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon Kayaku); Adeka Resin EP-4000 ADEKARESIN EP-4005, ADEKARESIN EP-4100, ADEKARESIN EP-4901, ADEKARESIN EP-3300E, ADEKARESIN EP-3950S, KRM-430, KRM-501 (manufactured by ADEKA); TECHMORE @ VG-3101L (purine) Click Co., Ltd.), and the like.
　芳香族エポキシ化合物の含有量としては、所望の硬化速度および接着力を得られればよく、例えば、化合物（Ｂ）１００質量部中に０質量部以上９０質量部以下とすることができ、なかでも、１０質量部以上５０質量部以下であることが好ましい。含有量がかかる範囲であることで、本発明の組成物は、硬化速度および接着力に優れたものとなる。 The content of the aromatic epoxy compound may be any as long as the desired curing rate and adhesive strength can be obtained. For example, the content can be 0 to 90 parts by mass per 100 parts by mass of the compound (B). It is preferably from 10 parts by mass to 50 parts by mass. When the content is in such a range, the composition of the present invention has excellent curing speed and adhesive strength.
　化合物（Ｂ３）としてのオキセタン化合物とは、オキセタニル基を有し、架橋縮合環を有さない重量平均分子量２００以上１，０００未満のオキセタン化合物を意味する。 オ The oxetane compound as the compound (B3) means an oxetane compound having an oxetanyl group and having no crosslinked condensed ring and having a weight average molecular weight of 200 or more and less than 1,000.
　硬化性および塗布性のバランスに優れることから、オキセタニル基を１～３含有するオキセタン化合物が好ましく、オキセタニル基を２つ含有するオキセタン化合物が特に好ましい。 Oxetane compounds containing 1 to 3 oxetanyl groups are preferred, and oxetane compounds containing two oxetanyl groups are particularly preferred because of their excellent balance between curability and coatability.
　オキセタン化合物としては、３，３’－［オキシビス（メチレン）］ビス（３－エチルオキセタン）、（３，７－ビス（３－オキセタニル）－５－オキサ－ノナン、１，４－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］ベンゼン、１，２－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］エタン、１，３－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］プロパン、エチレングリコールビス（３－エチル－３－オキセタニルメチル）エーテル、トリエチレングリコールビス（３－エチル－３－オキセタニルメチル）エーテル、テトラエチレングリコールビス（３－エチル－３－オキセタニルメチル）エーテル、１，４－ビス（３－エチル－３－オキセタニルメトキシ）ブタン、１，６－ビス（３－エチル－３－オキセタニルメトキシ）ヘキサン、３－エチル－３－（３－エチル－３－オキセタニルメチルオキシメチル）オキセタン、キシリレンビスオキセタン等の二官能オキセタン化合物、３－エチル－３－［（フェノキシ）メチル］オキセタン、３－エチル－３－（ヘキシロキシメチル）オキセタン、３－エチル－３－（２－エチルヘキシロキシメチル）オキセタン、３－エチル－３－（ヒドロキシメチル）オキセタン、３－エチル－３－（クロロメチル）オキセタン等の一官能オキセタン化合物等が挙げられ、一官能脂肪族オキセタン化合物が、粘度および反応性の点から好ましい。これらは１種単独あるいは２種以上を組み合わせて用いることができる。 Examples of the oxetane compound include 3,3 ′-[oxybis (methylene)] bis (3-ethyloxetane), (3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3 -Ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] Propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1 , 4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl Bifunctional oxetane compounds such as -3-oxetanylmethoxy) hexane, 3-ethyl-3- (3-ethyl-3-oxetanylmethyloxymethyl) oxetane and xylylenebisoxetane; 3-ethyl-3-[(phenoxy) methyl Oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3- Monofunctional oxetane compounds such as (chloromethyl) oxetane are preferable, and monofunctional aliphatic oxetane compounds are preferable in terms of viscosity and reactivity, and these can be used alone or in combination of two or more.
　オキセタン化合物としては、カチオン重合性モノマーを主成分とする市販品のものを用いることができ、例えば、アロンオキセタンＯＸＴ－１２１、ＯＸＴ－２２１、ＥＸＯＨ、ＰＯＸ、ＯＸＡ、ＯＸＴ－１０１、ＯＸＴ－２１１、ＯＸＴ－２１２、ＯＸＴ－２２１（東亞合成社製）、エタナコールＯＸＢＰ、ＯＸＴＰ（宇部興産社製）等が挙げられる。 As the oxetane compound, a commercially available product containing a cationic polymerizable monomer as a main component can be used. For example, Alonoxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212, OXT-221 (manufactured by Toagosei Co., Ltd.), etanacol OXBP, OXTP (manufactured by Ube Industries) and the like.
　オキセタン化合物の含有量としては、所望の硬化速度および接着力を得られるものであればよく、例えば、化合物（Ｂ）１００質量部中に０質量部以上５０質量部以下とすることができ、なかでも、５質量部以上３０質量部以下であることが好ましい。含有量がかかる範囲であることで、本発明の組成物は、塗工性および硬化速度に優れたものとなる。 The content of the oxetane compound is not particularly limited as long as the desired curing rate and adhesive strength can be obtained. For example, the content of the oxetane compound can be 0 to 50 parts by mass in 100 parts by mass of the compound (B). However, it is preferably from 5 parts by mass to 30 parts by mass. When the content is within such a range, the composition of the present invention has excellent coatability and curing speed.
＜ラジカル重合性開始剤（Ｃ）＞
　本発明の組成物に用いられる成分（Ｃ）としては、従来既知のラジカル重合性開始剤を用いることが可能である。 <Radical polymerizable initiator (C)>
As the component (C) used in the composition of the present invention, a conventionally known radically polymerizable initiator can be used.
　成分（Ｃ）とは、光ラジカル重合性開始剤と熱ラジカル重合性開始剤である。反応性が高いことから光ラジカル重合性開始剤がより好ましい。 Component (C) is a photoradical polymerizable initiator and a thermal radical polymerizable initiator. The photo-radical polymerization initiator is more preferable because of its high reactivity.
　成分（Ｃ）としては、光照射によりラジカルを発生するものであれば特に制限されず従来既知の化合物を用いることが可能であり、例えば、アセトフェノン系化合物、ベンジル系化合物、ベンゾフェノン系化合物、チオキサントン系化合物およびオキシムエステル系化合物等を好ましいものとして例示することができる。 The component (C) is not particularly limited as long as it generates a radical by light irradiation, and a conventionally known compound can be used. For example, an acetophenone-based compound, a benzyl-based compound, a benzophenone-based compound, and a thioxanthone-based compound can be used. Compounds and oxime ester compounds can be exemplified as preferred ones.
　アセトフェノン系化合物としては例えば、ベンゾイン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、４’－イソプロピル－２－ヒドロキシ－２－メチルプロピオフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシメチル－２－メチルプロピオフェノンおよび１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン等のα－ヒドロキシアセトフェノン系化合物；ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン－ｎ－ブチルエーテル、ベンゾインイソブチルエーテルジエトキシアセトフェノンおよび２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン等のα－アルコキシアセトフェノン系化合物；ｐ－ジメチルアミノアセトフェノン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパノン－１、および２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１等のα－アミノアセトフェノン系化合物；ｐ－ターシャリブチルジクロロアセトフェノン、ｐ－ターシャリブチルトリクロロアセトフェノン、ｐ－アジドベンザルアセトフェノン、が挙げられる。 Examples of the acetophenone-based compound include benzoin, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, Α-hydroxyacetophenone-based compounds such as -hydroxymethyl-2-methylpropiophenone and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one; Α-alkoxyacetates such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether diethoxyacetophenone and 2,2-dimethoxy-1,2-diphenylethan-1-one Phenone compounds; p-dimethylaminoacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, and 2-benzyl-2-dimethylamino-1- (4-morpholino Α-aminoacetophenone-based compounds such as phenyl) -butanone-1; p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, and p-azidobenzalacetophenone.
　本発明の組成物においては、得られる硬化物が透明性に優れることからアセトフェノン系化合物が好ましく、特にα－ヒドロキシアセトフェノン系化合物が特に好ましい。 ア セ ト In the composition of the present invention, an acetophenone-based compound is preferable, and an α-hydroxyacetophenone-based compound is particularly preferable because the obtained cured product has excellent transparency.
　ベンジル系化合物としては、ベンジル等が挙げられる。 Benzyl compounds include benzyl and the like.
　ベンゾフェノン系化合物としては、例えば、ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、ミヒラーケトン、４，４’－ビスジエチルアミノベンゾフェノン、４，４’－ジクロロベンゾフェノンおよび４－ベンゾイル－４’－メチルジフェニルスルフィド等が挙げられる。 Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide. .
　チオキサントン系化合物としては、チオキサントン、２－メチルチオキサントン、２－エチルチオキサントン、２－クロロチオキサントン、２－イソプロピルチオキサントン、２，４－ジエチルチオキサントン等が挙げられる。 Thioxanthones include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone and the like.
　オキシムエステル系化合物とは、オキシムエステル基を有する化合物を意味し、光ラジカル重合性開始剤の中でも感度が良好であることから、好ましい。 The oxime ester-based compound means a compound having an oxime ester group, and is preferable since it has good sensitivity among photo-radical polymerization initiators.
　好ましいオキシムエステル系化合物としては、例えば下記に示す化合物Ｎｏ．Ｃ１～Ｎｏ．Ｃ１４が挙げられる。  {Preferred oxime ester-based compounds include, for example, Compound No. C1 to No. C14.
Figure JPOXMLDOC01-appb-I000011
Figure JPOXMLDOC01-appb-I000011
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000012
　その他のラジカル重合性開始剤としては、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド等のホスフィンオキサイド系化合物およびビス（シクロペンタジエニル）－ビス［２，６－ジフルオロ－３－（ピル－１－イル）］チタニウム等のチタノセン系化合物等が挙げられる。 Other radically polymerizable initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyr- 1-yl)] titanocene compounds such as titanium.
　市販のラジカル開始剤としては、アデカオプトマーＮ－１４１４、Ｎ－１７１７、Ｎ－１９１９、アデカアークルズＮＣＩ－８３１、ＮＣＩ－９３０（以上、ＡＤＥＫＡ製）；ＩＲＧＡＣＵＲＥ１８４、ＩＲＧＡＣＵＲＥ３６９、ＩＲＧＡＣＵＲＥ６５１、ＩＲＧＡＣＵＲＥ９０７、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０１、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０２、ＩＲＧＡＣＵＲＥ７８４（以上、ＢＡＳＦ製）；ＴＲ－ＰＢＧ－３０４、ＴＲ－ＰＢＧ－３０５、ＴＲ－ＰＢＧ－３０９およびＴＲ－ＰＢＧ－３１４（以上、Ｔｒｏｎｌｙ製）等が挙げられる。 Commercially available radical initiators include ADEKA OPTOMER N-1414, N-1717, N-1919, ADEKA ARKULS NCI-831 and NCI-930 (all manufactured by ADEKA); 01, IRGACURE OXE 02, IRGACURE 784 (all manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (all manufactured by Tronly).
　熱ラジカル重合性開始剤としては、加熱によりラジカルを発生するものであれば特に制限されず従来既知の化合物を用いることが可能であり、例えば、アゾ系化合物、過酸化物および過硫酸塩等を好ましいものとして例示することができる。 The heat radical polymerizable initiator is not particularly limited as long as it generates a radical by heating, and a conventionally known compound can be used.Examples include an azo compound, a peroxide, and a persulfate. It can be exemplified as a preferable one.
　アゾ系化合物としては、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（メチルイソブチレ－ト）、２，２’－アゾビス－２，４－ジメチルバレロニトリル、１，１’－アゾビス（１－アセトキシ－１－フェニルエタン）等が挙げられる。 Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'- Azobis (1-acetoxy-1-phenylethane) and the like.
　過酸化物としては、ベンゾイルパーオキサイド、ジ－ｔ－ブチルベンゾイルパーオキサイド、ｔ－ブチルパーオキシピバレートおよびジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート等が挙げられる。 Examples of the peroxide include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butylperoxypivalate, di (4-t-butylcyclohexyl) peroxydicarbonate, and the like.
　過硫酸塩としては、過硫酸アンモニウム、過硫酸ナトリウムおよび過硫酸カリウム等の過硫酸塩等が挙げられる。 Examples of the persulfate include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.
　本発明の組成物においては、成分（Ｃ）は、これまでに例示した一種または二種以上を混合して用いることができる。 に お い て In the composition of the present invention, the component (C) can be used singly or as a mixture of two or more.
　本発明の組成物において、成分（Ｃ）の含有量は、特に限定されるものではないが、成分（Ａ）～（Ｄ）の総量１００質量部中、１～１０質量部が好ましく、また、成分（Ａ）１００質量部に対して硬化性が良好なことから好ましくは、１～１０質量部であり、さらに好ましくは３～８質量部である。成分（Ｃ）の含有量が、上記の範囲内の場合、硬化性が良好で重合性開始剤の析出を伴わない保存安定性に優れる重合性組成物が得られるので好ましい。 In the composition of the present invention, the content of the component (C) is not particularly limited, but is preferably 1 to 10 parts by mass in a total of 100 parts by mass of the components (A) to (D). The amount is preferably from 1 to 10 parts by mass, more preferably from 3 to 8 parts by mass, because the curability is good with respect to 100 parts by mass of the component (A). When the content of the component (C) is within the above range, a curable composition having good curability and excellent storage stability without precipitation of a polymerizable initiator is obtained, which is preferable.
＜カチオン重合性開始剤（Ｄ）＞
　本発明の組成物に用いられる成分（Ｄ）は、可視光線、紫外線、Ｘ線、電子線、高周波のような活性エネルギー線（以下、単に「活性エネルギー線」とも称する。）照射により酸を発生させることが可能な化合物（以下、「光カチオン重合性開始剤」とも称する。）、または加熱により酸を発生させることが可能な化合物（以下、「熱カチオン重合性開始剤」とも称する。）である。 <Cationically polymerizable initiator (D)>
The component (D) used in the composition of the present invention generates an acid upon irradiation with an active energy ray (hereinafter, also simply referred to as “active energy ray”) such as visible light, ultraviolet light, X-ray, electron beam, or high frequency. Compound (hereinafter, also referred to as "photo-cationic polymerizable initiator") or a compound capable of generating an acid by heating (hereinafter, also referred to as "thermal-cationic polymerizable initiator"). is there.
　本発明の組成物においては、成分（Ｄ）は、芳香環を有し、芳香環の数が３以上である。芳香環としては、ベンゼン環、ナフタレン環、アントラセン環等の環構造を形成する原子が全て炭素原子である芳香族炭化水素環、フラン環、ベンゾフラン環、ジベンゾフラン環、チオフェン環等の環構造を形成する原子に炭素原子以外の原子を含む芳香族複素環を挙げることができる。 に お い て In the composition of the present invention, the component (D) has an aromatic ring and the number of aromatic rings is 3 or more. The aromatic ring forms a ring structure such as an aromatic hydrocarbon ring, a furan ring, a benzofuran ring, a dibenzofuran ring, and a thiophene ring in which all atoms forming the ring structure such as a benzene ring, a naphthalene ring, and an anthracene ring are carbon atoms. And aromatic heterocycles containing atoms other than carbon atoms.
　本発明の組成物においては、成分（Ｄ）の種類としては、光カチオン重合性開始剤および熱カチオン重合性開始剤のいずれも用いることができるが、感度の観点からは、光カチオン重合性開始剤であることが好ましい。 In the composition of the present invention, as the type of the component (D), any of a cationic photopolymerizable initiator and a thermal cationic polymerizable initiator can be used. It is preferably an agent.
　光カチオン重合性開始剤としては、オニウム塩である複塩またはその誘導体、あるいはオキシムスルホネート化合物、ハロゲン含有化合物、ジアゾケトン化合物、スルホン化合物、スルホン酸化合物、ジアゾメタン化合物、ニトロベンジル化合物、ベンゾイントシレート化合物、鉄アレーン錯体、アセトフェノン誘導体化合物等を用いることができ、これらは単独でまたは２種以上を混合して使用することができる。 As the photocationic polymerization initiator, a double salt or a derivative thereof, which is an onium salt, or 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 benzoin tosylate compound, An iron arene complex, an acetophenone derivative compound, or the like can be used, and these can be used alone or as a mixture of two or more.
　本発明の組成物においては、なかでも、光カチオン重合性開始剤が、オニウム塩である複塩またはその誘導体であることが好ましい。かかる光カチオン重合性開始剤であることで、本発明の組成物は、硬化速度および接着力に優れたものとなるからである。 に お い て In the composition of the present invention, it is particularly preferable that the photocationically polymerizable initiator is an onium salt double salt or a derivative thereof. This is because the composition of the present invention is excellent in curing speed and adhesive force by being such a photocationic polymerizable initiator.
　オニウム塩である複塩またはその誘導体のうち、芳香環の数が３以上である化合物としては、下記一般式（１）で表される陽イオンと陰イオンの塩を挙げることができる。 Among the double salts or derivatives thereof that are onium salts, examples of the compound having three or more aromatic rings include cation and anion salts represented by the following general formula (1).
［Ａ］ｍ＋［Ｂ］ｍ－　　（１） [A] m + [B] m- (1)
　ここで陽イオン［Ａ］ｍ＋はオニウムであることが好ましく、その構造は、例えば、下記一般式（２）で表すことができる。 Here, the cation [A] m + is preferably onium, and its structure can be represented by, for example, the following general formula (2).
［（Ｒ１０）ａＱ］ｍ＋　　（２） [(R 10 ) a Q] m + (2)
　ここで、Ｒ１０は炭素原子数が１～６０であり、炭素原子以外の原子をいくつ含んでいても構わない有機基である。
　ａは１～５の整数である。
　ａ個のＲ１０は各々独立で、同一でも異なっていても構わない。
　ａ個のＲ１０は、少なくとも１つが、芳香環を有する上記有機基であり、ａ個のＲ１０中に含まれる芳香環の数が３以上である。ＱはＳ，Ｎ，Ｓｅ，Ｔｅ，Ｐ，Ａｓ，Ｓｂ，Ｂｉ，Ｏ，Ｉ，Ｂｒ，Ｃｌ，Ｆ，Ｎ＝Ｎからなる群から選ばれる原子あるいは原子団である。また、陽イオン［Ａ］ｍ＋中のＱの原子価をｑとしたとき、ｍ＝ａ－ｑなる関係が成り立つことが必要である。ただし、Ｎ＝Ｎは原子価０として扱う。 Here, R 10 is an organic group having 1 to 60 carbon atoms and which may contain any number of atoms other than carbon atoms.
a is an integer of 1 to 5.
a number of R 10 are each independently, it may be the same or different.
At least one R 10 is the above-mentioned organic group having an aromatic ring, and the number of aromatic rings contained in the a R 10 is 3 or more. Q is an atom or an atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Further, when the valence of Q in the cation [A] m + is q, it is necessary that the relationship m = aq holds. However, N = N is treated as valence 0.
　また、陰イオン［Ｂ］ｍ－は、ハロゲン化物錯体であることが好ましく、その構造は、例えば、下記一般式（３）で表すことができる。 The anion [B] m- is preferably a halide complex, and its structure can be represented by, for example, the following general formula (3).
［ＬＸｂ］ｍ－　　（３） [LX b ] m- (3)
　ここで、Ｌはハロゲン化物錯体の中心原子である金属または半金属（Ｍｅｔａｌｌｏｉｄ）であり、Ｂ，Ｐ，Ａｓ，Ｓｂ，Ｆｅ，Ｓｎ，Ｂｉ，Ａｌ，Ｃａ，Ｉｎ，Ｔｉ，Ｚｎ，Ｓｃ，Ｖ，Ｃｒ，Ｍｎ，Ｃｏ等である。Ｘはハロゲン原子である。ｂは３～７の整数である。また、陰イオン［Ｂ］ｍ－中のＬの原子価をｐとしたとき、ｍ＝ｂ－ｐなる関係が成り立つことが必要である。 Here, L is a metal or metalloid (Metalloid) which is the central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V , Cr, Mn, Co and the like. X is a halogen atom. b is an integer of 3 to 7. Further, when the valence of L in the anion [B] m− is p, it is necessary that the relationship m = bp holds.
　一般式（３）の陰イオン［ＬＸｂ］ｍ－の具体例としては、テトラキス（ペンタフルオロフェニル）ボレート［（Ｃ６Ｆ５）４Ｂ］－、テトラフルオロボレート（ＢＦ４）－、ヘキサフルオロホスフェート（ＰＦ６）－、ヘキサフルオロアンチモネート（ＳｂＦ６）－、ヘキサフルオロアルセネート（ＡｓＦ６）－、ヘキサクロロアンチモネート（ＳｂＣｌ６）－、トリス（ペンタフルオロメチル）トリフルオロリン酸イオン（ＦＡＰアニオン）等を挙げることができる。 Specific examples of the anion [LX b ] m- in the general formula (3) include tetrakis (pentafluorophenyl) borate [(C 6 F 5 ) 4 B] − , tetrafluoroborate (BF 4 ) − , and hexafluoro Phosphate (PF 6 ) − , hexafluoroantimonate (SbF 6 ) − , hexafluoroarsenate (AsF 6 ) − , hexachloroantimonate (SbCl 6 ) − , tris (pentafluoromethyl) trifluorophosphate ion (FAP anion) And the like.
　また、陰イオン［Ｂ］ｍ－は、下記一般式（４）で表される構造のものも好ましく用いることができる。 Further, as the anion [B] m- , those having a structure represented by the following general formula (4) can also be preferably used.
［ＬＸｂ－１（ＯＨ）］ｍ－　　（４） [LX b-1 (OH)] m- (4)
　ここで、Ｌ，Ｘ，ｂは上記と同様である。また、その他用いることのできる陰イオンとしては、過塩素酸イオン（ＣｌＯ４）－、トリフルオロメチル亜硫酸イオン（ＣＦ３ＳＯ３）－、フルオロスルホン酸イオン（ＦＳＯ３）－、トルエンスルホン酸陰イオン、トリニトロベンゼンスルホン酸陰イオン、カンファースルフォネート、ノナフロロブタンスルフォネート、ヘキサデカフロロオクタンスルフォネート、テトラアリールボレート、テトラキス（ペンタフルオロフェニル）ボレート等を挙げることができる。 Here, L, X and b are the same as above. Other usable anions include perchlorate ion (ClO 4 ) − , trifluoromethyl sulfite ion (CF 3 SO 3 ) − , fluorosulfonic acid ion (FSO 3 ) − , and toluenesulfonic acid anion , Trinitrobenzenesulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.
　本発明の組成物では、このようなオニウム塩の中でも、下記群Ｉまたは群ＩＩで表されるスルホニウムカチオンとヘキサフルオロアンチモンイオン、テトラキス（ペンタフルオロフェニル）ボレートイオン等のスルホニウム塩を使用することが特に有効である。これらの中から、その１種を単独で、または２種以上を混合して使用することができる。  In the composition of the present invention, among such onium salts, a sulfonium cation represented by the following Group I or Group II and a sulfonium salt such as hexafluoroantimony ion or tetrakis (pentafluorophenyl) borate ion may be used. Especially effective. Among these, one kind can be used alone, or two or more kinds can be used in combination.
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000014
　これらの中でも、実用面と光感度の観点から、芳香族ヨードニウム塩、芳香族スルホニウム塩を用いることが好ましく、特に、芳香族スルホニウム塩であることが好ましく、下記一般式（５）で表される芳香族スルホニウム塩が、感度の点からさらに好ましい。また、光カチオン重合性開始剤が芳香族スルホニウム塩であることで、本発明の組成物は、硬化速度および接着力に優れたものとなるからである。　  Among these, from the viewpoints of practical use and photosensitivity, it is preferable to use an aromatic iodonium salt or an aromatic sulfonium salt, particularly preferably an aromatic sulfonium salt, and represented by the following general formula (5). Aromatic sulfonium salts are more preferred in terms of sensitivity. Further, when the cationic photopolymerizable initiator is an aromatic sulfonium salt, the composition of the present invention becomes excellent in curing speed and adhesive strength.
Figure JPOXMLDOC01-appb-I000015
Figure JPOXMLDOC01-appb-I000015
　ここで、一般式（５）中、Ｒ１２１、Ｒ１２２、Ｒ１２３、Ｒ１２４、Ｒ１２５、Ｒ１２６、Ｒ１２７、Ｒ１２８、Ｒ１２９およびＲ１３０は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基または炭素原子数２～１０のエステル基を表し、
　Ｒ１３１、Ｒ１３２、Ｒ１３３およびＲ１３４は、それぞれ独立に、水素原子、ハロゲン原子または炭素原子数１～１０のアルキル基を表し、
　Ｒ１３５は、水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基または下記化学式（Ａ）～（Ｃ）より選択されるいずれかの置換基を表し、Ａｎｑ－はｑ価の陰イオンを表し、ｐは電荷を中性にする係数を表す。 Here, in the general formula (5), R 121 , R 122 , R 123 , R 124 , R 125 , R 126 , R 127 , R 128 , R 129 and R 130 each independently represent a hydrogen atom or a halogen atom Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an ester group having 2 to 10 carbon atoms,
R 131 , R 132 , R 133 and R 134 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms;
R 135 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or any substituent selected from the following chemical formulas (A) to (C), and An q- is a q-valent anion. And p represents a coefficient for neutralizing the charge.
Figure JPOXMLDOC01-appb-I000016
Figure JPOXMLDOC01-appb-I000016
　化学式（Ａ）～（Ｃ）中、Ｒ２２１、Ｒ２２２、Ｒ２２３、Ｒ２２４、Ｒ２２５、Ｒ２２６、Ｒ２２７、Ｒ２２８、Ｒ２２９、Ｒ２３０、Ｒ２３１、Ｒ２３２、Ｒ２３３、Ｒ２３４、Ｒ２３６、Ｒ２３７、Ｒ２３８、Ｒ２３９、Ｒ２４５、Ｒ２４６、Ｒ２４７、Ｒ２４８およびＲ２４９は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基または炭素原子数２～１０のエステル基を表し、
　Ｒ２４０、Ｒ２４１、Ｒ２４２、Ｒ２４３およびＲ２４４は、それぞれ独立に、水素原子、ハロゲン原子または炭素原子数１～１０のアルキル基を表し、＊は、一般式（５）中のＳとの結合位置を表す。 In the chemical formulas (A) to (C), R 221 , R 222 , R 223 , R 224 , R 225 , R 226 , R 227 , R 228 , R 229 , R 230 , R 231 , R 232 , R 233 , R 234 , R 236 , R 237 , R 238 , R 239 , R 245 , R 246 , R 247 , R 248 and R 249 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, Represents an alkoxy group having 1 to 10 carbon atoms or an ester group having 2 to 10 carbon atoms,
R 240 , R 241 , R 242 , R 243 and R 244 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms, and * represents S in the general formula (5). Represents the bonding position of
　一般式（５）で表される化合物において、Ｒ１２１、Ｒ１２２、Ｒ１２３、Ｒ１２４、Ｒ１２５、Ｒ１２６、Ｒ１２７、Ｒ１２８、Ｒ１２９、Ｒ１３０、Ｒ１３１、Ｒ１３２、Ｒ１３３、Ｒ１３４、Ｒ１３５、Ｒ２２１、Ｒ２２２、Ｒ２２３、Ｒ２２４、Ｒ２２５、Ｒ２２６、Ｒ２２７、Ｒ２２８、Ｒ２２９、Ｒ２３０、Ｒ２３１、Ｒ２３２、Ｒ２３３、Ｒ２３４、Ｒ２３６、Ｒ２３７、Ｒ２３８、Ｒ２３９、Ｒ２４０、Ｒ２４１、Ｒ２４２、Ｒ２４３、Ｒ２４４、Ｒ２４５、Ｒ２４６、Ｒ２４７、Ｒ２４８およびＲ２４９で表されるハロゲン原子としては、フッ素、塩素、臭素、ヨウ素等が挙げられる。 In the compound represented by the general formula (5), 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 , R134 , R135 , R221 , R222 , R223 , R224 , R225 , R226 , R227 , R228 , R229 , R230 , R231 , R232 , R233 , R234 , R The halogen atom represented by 236 , R237 , R238 , R239 , R240 , R241 , R242 , R243 , R244 , R245 , R246 , R247 , R248 and R249 is fluorine. , Chlorine, bromine, iodine and the like.
　Ｒ１２１、Ｒ１２２、Ｒ１２３、Ｒ１２４、Ｒ１２５、Ｒ１２６、Ｒ１２７、Ｒ１２８、Ｒ１２９、Ｒ１３０、Ｒ１３１、Ｒ１３２、Ｒ１３３、Ｒ１３４、Ｒ１３５、Ｒ２２１、Ｒ２２２、Ｒ２２３、Ｒ２２４、Ｒ２２５、Ｒ２２６、Ｒ２２７、Ｒ２２８、Ｒ２２９、Ｒ２３０、Ｒ２３１、Ｒ２３２、Ｒ２３３、Ｒ２３４、Ｒ２３６、Ｒ２３７、Ｒ２３８、Ｒ２３９、Ｒ２４０、Ｒ２４１、Ｒ２４２、Ｒ２４３、Ｒ２４４、Ｒ２４５、Ｒ２４６、Ｒ２４７、Ｒ２４８およびＲ２４９で表される炭素原子数１～１０のアルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、ｓ－ブチル、ｔ－ブチル、イソブチル、アミル、イソアミル、ｔ－アミル、ヘキシル、シクロヘキシル、ヘプチル、オクチル、ノニル、エチルオクチル、２－メトキシエチル、３－メトキシプロピル、４－メトキシブチル、２－ブトキシエチル、メトキシエトキシエチル、メトキシエトキシエトキシエチル、３－メトキシブチル、２－メチルチオエチル、フルオロメチル、ジフルオロメチル、トリフルオロメチル、クロロメチル、ジクロロメチル、トリクロロメチル、ブロモメチル、ジブロモメチル、トリブロモメチル、ジフルオロエチル、トリクロロエチル、ジクロロジフルオロエチル、ペンタフルオロエチル、ヘプタフルオロプロピル、ノナフルオロブチル、デカフルオロペンチル、トリデカフルオロヘキシル、ペンタデカフルオロヘプチル、ヘプタデカフルオロオクチル、メトキシメチル、１，２－エポキシエチル、メトキシエチル、メトキシエトキシメチル、メチルチオメチル、エトキシエチル、ブトキシメチル、ｔ－ブチルチオメチル、４－ペンテニルオキシメチル、トリクロロエトキシメチル、ビス（２－クロロエトキシ）メチル、メトキシシクロヘキシル、１－（２－クロロエトキシ）エチル、１－メチル－１－メトキシエチル、エチルジチオエチル、トリメチルシリルエチル、ｔ－ブチルジメチルシリルオキシメチル、２－（トリメチルシリル）エトキシメチル、ｔ－ブトキシカルボニルメチル、エチルオキシカルボニルメチル、エチルカルボニルメチル、ｔ－ブトキシカルボニルメチル、アクリロイルオキシエチル、メタクリロイルオキシエチル、２－メチル－２－アダマンチルオキシカルボニルメチル、アセチルエチル、２－メトキシ－１－プロペニル、ヒドロキシメチル、２－ヒドロキシエチル、１－ヒドロキシエチル、２－ヒドロキシプロピル、３－ヒドロキシプロピル、３－ヒドロキシブチル、４－ヒドロキシブチル、１，２－ジヒドロキシエチル等が挙げられる。 R 121 , R 122 , R 123 , R 124 , R 125 , R 126 , R 127 , R 128 , R 129 , R 130 , R 131 , R 132 , R 133 , R 134 , R 135 , R 221 , R 222 , R223 , R224 , R225 , R226 , R227 , R228 , R229 , R230 , R231 , R232 , R233 , R234 , R236 , R237 , R238 , R239 , R239 Examples of the alkyl group having 1 to 10 carbon atoms represented by 240 , R 241 , R 242 , R 243 , R 244 , R 245 , R 246 , R 247 , R 248 and R 249 include methyl, ethyl, propyl, Isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, Rohexyl, heptyl, octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, Fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, Decafluoropentyl, tridecafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl, methoxymethyl, 1,2-epoxyethyl, methoxy Ethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, t-butylthiomethyl, 4-pentenyloxymethyl, trichloroethoxymethyl, bis (2-chloroethoxy) methyl, methoxycyclohexyl, 1- (2-chloroethoxy ) Ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl, trimethylsilylethyl, t-butyldimethylsilyloxymethyl, 2- (trimethylsilyl) ethoxymethyl, t-butoxycarbonylmethyl, ethyloxycarbonylmethyl, ethylcarbonylmethyl, t-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl, acetylethyl, 2-methoxy-1-propeni , Hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, 1,2-dihydroxyethyl and the like.
　Ｒ１２１、Ｒ１２２、Ｒ１２３、Ｒ１２４、Ｒ１２５、Ｒ１２６、Ｒ１２７、Ｒ１２８、Ｒ１２９、Ｒ１３０、Ｒ２２１、Ｒ２２２、Ｒ２２３、Ｒ２２４、Ｒ２２５、Ｒ２２６、Ｒ２２７、Ｒ２２８、Ｒ２２９、Ｒ２３０、Ｒ２３１、Ｒ２３２、Ｒ２３３、Ｒ２３４、Ｒ２３６、Ｒ２３７、Ｒ２３８、Ｒ２３９、Ｒ２４５、Ｒ２４６、Ｒ２４７、Ｒ２４８およびＲ２４９で表される炭素原子数１～１０のアルコキシ基としては、メトキシ、エトキシ、プロピルオキシ、イソプロピルオキシ、ブチルオキシ、ｓ－ブチルオキシ、ｔ－ブチルオキシ、イソブチルオキシ、ペンチルオキシ、イソアミルオキシ、ｔ－アミルオキシ、ヘキシルオキシ、シクロヘキシルオキシ、シクロヘキシルメチルオキシ、テトラヒドロフラニルオキシ、テトラヒドロピラニルオキシ、２－メトキシエチルオキシ、３－メトキシプロピルオキシ、４－メトキシブチルオキシ、２－ブトキシエチルオキシ、メトキシエトキシエチルオキシ、メトキシエトキシエトキシエチルオキシ、３－メトキシブチルオキシ、２－メチルチオエチルオキシ、トリフルオロメチルオキシ等が挙げられる。 R121 , R122 , R123 , R124 , R125 , R126 , R127 , R128 , R129 , R130 , R221 , R222 , R223 , R224 , R225 , R226 , R227 , R228 , R229 , R230 , R231 , R232 , R233 , R234 , R236 , R237 , R238 , R239 , R245 , R246 , R247 , R248 , R248 and R249 . Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, s-butyloxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, Cyclohexyloxy, cyclohexylmethyloxy , Tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethyloxy, 3-methoxypropyloxy, 4-methoxybutyloxy, 2-butoxyethyloxy, methoxyethoxyethyloxy, methoxyethoxyethoxyethyloxy, 3-methoxybutyloxy , 2-methylthioethyloxy, trifluoromethyloxy and the like.
　Ｒ１２１、Ｒ１２２、Ｒ１２３、Ｒ１２４、Ｒ１２５、Ｒ１２６、Ｒ１２７、Ｒ１２８、Ｒ１２９、Ｒ１３０、Ｒ２２１、Ｒ２２２、Ｒ２２３、Ｒ２２４、Ｒ２２５、Ｒ２２６、Ｒ２２７、Ｒ２２８、Ｒ２２９、Ｒ２３０、Ｒ２３１、Ｒ２３２、Ｒ２３３、Ｒ２３４、Ｒ２３６、Ｒ２３７、Ｒ２３８、Ｒ２３９、Ｒ２４５、Ｒ２４６、Ｒ２４７、Ｒ２４８およびＲ２４９で表される炭素原子数２～１０のエステル基としては、メトキシカルボニル、エトキシカルボニル、イソプロピルオキシカルボニル、フェノキシカルボニル、アセトキシ、プロピオニルオキシ、ブチリルオキシ、クロロアセチルオキシ、ジクロロアセチルオキシ、トリクロロアセチルオキシ、トリフルオロアセチルオキシ、ｔ－ブチルカルボニルオキシ、メトキシアセチルオキシ、ベンゾイルオキシ等が挙げられる。 R121 , R122 , R123 , R124 , R125 , R126 , R127 , R128 , R129 , R130 , R221 , R222 , R223 , R224 , R225 , R226 , R227 , R228 , R229 , R230 , R231 , R232 , R233 , R234 , R236 , R237 , R238 , R239 , R245 , R246 , R247 , R248 , R248 and R249 . Examples of the ester group having 2 to 10 carbon atoms include methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy, propionyloxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy , T -Butylcarbonyloxy, methoxyacetyloxy, benzoyloxy and the like.
　一般式（５）中のｐＡｎｑ－で表されるｑ価のアニオンとしては、上述の陰イオン［Ｂ］ｍ－として挙げたもののうち、所定の価数のアニオンを用いることができる。 As the q-valent anion represented by pAn q- in the general formula (5), an anion having a predetermined valence can be used among the above-mentioned anions [B] m- .
　本発明の組成物においては、Ｒ１３５が、化学式（Ａ）～（Ｃ）より選択されるものであることが好ましく、なかでも、化学式（Ａ）または（Ｃ）より選択されるものであることが好ましい。Ｒ１３５が上述の構造を有することにより、成分（Ｄ）の分散安定性と硬化速度および接着力とのバランスに優れたものとなるからである。本発明の組成物においては、成分（Ｄ）の分散安定性の観点からは、Ｒ１３５が化学式（Ｃ）であるものであることが好ましい。一方、硬化速度および接着力により優れたものとする観点からは、Ｒ１３５が化学式（Ａ）であるものであることが好ましい。本発明の組成物においては、成分（Ｄ）の分散安定性と硬化速度および接着力とのバランスに優れたものとする観点からは、成分（Ｄ）は、Ｒ１３５が化学式（Ａ）であるものと、化学式（Ｃ）であるものとの両者を含むことが好ましい。 In the composition of the present invention, R 135 is preferably selected from the chemical formulas (A) to (C), and particularly preferably selected from the chemical formulas (A) or (C). Is preferred. This is because when R 135 has the above-mentioned structure, the dispersion stability of the component (D) and the balance between the curing speed and the adhesive strength are excellent. In the composition of the present invention, from the viewpoint of the dispersion stability of the component (D), it is preferable that R 135 is a compound represented by the chemical formula (C). On the other hand, from the viewpoint of improving the curing speed and the adhesive strength, it is preferable that R 135 is a compound represented by the chemical formula (A). In the composition of the present invention, R 135 of the component (D) is represented by the chemical formula (A) from the viewpoint of achieving an excellent balance between the dispersion stability of the component (D), the curing speed, and the adhesive strength. It is preferable to include both the compound represented by the formula (C)
　成分（Ｄ）は、Ｒ１３５が化学式（Ａ）であるものと、化学式（Ｃ）であるものとの両者を含む場合、Ｒ１３５が化学式（Ａ）であるものの含有量は、化学式（Ｃ）であるもの１００質量部に対して、１０質量部以上２００質量部以下とすることができ、なかでも、５０質量部以上、２００質量部以下であることが好ましく、８０質量部以上１２０質量部以下であることが好ましい。かかる範囲の含有量であることで、成分（Ｄ）の分散安定性と硬化速度および接着力とのバランスに優れたものとなるからである。 Component (D), if it contains both as R 135 is as a chemical formula (A), Formula (C), the content of those R 135 is a chemical formula (A), formula (C) It can be 10 parts by mass or more and 200 parts by mass or less, preferably 50 parts by mass or more and 200 parts by mass or less, and preferably 80 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass. It is preferred that When the content is in such a range, the dispersion stability of the component (D), the curing speed, and the balance between the adhesive strength are excellent.
　Ｒ１２１、Ｒ１２２、Ｒ１２３、Ｒ１２４、Ｒ１２５、Ｒ１２６、Ｒ１２７、Ｒ１２８、Ｒ１２９、Ｒ１３０、Ｒ１３１、Ｒ１３２、Ｒ１３３およびＲ１３４は、水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基または炭素原子数２～１０のエステル基であるが、なかでも、水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基であることが好ましく、特に、水素原子であることが好ましい。上述の官能基であることで、本発明の組成物は、成分（Ｄ）の分散安定性と硬化速度および接着力とのバランスに優れたものとなるからである。また、上記カチオン重合性開始剤が合成容易なものとなるからである。 R 121 , R 122 , R 123 , R 124 , R 125 , R 126 , R 127 , R 128 , R 129 , R 130 , R 131 , R 132 , R 133 and R 134 are a hydrogen atom, a halogen atom, a carbon atom An alkyl group having 1 to 10 atoms, an alkoxy group having 1 to 10 carbon atoms or an ester group having 2 to 10 carbon atoms, and among them, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms It is preferably an alkoxy group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom. This is because the composition of the present invention has an excellent balance between the dispersion stability of the component (D), the curing speed, and the adhesive strength due to the above-mentioned functional group. Also, the above-mentioned cationically polymerizable initiator can be easily synthesized.
　Ｒ２２１、Ｒ２２２、Ｒ２２３、Ｒ２２４、Ｒ２２５、Ｒ２２６、Ｒ２２７、Ｒ２２８、Ｒ２２９、Ｒ２３０、Ｒ２３１、Ｒ２３２、Ｒ２３３、Ｒ２３４、Ｒ２３６、Ｒ２３７、Ｒ２３８、Ｒ２３９、Ｒ２４０、Ｒ２４１、Ｒ２４２、Ｒ２４３、Ｒ２４４、Ｒ２４５、Ｒ２４６、Ｒ２４７、Ｒ２４８およびＲ２４９は水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基であることが好ましく、特に、水素原子であることが好ましい。上述の官能基であることで、本発明の組成物は、成分（Ｄ）の分散安定性と硬化速度および接着力とのバランスに優れたものとなるからである。また、上記カチオン重合性開始剤が合成容易なものとなるからである。 R 221 , R 222 , R 223 , R 224 , R 225 , R 226 , R 227 , R 228 , R 229 , R 230 , R 231 , R 232 , R 233 , R 234 , R 236 , R 237 , R 238 , R 239 , R 240 , R 241 , R 242 , R 243 , R 244 , R 245 , R 246 , R 247 , R 248 and R 249 are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, It is preferably an alkoxy group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom. This is because the composition of the present invention has an excellent balance between the dispersion stability of the component (D), the curing speed, and the adhesive strength due to the above-mentioned functional group. Also, the above-mentioned cationically polymerizable initiator can be easily synthesized.
　本発明の組成物においては、成分（Ｄ）の含有量としては、所望の硬化速度および接着力を得られるものであればよく、例えば、本発明の組成物の固形分１００質量部中に、０．１質量部以上１０質量部以下であることが好ましく、なかでも、０．５質量部以上８質量部以下であることが好ましく、特に、１．０質量部以上７質量部以下であることが好ましく、なかでも特に１．５質量部以上６質量部以下であることが好ましく、なかでも特に、２．０質量部以上５質量部以下であることが好ましい。かかる範囲の含有量であることで、本発明の組成物は、成分（Ｄ）の分散安定性と硬化速度および接着力とのバランスに優れたものとなる。なお、本発明の組成物の固形分とは、溶剤以外の全ての成分を含むものである。 In the composition of the present invention, the content of the component (D) is not particularly limited as long as a desired curing rate and adhesive strength can be obtained. For example, in the solid content of 100 parts by mass of the composition of the present invention, It is preferably from 0.1 to 10 parts by mass, more preferably from 0.5 to 8 parts by mass, and particularly preferably from 1.0 to 7 parts by mass. And more preferably 1.5 to 6 parts by mass, and particularly preferably 2.0 to 5 parts by mass. When the content is in such a range, the composition of the present invention has an excellent balance between the dispersion stability of the component (D), the curing speed, and the adhesive strength. In addition, the solid content of the composition of the present invention includes all components other than the solvent.
　カチオン重合性開始剤（Ｄ）の市販品としては、例えば、「ＣＰＩ－１００Ｐ」、「ＣＰＩ－１０１Ａ」（以上、サンアプロ株式会社製）、；「ＩＲＧＡＣＵＲＥ　２５０」（ＢＡＳＦ　ＳＥ社製）、「アデカオプトマーＳＰ－１７２」、「アデカオプトマーＳＰ－１７０」、「アデカオプトマーＳＰ－１５２」、「アデカオプトマーＳＰ－１５０」（以上、株式会社ＡＤＥＫＡ製）、；「サンエイド　ＳＩ－６０Ｌ」、「サンエイド　ＳＩ－８０Ｌ」、「サンエイド　ＳＩ－１００Ｌ」、「サンエイド　ＳＩ－１５０Ｌ」（以上、三新化学工業株式会社製）等が挙げられる。 Commercial products of the cationically polymerizable initiator (D) include, for example, “CPI-100P” and “CPI-101A” (manufactured by San-Apro Co., Ltd.); “IRGACURE 250” (manufactured by BASF SE), “ADEKA "Optomer SP-172", "ADEKA OPTOMER SP-170", "ADEKA OPTOMER SP-152", "ADEKA OPTOMER SP-150" (all manufactured by ADEKA CORPORATION); "SAN AID @ SI-60L"; "Sun-Aid SI-80L", "Sun-Aid SI-100L", "Sun-Aid SI-150L" (all manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.
　本発明の組成物は、硬化速度および接着力に優れたものとの観点から、成分（Ｄ）の含有量としては、成分（Ａ）～（Ｄ）の総量１００質量部中、１～１０質量部が好ましく、また、成分（Ｂ）１００質量部に対して、１質量部以上８質量部以下であることが好ましく、特に、１．５質量部以上７質量部以下であることが好ましく、なかでも特に２．０質量部以上６質量部以下であることが好ましく、なかでも特に、３．０質量部以上５質量部以下であることが好ましい。 The composition of the present invention has a component (D) content of 1 to 10 parts by mass in a total of 100 parts by mass of the components (A) to (D) from the viewpoint of excellent curing speed and adhesive strength. Is preferably 1 part by mass to 8 parts by mass, more preferably 1.5 parts by mass to 7 parts by mass with respect to 100 parts by mass of the component (B). However, it is particularly preferably from 2.0 parts by mass to 6 parts by mass, and particularly preferably from 3.0 parts by mass to 5 parts by mass.
＜溶剤＞
　本発明の組成物には溶剤を用いてもよく、溶剤は、組成物中の各成分を分散または溶解可能なものであり、常温常圧下で液体の化合物である。なお、溶剤としては、アクリル基、メタクリル基、ビニル基、エポキシ基、オキセタン基を有する化合物を含まないものを用いることができる。 <Solvent>
A solvent may be used in the composition of the present invention. The solvent is a compound capable of dispersing or dissolving each component in the composition, and is a liquid compound at normal temperature and normal pressure. Note that as the solvent, a solvent that does not include a compound having an acryl group, a methacryl group, a vinyl group, an epoxy group, or an oxetane group can be used.
　このような溶剤としては、水、有機溶剤のいずれも用いることができるが、有機溶剤を好ましく用いることができる。有機溶剤の含有量としては、所望の硬化速度および接着力が得られるものであればよく、溶剤１００質量部中に８０質量部以上であることが好ましく、９０質量部以上であることが好ましく、なかでも９５質量部以上であることが好ましく、特に、１００質量部、すなわち、溶剤として有機溶剤のみを含むことが好ましい。含有量がかかる範囲であることで、本発明の組成物は、成分（Ｃ）および成分（Ｄ）の分散安定性と硬化速度および接着力とのバランスに優れたものとなるからである。 水 Either water or an organic solvent can be used as such a solvent, but an organic solvent can be preferably used. The content of the organic solvent is not particularly limited as long as a desired curing rate and adhesive strength can be obtained, and is preferably 80 parts by mass or more, more preferably 90 parts by mass or more in 100 parts by mass of the solvent, Among them, the amount is preferably 95 parts by mass or more, particularly preferably 100 parts by mass, that is, it is preferable to contain only an organic solvent as a solvent. When the content is in such a range, the composition of the present invention becomes excellent in the balance between the dispersion stability of the component (C) and the component (D), the curing speed, and the adhesive strength.
　有機溶剤としては、プロピレンカーボネート、エチレンカーボネート、１，２－ブチレンカーボネート、ジメチルカーボネートおよびジエチルカーボネート等のカーボネート類；アセトン、メチルエチルケトン、シクロヘキサノン、メチルイソアミルケトン、２－ヘプタノン等のケトン類；エチレングリコール、エチレングリコールモノアセテート、ジエチレングリコール、ジエチレングリコールモノアセテート、プロピレングリコール、プロピレングリコールモノアセテート、ジプロピレングリコールおよびジプロピレングリコールモノアセテートのモノメチルエーテル、モノエチルエーテル、モノプロピルエーテル、モノブチルエーテルまたはモノフェニルエーテル等の多価アルコール類およびその誘導体；ジオキサンのような環式エーテル類；蟻酸エチル、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸ブチル、ピルビン酸メチル、アセト酢酸メチル、アセト酢酸エチル、ピルビン酸エチル、エトキシ酢酸エチル、メトキシプロピオン酸メチル、エトキシプロピオン酸エチル、２－ヒドロキシプロピオン酸メチル、２－ヒドロキシプロピオン酸エチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、２－ヒドロキシ－３－メチルブタン酸メチル、３－メトキシブチルアセテート、３－メチル－３－メトキシブチルアセテート等のエステル類；トルエン、キシレン等の芳香族炭化水素類；γ－カプロラクトン、δ－カプロラクトン、ε－カプロラクトン、ジメチル－ε－カプロラクトン、δ－バレロラクトン、γ－バレロラクトン、およびγ－ブチロラクトン等のラクトン類等が挙げられ、これらの溶媒は１種または２種以上の混合溶媒として使用することができる。有機溶剤の中でも、多価アルコール類の誘導体、ラクトン類、カーボネート類であることが好ましく、特に、カーボネート類であることが好ましく、なかでも特に、プロピレンカーボネートであることが好ましい。これらの有機溶剤を用いることで、本発明の組成物は、成分（Ｃ）および成分（Ｄ）の分散安定性と硬化速度および接着力とのバランスに優れたものとなるからである。 Examples of the organic solvent include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate and diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and 2-heptanone; ethylene glycol, ethylene Polyhydric alcohols such as glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol and dipropylene glycol monoacetate, such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether and monophenyl ether And derivatives thereof; cyclic ethers such as dioxane Ters: ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Esters such as acetate; aromatic hydrocarbons such as toluene and xylene; γ-caprolactone, δ-caprolactone, ε-caprolactone, dimethyl-ε-caprolactone, δ-valerolactone, γ-valerolactone, and γ-butyrolactone No These solvents may be used as one kind or a mixed solvent of two or more kinds. Among the organic solvents, derivatives of polyhydric alcohols, lactones, and carbonates are preferable, particularly, carbonates are preferable, and propylene carbonate is particularly preferable. By using these organic solvents, the composition of the present invention has an excellent balance between the dispersion stability of the component (C) and the component (D) and the curing speed and adhesive strength.
　有機溶剤の分子量としては、成分（Ａ）～成分（Ｄ）の溶解性または分散安定性と硬化速度および接着力とのバランスに優れたものとなる観点からは、５０以上３００以下であることが好ましく、なかでも、８０以上２００以下であることが好ましく、９０以上１５０以下であることが好ましい。 The molecular weight of the organic solvent is preferably 50 or more and 300 or less from the viewpoint of achieving an excellent balance between the solubility or dispersion stability of the components (A) to (D) and the curing speed and adhesive strength. Preferably, it is preferably 80 or more and 200 or less, and more preferably 90 or more and 150 or less.
　有機溶剤の沸点としては、硬化物からの揮散の少ないものとする観点からは、１００℃以上３５０℃以下であることが好ましく、なかでも、１３０℃以上３００℃以下であることが好ましく、特に、２００℃以上３００℃以下であることが好ましく、中でも特に２００℃以上２５０℃以下であることが好ましい。なお、沸点は、大気圧下における値を表すものである。 The boiling point of the organic solvent is preferably from 100 ° C. to 350 ° C., and more preferably from 130 ° C. to 300 ° C., particularly from the viewpoint of reducing the volatilization from the cured product. The temperature is preferably from 200 ° C to 300 ° C, particularly preferably from 200 ° C to 250 ° C. The boiling point indicates a value under the atmospheric pressure.
＜その他の成分＞
　本発明の組成物は、上記の成分以外も必要に応じてその他の成分を含むことができる。その他の成分は、必要に応じて、無機フィラー、有機フィラー、顔料、シランカップリング剤、染料等の着色剤、光増感剤、消泡剤、増粘剤、チクソ剤、界面活性剤、レベリング剤、難燃剤、可塑剤、安定剤、重合禁止剤、紫外線吸収剤、酸化防止剤、静電防止剤、流動調整剤および接着促進剤等の各種樹脂添加物等を含むことができる。その他の成分の合計の含有量は、本発明の組成物の固形分中に３０質量％以下が好ましい。 <Other ingredients>
The composition of the present invention can contain other components as required in addition to the above components. Other components, if necessary, include inorganic fillers, organic fillers, pigments, silane coupling agents, coloring agents such as dyes, photosensitizers, defoamers, thickeners, thixotropic agents, surfactants, and leveling. Agents, flame retardants, plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow regulators, adhesion promoters, and other various resin additives. The total content of other components is preferably 30% by mass or less in the solid content of the composition of the present invention.
　本発明の組成物の製造方法としては、上記各成分を均一に混合できる方法であれば特に限定されるものではなく、例えば、成分（Ａ）および成分（Ｂ）に対して、成分（Ｃ）、成分（Ｄ）および溶剤を添加して混合する方法を挙げることができる。なお、混合方法については、公知の混合装置を用いる方法を採用でき、例えば、３本ロール、サンドミル、ボールミル等を用いる方法を挙げることができる。 The method for producing the composition of the present invention is not particularly limited as long as the above components can be uniformly mixed. For example, the components (C) and (B) may be added to the components (A) and (B). , Component (D) and a solvent. In addition, as a mixing method, a method using a known mixing device can be adopted, and for example, a method using a three-roll, sand mill, ball mill, or the like can be used.
　本発明の組成物の硬化方法としては、成分（Ｃ）および成分（Ｄ）の種類に応じて適宜設定されるものである。硬化方法としては、成分（Ｃ）および成分（Ｄ）が光ラジカル重合開始剤および光カチオン重合性開始剤である場合には、本発明の組成物に対して、活性エネルギー線を照射する活性エネルギー線照射処理を行う方法を用いることができる。 硬化 The method of curing the composition of the present invention is appropriately set according to the types of the components (C) and (D). As the curing method, when the component (C) and the component (D) are a photoradical polymerization initiator and a photocationic polymerization initiator, the active energy of irradiating the composition of the present invention with an active energy ray is used. A method of performing a line irradiation treatment can be used.
　活性エネルギー線としては、可視光線、紫外線、電子線、Ｘ線、放射線、高周波等を挙げることができ、紫外線が経済的に最も好ましい。紫外線の光源としては、紫外線レーザー、水銀ランプ、キセノンレーザ、メタルハライドランプ等が挙げられる。また、本発明の組成物はＬＥＤ光源を照射により硬化させることが可能である。ＬＥＤ光源からの活性エネルギー線としては、紫外線が挙げられる。ＬＥＤ光源からの活性エネルギー線の波長としては、３５０ｎｍ～４０５ｎｍが挙げられる。本発明の組成物は、カチオン重合性開始剤が光カチオン重合性開始剤である場合には、活性エネルギー線照射により通常は０．１秒～数分後に指触乾燥状態或いは溶媒不溶性の状態に硬化することができる。活性エネルギー線および活性エネルギー線への暴露時間としては、国際公開２０１３／１７２１４５号公報等に記載の内容と同様とすることができる。 The active energy ray includes visible light, ultraviolet light, electron beam, X-ray, radiation, high frequency and the like, and ultraviolet light is most economically preferable. Examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp. Further, the composition of the present invention can be cured by irradiation with an LED light source. The active energy rays from the LED light source include ultraviolet rays. The wavelength of the active energy ray from the LED light source may be 350 nm to 405 nm. When the cationically polymerizable initiator is a photo-cationically polymerizable initiator, the composition of the present invention is usually brought into a dry state to the touch or a solvent-insoluble state after 0.1 seconds to several minutes by irradiation with active energy rays. Can be cured. The active energy ray and the exposure time to the active energy ray can be the same as those described in WO 2013/172145 or the like.
　本発明の組成物の硬化方法としては、成分（Ｃ）が熱ラジカル重合性開始剤である場合、または成分（Ｄ）が熱カチオン重合性開始剤である場合には、本発明の組成物に対して、加熱処理を行う方法を用いることができる。本発明の組成物を加熱により硬化させる場合の条件は、７０℃～２５０℃で１～１００分とすることができる。プレベイク（ＰＡＢ；Ｐｒｅ　ａｐｐｌｉｅｄ　ｂａｋｅ）した後、加圧して、ポストベイク（ＰＥＢ；Ｐｏｓｔ　ｅｘｐｏｓｕｒｅ　ｂａｋｅ）してもよいし、異なる数段階の温度でベイクしてもよい。加熱条件は各成分の種類および配合割合によって異なるが、例えば、７０℃～１８０℃で、オーブンなら５分間～１５分間、ホットプレートなら１～５分間とすることができる。その後、塗膜を硬化させるために１８０℃～２５０℃、好ましくは２００℃～２５０℃で、オーブンなら３０分間～９０分間、ホットプレートなら５分間～３０分間加熱処理することによって硬化膜を得ることができる。 As a method for curing the composition of the present invention, when the component (C) is a thermal radically polymerizable initiator, or when the component (D) is a thermocationically polymerizable initiator, the composition of the present invention On the other hand, a method of performing a heat treatment can be used. The conditions for curing the composition of the present invention by heating may be from 70 ° C. to 250 ° C. for 1 to 100 minutes. After pre-baking (PAB; Pre-applied bake), pressure may be applied to perform post-baking (PEB; Post-exposure bake), or baking may be performed at several different temperatures. The heating conditions vary depending on the type and mixing ratio of each component. For example, the heating temperature may be 70 ° C. to 180 ° C., 5 minutes to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Then, a cured film is obtained by heating at 180 ° C. to 250 ° C., preferably 200 ° C. to 250 ° C. for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate to cure the coating film. Can be.
　本発明の組成物の用途としては、硬化物を形成して使用する用途であれば特に限定されるものではなく、光学フィルム、接着剤、メガネ、撮像用レンズに代表される光学材料、塗料、コーティング剤、ライニング剤、インキ、高屈折材料、水溶性材料、半導体・ディスプレイ・ＭＥＭＳ・医療機器用レジスト、液状レジスト、印刷版、絶縁ワニス、絶縁シート、積層板、プリント基盤、半導体装置用・ＬＥＤパッケージ用・液晶注入口用・有機ＥＬ用・光素子用・電気絶縁用・電子部品用・分離膜用等の封止剤、成形材料、パテ、ガラス繊維含浸剤、目止め剤、半導体用・太陽電池用等のパッシベーション膜、層間絶縁膜、保護膜、カラーフィルターの保護膜、スペーサー、ＤＮＡ分離チップ、マイクロリアクター、ナノバイオデバイス、ハードディスク用記録材料、固体撮像素子、発光ダイオード、有機発光デバイス、ルミネセントフィルム、蛍光フィルム、アクチュエーター、ホログラム、プラズモンデバイス、偏光板、偏光フィルム、位相差フィルム、液晶表示装置のバックライトに使用されるプリズムレンズシート、プロジェクションテレビ等のスクリーンに使用されるフレネルレンズシート、レンチキュラーレンズシート等のレンズシートのレンズ部、またはこのようなシートを用いたバックライト等、マイクロレンズ等の光学レンズ、光学素子、光コネクター、光導波路、光学的造形用注型剤等を挙げることができる。 The use of the composition of the present invention is not particularly limited as long as it is used to form and use a cured product.Optical films, adhesives, glasses, optical materials represented by imaging lenses, paints, Coating agents, lining agents, inks, high refractive materials, water-soluble materials, resists for semiconductors, displays, MEMS, medical equipment, liquid resists, printing plates, insulating varnishes, insulating sheets, laminates, printed boards, semiconductor devices, LEDs Sealants, molding materials, putties, glass fiber impregnants, fillers, semiconductors, etc. for packages, liquid crystal fillers, organic EL, optical devices, electrical insulation, electronic components, separation membranes, etc. Passivation films for solar cells, interlayer insulating films, protective films, protective films for color filters, spacers, DNA separation chips, microreactors, nanobio devices, Used for hard disk recording materials, solid-state imaging devices, light-emitting diodes, organic light-emitting devices, luminescent films, fluorescent films, actuators, holograms, plasmon devices, polarizing plates, polarizing films, retardation films, and backlights for liquid crystal displays Prism lens sheets, Fresnel lens sheets used for screens of projection televisions, etc., lens parts of lens sheets such as lenticular lens sheets, or backlights using such sheets, optical lenses such as microlenses, optical elements, Examples include an optical connector, an optical waveguide, and a casting agent for optical modeling.
　本発明の組成物は、硬化速度および接着力に優れているとの効果をより効果的に発揮できる観点から、接着剤に用いられることが好ましい。接着剤の具体的な用途としては、メガネや撮像用レンズに代表される光学材料、積層板やプリント基盤に代表される電子材料用途、ヘッドアップディスプレイやカーナビゲーションに代表される車載用機器および有機ＥＬや液晶に代表されるディスプレイパネル等の各種の用途に使用することができる。なかでも、透明性が要求される用途に用いられることが好ましく、特に、光学材料、車載用機器、ディスプレイパネル等の用途に用いられることが好ましい。 組成 The composition of the present invention is preferably used for an adhesive from the viewpoint of more effectively exhibiting the effects of excellent curing speed and adhesive strength. Specific applications of the adhesive include optical materials such as glasses and imaging lenses, electronic materials such as laminates and printed boards, in-vehicle devices such as head-up displays and car navigation systems, and organic materials. It can be used for various applications such as display panels represented by EL and liquid crystal. Above all, it is preferably used for applications requiring transparency, and particularly preferably used for applications such as optical materials, in-vehicle equipment, and display panels.
　本発明の組成物を接着剤として用いる場合、本発明の接着剤により接着される被着体は、無機材料、有機材料のいずれも用いることができる。 (4) When the composition of the present invention is used as an adhesive, an adherend adhered by the adhesive of the present invention may be an inorganic material or an organic material.
　有機材料としては、例えば、ジアセチルセルロース、トリアセチルセルロース（ＴＡＣ）、プロピオニルセルロース、ブチリルセルロース、アセチルプロピオニルセルロース、ニトロセルロース等のセルロースエステル；ポリアミド；ポリイミド；ポリウレタン；エポキシ化合物；ポリカーボネート；ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリ－１，４－シクロヘキサンジメチレンテレフタレート、ポリエチレン－１，２－ジフェノキシエタン－４，４’－ジカルボキシレート、ポリブチレンテレフタレート等のポリエステル；ポリスチレン；ポリエチレン、ポリプロピレン、ポリメチルペンテン、ポリテトラフルオロエチレン、シクロオレフィンポリマー等のポリオレフィン；ポリビニルアルコール、ポリ酢酸ビニル、ポリ塩化ビニル、ポリフッ化ビニル等のビニル化合物；ポリメチルメタクリレート、ポリアクリル酸エステル等のアクリル系樹脂；ポリカーボネート；ポリスルホン；ポリエーテルスルホン；ポリエーテルケトン；ポリエーテルイミド；ポリオキシエチレン、ノルボルネン樹脂等の高分子材料が挙げられる。また、無機材料としては、例えば、ソーダガラスおよび石英ガラス等のガラス、金属、金属酸化物等を挙げることができる。 Examples of the organic material include cellulose esters such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, and nitrocellulose; polyamides; polyimides; polyurethanes; epoxy compounds; polycarbonates; Polyesters such as naphthalate, polybutylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate; polystyrene; polyethylene, polypropylene, Polyolefins such as polymethylpentene, polytetrafluoroethylene and cycloolefin polymers; Vinyl compounds such as alcohol, polyvinyl acetate, polyvinyl chloride and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; Polymer materials such as oxyethylene and norbornene resin are exemplified. Examples of the inorganic material include glass such as soda glass and quartz glass, metal, and metal oxide.
＜接着剤＞
　次に、本発明の接着剤について説明する。
　本発明の接着剤は、本発明の組成物を含むものである。本発明の組成物を含むものであることで、本発明の接着剤は、硬化速度、接着力および耐水性に優れている。 <Adhesive>
Next, the adhesive of the present invention will be described.
The adhesive of the present invention contains the composition of the present invention. By containing the composition of the present invention, the adhesive of the present invention is excellent in curing speed, adhesive strength and water resistance.
　本発明の接着剤は、本発明の組成物を用いて製造することができる。本発明の接着剤は、本発明の組成物のみからなるものであってもよく、本発明の組成物と、接着剤を製造する際に用いられることが知られている各種の添加剤等を公知の混合装置を用いて混合することで製造することができる。なお、本発明の組成物および接着剤の用途については、組成物の項に記載の内容と同様とすることができるので、ここでの説明は省略する。 接着 The adhesive of the present invention can be produced using the composition of the present invention. The adhesive of the present invention may be composed of only the composition of the present invention, and the composition of the present invention and various additives known to be used when manufacturing the adhesive. It can be manufactured by mixing using a known mixing device. The use of the composition and the adhesive of the present invention can be the same as those described in the section of the composition, and thus the description thereof is omitted.
　本発明の接着剤が、２つの部材を接着する接着剤として用いられる場合、本発明の接着剤の硬化後の厚みとしては、本発明の接着剤の用途等に応じて適宜設定されるものであるが、例えば、０．５μｍ以上１０μｍ以下とすることができる。 When the adhesive of the present invention is used as an adhesive for bonding two members, the thickness after curing of the adhesive of the present invention is appropriately set according to the use of the adhesive of the present invention. However, for example, the thickness can be set to 0.5 μm or more and 10 μm or less.
＜硬化物＞
次に、本発明の硬化物について説明する。
　本発明の硬化物は、本発明の組成物の硬化物である。本発明の硬化物は、例えば、硬化速度および接着力に優れた接着層として用いることができる。なお、本発明の組成物については、「組成物」の項に記載の内容と同様とすることができるので、ここでの説明は省略する。 <Cured product>
Next, the cured product of the present invention will be described.
The cured product of the present invention is a cured product of the composition of the present invention. The cured product of the present invention can be used, for example, as an adhesive layer having excellent curing speed and adhesive strength. Note that the composition of the present invention can be the same as the content described in the section of “composition”, and the description is omitted here.
　本発明の硬化物は、本発明の組成物の硬化物であり、本発明の組成物の重合物を含むものである。すなわち、本発明の硬化物は、架橋縮合環を有する。 (4) The cured product of the present invention is a cured product of the composition of the present invention, and includes a polymer of the composition of the present invention. That is, the cured product of the present invention has a crosslinked condensed ring.
　本発明の硬化物の平面視形状、厚み等については、硬化物の用途等に応じて適宜設定することができる。 平面 The plan view shape, thickness, and the like of the cured product of the present invention can be appropriately set according to the use of the cured product.
　本発明の硬化物は、本発明の組成物を所望の形状となるように形成し、硬化させたものであり、製造方法については特に限定されるものではない。このような製造方法としては、例えば、後述する硬化物の製造方法の項に記載の内容と同様とすることができるため、ここでの説明は省略する。 The cured product of the present invention is obtained by forming the composition of the present invention into a desired shape and curing the composition, and the production method is not particularly limited. Such a production method can be, for example, the same as the content described in the section of the method for producing a cured product described below, and thus the description thereof is omitted here.
　本発明の硬化物の用途等については、組成物の項に記載の内容と同様とすることができる。 用途 The use of the cured product of the present invention can be the same as the content described in the section of the composition.
＜硬化物の製造方法＞
　次に、本発明の硬化物の製造方法について説明する。
　本発明の硬化物の製造方法は、本発明の組成物を硬化する硬化工程を有する。本発明の硬化物の製造方法によれば、硬化工程が本発明の組成物を用いるものであるため、硬化速度および接着力を有する硬化物を得ることができる。以下、本発明の硬化物の製造方法の各工程について詳細に説明する。 <Production method of cured product>
Next, a method for producing a cured product of the present invention will be described.
The method for producing a cured product of the present invention has a curing step of curing the composition of the present invention. According to the method for producing a cured product of the present invention, since the curing step uses the composition of the present invention, a cured product having a curing speed and adhesive strength can be obtained. Hereinafter, each step of the method for producing a cured product of the present invention will be described in detail.
１．硬化工程
　硬化工程は、本発明の組成物を硬化する工程であり、活性エネルギー線を照射または加熱する工程を含む。このような硬化方法については、「Ａ．組成物」の項に記載の内容と同様とすることができる。 1. Curing Step The curing step is a step of curing the composition of the present invention, and includes a step of irradiating or heating with active energy rays. Such a curing method can be the same as that described in the section “A. Composition”.
２．その他の工程
　本発明の硬化物の製造方法は、必要に応じてその他の工程を有するものであってもよい。このような工程としては、本発明の組成物を硬化する工程の前に、本発明の組成物を塗布する工程等を挙げることができる。本発明の組成物を塗布する方法としては、スピンコーター、ロールコーター、バーコーター、ダイコーター、カーテンコーター、各種の印刷、浸漬等の公知の方法を用いることができる。塗布する工程は、本発明の組成物を基材上に塗布することができる。 2. Other Steps The method for producing a cured product of the present invention may have other steps as necessary. Examples of such a step include a step of applying the composition of the present invention before the step of curing the composition of the present invention. As a method of applying the composition of the present invention, known methods such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing and dipping can be used. In the applying step, the composition of the present invention can be applied on a substrate.
　基材としては、硬化物の用途等に応じて適宜設定することができ、ソーダガラス、石英ガラス、半導体基板、金属、紙、プラスチック等を含むものを挙げることができる。また、硬化物は、基材上で形成された後、基材から剥離して用いても、基材から他の被着体に転写して用いてもよい。 The base material can be appropriately set according to the use of the cured product and the like, and examples include those containing soda glass, quartz glass, semiconductor substrates, metal, paper, plastic, and the like. Further, after the cured product is formed on the base material, the cured product may be peeled off from the base material or used by transferring from the base material to another adherend.
　本発明の製造方法により製造される硬化物および用途等については、硬化物の項に記載の内容と同様とすることができる。 硬化 The cured product produced by the production method of the present invention, its use, and the like can be the same as those described in the section of the cured product.
　本発明の組成物、これを含有する接着剤、その硬化物およびその製造方法は、上記実施形態に限定されるものではない。上記実施形態は、例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。 組成 The composition of the present invention, the adhesive containing the same, the cured product thereof, and the method for producing the same are not limited to the above embodiments. The above embodiment is an exemplification, and has substantially the same configuration as the technical idea described in the scope of the claims of the present invention. It is included in the technical scope of the invention.
　以下、本発明を、実施例等を挙げてさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to these examples.
［実施例１～２８および比較例１～７］
　下記表１～表５に記載の配合に従って、各成分を配合して組成物を得た。各成分は以下の材料を用いた。なお、表中の配合量は、各成分の質量部を表す。 [Examples 1 to 28 and Comparative Examples 1 to 7]
According to the formulations shown in Tables 1 to 5, the components were blended to obtain compositions. The following materials were used for each component. In addition, the compounding amount in a table | surface represents the mass part of each component.
成分（Ａ）
Ａ１－１：トリシクロデカンジメタノールジアクリレート
Ａ１－２：ジシクロペンタニルアクリレ－ト
Ａ２－１：４－ｎ－ヒドロキシブチルアクリレート
Ａ２－２：化合物（Ａ２）Ｎｏ．１
Ａ３－１：トリ（アクリロイルエチル）イソシアヌレート
Ａ３－２：ε－カプロラクトン変性トリス（２－アクリロキシエチル）
　　　　　イソシアヌレート
Ａ４－１：１，６－ヘキサンジオールジアクリレート
Ａ４－２：１，１０－デカンジオールジアクリレート Component (A)
A1-1: Tricyclodecane dimethanol diacrylate A1-2: Dicyclopentanyl acrylate A2-1: 4-n-hydroxybutyl acrylate A2-2: Compound (A2) No. 1
A3-1: Tri (acryloylethyl) isocyanurate A3-2: ε-caprolactone-modified tris (2-acryloxyethyl)
Isocyanurate A4-1: 1,6-hexanediol diacrylate A4-2: 1,10-decanediol diacrylate
成分（Ｂ）
Ｂ１－１：化合物（Ｂ１）Ｎｏ．１
Ｂ１－２：化合物（Ｂ１）Ｎｏ．２
Ｂ２－１：グリシジルメタクリレートとメチルメタクリレートの共重合物
　　　　（重量平均分子量８，０００、エポキシ当量５００～６００ｇ／
　　　　　ｅｑ．）
Ｂ２－２：グリシジルメタクリレートとメチルメタクリレートの共重合物
　　　　（重量平均分子量１５，０００、エポキシ当量５００～６００ｇ／
　　　　　ｅｑ．）
Ｂ３－１：１，４－ブタンジオールジグリシジレート
Ｂ３－２：３，４－エポキシシクロヘキシルメチル－３，４－エポキシ
　　　　　シクロヘキシルカルボキシレート
Ｂ３－３：トリメチロールプロパントリグリシジルエーテル
Ｂ３－４：３，３’－［オキシビス（メチレン）］ビス（３－エチルオキセ
　　　　　タン）
Ｂ３－５：ビスフェノールＡのジグリシジエーテル Component (B)
B1-1: Compound (B1) No. 1
B1-2: Compound (B1) No. 2
B2-1: Copolymer of glycidyl methacrylate and methyl methacrylate (weight average molecular weight 8,000, epoxy equivalent 500-600 g /
eq. )
B2-2: Copolymer of glycidyl methacrylate and methyl methacrylate (weight average molecular weight 15,000, epoxy equivalent 500-600 g /
eq. )
B3-1: 1,4-butanediol diglycidylate B3-2: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate B3-3: trimethylolpropane triglycidyl ether B3-4: 3,3 '-[Oxybis (methylene)] bis (3-ethyloxetane)
B3-5: Diglycidyl ether of bisphenol A
成分（Ｃ）
Ｃ－１：１－ヒドロキシシクロヘキシルフェニルケトン Component (C)
C-1: 1-hydroxycyclohexyl phenyl ketone
成分（Ｄ）
Ｄ－１：ＣＰＩ－１００Ｐ（サンアプロ株式製） Component (D)
D-1: CPI-100P (manufactured by San Apro)
添加剤
Ｅ－１：レベリング剤（東レ・ダウコーニング社製ＳＨ－２９ＰＡ） Additive E-1: Leveling agent (SH-29PA manufactured by Dow Corning Toray)
［評価］
　得られた各組成物につき、粘度、初期硬化性、接着力および耐水性を、下記の手順に従って評価した。 [Evaluation]
The viscosity, initial curability, adhesive strength and water resistance of each of the obtained compositions were evaluated according to the following procedures.
（粘度）
　得られた各組成物を、それぞれ２５℃においてＥ型粘度計で粘度を測定した。粘度が３０～８０ｍＰａ・ｓの組成物は塗工性に優れることから好ましく、４０～７０ｍＰａ・ｓの組成物は、特に好ましい。 (viscosity)
The viscosity of each of the obtained compositions was measured at 25 ° C. using an E-type viscometer. A composition having a viscosity of 30 to 80 mPa · s is preferable because of excellent coating properties, and a composition having a viscosity of 40 to 70 mPa · s is particularly preferable.
（評価用サンプルの作製方法）
　得られた各組成物を、硬化後の厚みが３μｍとなるように、一枚のＰＭＭＡフィルム（住友化学（株）製テクノロイ１２５Ｓ００１）にそれぞれ塗布した後、もう一枚のコロナ放電処理を施したＣＯＰ（シクロオレフィンポリマー、日本ゼオン（株）製：品番ゼオノアフィルム１４－０６０）フィルムとラミネーターを用いて貼り合わせ、無電極紫外光ランプを用いて１，０００ｍＪ／ｃｍ２に相当する光をＣＯＰフィルム越しに照射して評価用サンプルを得た。 (Method of preparing evaluation sample)
Each of the obtained compositions was applied to one PMMA film (Technoloy 125S001 manufactured by Sumitomo Chemical Co., Ltd.) so that the thickness after curing became 3 μm, and then another corona discharge treatment was performed. A COP (cycloolefin polymer, manufactured by Nippon Zeon Co., Ltd .: product number Zeonor Film 14-060) film and a laminator are bonded together, and light equivalent to 1,000 mJ / cm 2 is emitted from the COP film using an electrodeless ultraviolet lamp. Irradiation was performed to obtain a sample for evaluation.
　得られた評価用サンプルの９０°ピール試験を行い、下記基準で評価を行った。結果を下記表１～表５に併記する。なお、９０°ピール試験は、２５℃条件下、評価用サンプルを、引っ張り試験機ＦＴＮ１－１３Ａ（アイコーエンジニアリング社製）でＰＭＭＡフィルムを９０°方向に引っ張って剥がし、ＰＭＭＡフィルムがＣＯＰフィルムから剥離する際の最大強度を接着力として測定した。 ９０ A 90 ° peel test was performed on the obtained evaluation sample, and the evaluation was performed according to the following criteria. The results are shown in Tables 1 to 5 below. In the 90 ° peel test, the evaluation sample was peeled off at 25 ° C. by pulling the PMMA film in the 90 ° direction using a tensile tester FTN1-13A (manufactured by Aiko Engineering), and the PMMA film was peeled from the COP film. The maximum strength at that time was measured as the adhesive strength.
（初期硬化性）
　得られた評価用サンプルについて３０℃、５０％ＲＨ、大気圧条件下で露光から３分静置した後に、２．０ｃｍ幅に切り出して評価用サンプルを得た。この評価用サンプルを用いて９０°ピール試験を行い、下記基準で評価を行った。結果を下記表１～表５に併記する。 (Initial curing)
The obtained evaluation sample was allowed to stand at 30 ° C., 50% RH and atmospheric pressure for 3 minutes after exposure, and then cut into 2.0 cm width to obtain an evaluation sample. A 90 ° peel test was performed using this evaluation sample, and evaluation was performed according to the following criteria. The results are shown in Tables 1 to 5 below.
Ａ：接着力が０．６Ｎ／２０ｍｍ以上
Ｂ：接着力が０．４Ｎ／２０ｍｍ以上、０．６Ｎ／２０ｍｍ未満
Ｃ：接着力が０．４Ｎ／２０ｍｍ未満
評価がＡ、Ｂの物は接着剤として好ましく使用でき、評価がＡの物が特に好ましい。評価がＣのものは、使用できる用途が限定されるため好ましくない。 A: Adhesive force of 0.6 N / 20 mm or more B: Adhesive force of 0.4 N / 20 mm or more, less than 0.6 N / 20 mm C: Adhesive force of less than 0.4 N / 20 mm Evaluations of A and B are adhesives And those having an evaluation of A are particularly preferable. Those having an evaluation of C are not preferred because usable applications are limited.
（接着力）
　得られた評価用サンプルについて３０℃、５０％ＲＨ、大気圧条件下で露光から１２時間後に、２．０ｃｍ幅に切り出して接着力評価用サンプルを得た。得られたサンプルについて、上記の条件で９０°ピール試験を行い接着力を測定し、下記の基準で評価を行った。 (Adhesive strength)
The obtained evaluation sample was cut out to a width of 2.0 cm 12 hours after exposure under conditions of 30 ° C., 50% RH and atmospheric pressure to obtain a sample for evaluation of adhesive strength. The obtained sample was subjected to a 90 ° peel test under the above conditions to measure the adhesive strength, and evaluated according to the following criteria.
Ａ：接着力が２．５Ｎ／２０ｍｍ以上
Ｂ：接着力が１．５Ｎ／２０ｍｍ以上２．５Ｎ／２０ｍｍ未満
Ｃ：接着力が１．０Ｎ／２０ｍｍ以上１．５Ｎ／２０ｍｍ未満
Ｄ：接着力が１．０Ｎ／２０ｍｍ未満
接着力がＡまたはＢの物は接着剤として使用でき、特にＡのものが好ましい。接着力がＣ、Ｄのものは、接着剤として好ましくない。 A: The adhesive force is 2.5 N / 20 mm or more B: The adhesive force is 1.5 N / 20 mm or more and less than 2.5 N / 20 mm C: The adhesive force is 1.0 N / 20 mm or more and less than 1.5 N / 20 mm D: The adhesive force is An adhesive having an adhesive strength of A or B of less than 1.0 N / 20 mm can be used as an adhesive, and an adhesive of A is particularly preferable. Adhesives having C and D are not preferable as an adhesive.
（耐水性）
　耐水性については温水後接着力により評価した。得られた評価用サンプルについて３０℃、５０％ＲＨ、大気圧条件下で露光から１２時間後に、６０℃の温水に４８時間浸漬した後、温水から取り出して乾燥させたのち、２．０ｃｍ幅に切り出して温水後接着力評価用サンプルを得た。得られたサンプルについて、上記の方法で９０°ピール試験を行い、温水後接着力を測定し、下記の基準で評価を行った。 (water resistant)
The water resistance was evaluated by the adhesive strength after warm water. The obtained evaluation sample was immersed in warm water of 60 ° C. for 48 hours after exposure at 30 ° C., 50% RH and atmospheric pressure for 12 hours, taken out of the warm water and dried, and then reduced to 2.0 cm width. After cutting out, a sample for evaluation of adhesive strength after warm water was obtained. The obtained sample was subjected to a 90 ° peel test by the above-described method, and the adhesive strength after warm water was measured, and evaluated according to the following criteria.
Ａ：温水後接着力が２．５Ｎ／２０ｍｍ以上
Ｂ：温水後接着力が１．５Ｎ／２０ｍｍ以上２．５Ｎ／２０ｍｍ未満
Ｃ：温水後接着力が１．０Ｎ／２０ｍｍ以上１．５Ｎ／２０ｍｍ未満
Ｄ：温水後接着力が１．０Ｎ／２０ｍｍ未満
　温水後接着力がＡ、ＢまたはＣの物は耐水性に優れた接着剤として使用でき、ＡまたはＢのものが好ましく、特にＡのものが好ましい。温水後接着力がＤのものは、耐水性が求められる用途の接着剤として好ましくない。  A: Adhesion after warm water is 2.5 N / 20 mm or more B: Adhesion after warm water is 1.5 N / 20 mm or more and less than 2.5 N / 20 mm C: Adhesion after warm water is 1.0 N / 20 mm or more and 1.5 N / 20 mm Less than D: Adhesive strength after warm water is less than 1.0 N / 20 mm. Those having an adhesive strength after warm water of A, B or C can be used as an adhesive having excellent water resistance. Is preferred. Those having an adhesive strength after warm water of D are not preferred as adhesives for applications requiring water resistance.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
　表１～５より実施例の組成物は、塗工性、初期硬化性、接着力および耐水性に優れることが確認できた。よって本発明の組成物は、接着剤として有用である。 よ り From Tables 1 to 5, it was confirmed that the compositions of Examples were excellent in coating properties, initial curing properties, adhesive strength and water resistance. Therefore, the composition of the present invention is useful as an adhesive.

Claims (11)

  1. 　ラジカル重合性成分（Ａ）およびカチオン重合性成分（Ｂ）を含有する組成物において、
    　前記ラジカル重合性成分（Ａ）が、架橋縮合環を有するラジカル重合性化合物（Ａ１）をラジカル重合性成分（Ａ）１００質量部中に７０～１００質量部含有し、
    　前記カチオン重合性成分（Ｂ）が、架橋縮合環を有するカチオン重合性化合物（Ｂ１）をカチオン重合性成分（Ｂ）１００質量部中に１０～５０質量部含有することを特徴とする組成物。     In a composition containing a radically polymerizable component (A) and a cationically polymerizable component (B),
    The radical polymerizable component (A) contains 70 to 100 parts by mass of a radical polymerizable compound (A1) having a crosslinked condensed ring in 100 parts by mass of the radical polymerizable component (A).
    A composition characterized in that the cationically polymerizable component (B) contains 10 to 50 parts by mass of a cationically polymerizable compound (B1) having a crosslinked condensed ring per 100 parts by mass of the cationically polymerizable component (B).
  2. 　さらに、ラジカル重合性開始剤（Ｃ）およびカチオン重合性開始剤（Ｄ）を含有し、
    　前記ラジカル重合性成分（Ａ）、前記カチオン重合性成分（Ｂ）、前記ラジカル重合性開始剤（Ｃ）および前記カチオン重合性開始剤（Ｄ）の総量１００質量部中に、前記ラジカル重合性成分（Ａ）４０～６０質量部、前記カチオン重合性成分（Ｂ）３０～５０質量部、前記ラジカル重合性開始剤（Ｃ）１～１０質量部および前記カチオン重合性開始剤（Ｄ）１～１０質量部を含有する請求項１記載の組成物。     Further, it contains a radically polymerizable initiator (C) and a cationically polymerizable initiator (D),
    The radical polymerizable component (A), the cationic polymerizable component (B), the radical polymerizable initiator (C) and the cationic polymerizable initiator (D) in a total amount of 100 parts by mass contain the radical polymerizable component. (A) 40 to 60 parts by mass, the cationically polymerizable component (B) 30 to 50 parts by mass, the radically polymerizable initiator (C) 1 to 10 parts by mass, and the cationically polymerizable initiator (D) 1 to 10 The composition according to claim 1, which contains parts by mass.
  3. 　前記ラジカル重合性化合物（Ａ１）および前記カチオン重合性化合物（Ｂ１）に含まれる架橋縮合環が、下記式（Ｉ）で表される構造を有する架橋縮合環である請求項１または２記載の組成物。　
    Figure JPOXMLDOC01-appb-I000001
    The composition according to claim 1 or 2, wherein the crosslinked condensed ring contained in the radical polymerizable compound (A1) and the cationic polymerizable compound (B1) is a crosslinked condensed ring having a structure represented by the following formula (I). object.
    Figure JPOXMLDOC01-appb-I000001
  4. 　前記カチオン重合性成分（Ｂ）として、架橋縮合環を有さない重量平均分子量１，０００以上３０，０００未満のカチオン重合性化合物（Ｂ２）を含有する請求項１～３のうちいずれか一項記載の組成物。 The method according to any one of claims 1 to 3, wherein the cationically polymerizable component (B) contains a cationically polymerizable compound (B2) having no crosslinked condensed ring and having a weight average molecular weight of 1,000 or more and less than 30,000. A composition as described.
  5. 　前記カチオン重合性成分（Ｂ）として、架橋縮合環を有さない重量平均分子量２００以上１，０００未満のカチオン重合性化合物（Ｂ３）を含有する請求項１～４のうちいずれか一項記載の組成物。 The method according to any one of claims 1 to 4, wherein the cationically polymerizable component (B) contains a cationically polymerizable compound (B3) having no crosslinked condensed ring and having a weight average molecular weight of 200 or more and less than 1,000. Composition.
  6. 　前記カチオン重合性化合物（Ｂ３）が、オキセタニル基を有する化合物を含む請求項５記載の組成物。 The composition according to claim 5, wherein the cationically polymerizable compound (B3) includes a compound having an oxetanyl group.
  7. 　前記ラジカル重合性成分（Ａ）として、カチオン重合性基を有し、イソシアヌレート環および架橋縮合環を有さないラジカル重合性化合物（Ａ２）を含有する請求項１～６のうちいずれか一項記載の組成物。 7. The radical polymerizable component (A) according to claim 1, comprising a radical polymerizable compound (A2) having a cationic polymerizable group and not having an isocyanurate ring or a cross-linked condensed ring. A composition as described.
  8. 　前記ラジカル重合性成分（Ａ）として、イソシアヌレート環を含有し、架橋縮合環を有さないラジカル重合性化合物（Ａ３）を含有する請求項１～７のうちいずれか一項記載の組成物。 The composition according to any one of claims 1 to 7, wherein the radical polymerizable component (A) contains a radical polymerizable compound (A3) containing an isocyanurate ring and not having a cross-linked condensed ring.
  9. 　請求項１～８のうちいずれか一項記載の組成物を含有することを特徴とする接着剤。 接着 An adhesive comprising the composition according to any one of claims 1 to 8.
  10. 　請求項１～８のうちいずれか一項記載の組成物からなることを特徴とする硬化物。 A cured product comprising the composition according to any one of claims 1 to 8.
  11. 　請求項１～８のうちいずれか一項記載の組成物に対して、活性エネルギー線を照射または加熱する工程を含むことを特徴とする硬化物の製造方法。 A method for producing a cured product, comprising a step of irradiating or heating an active energy ray to the composition according to any one of claims 1 to 8.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015143352A (en) * 2013-12-25 2015-08-06 東亞合成株式会社 Photocurable adhesive composition, polarizing plate and method for manufacturing the same, optical member, and liquid crystal display device
JP2017149135A (en) * 2016-02-25 2017-08-31 協立化学産業株式会社 Method for producing layered body
JP2017179202A (en) * 2016-03-31 2017-10-05 株式会社Adeka Curable composition, manufacturing method of cured article and the cured article
JP2017193597A (en) * 2016-04-18 2017-10-26 株式会社Adeka Curable composition
JP2018165330A (en) * 2017-03-28 2018-10-25 株式会社Adeka Curable composition
JP2019048929A (en) * 2017-09-08 2019-03-28 株式会社ダイセル Composition for fiber reinforced composite material, prepreg, and fiber reinforced composite material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6400006B2 (en) * 2013-07-09 2018-10-03 株式会社Adeka Cationic polymerizable composition
JP6075237B2 (en) 2013-07-12 2017-02-08 東亞合成株式会社 Active energy ray-curable adhesive composition for plastic film or sheet
JP6369201B2 (en) 2013-08-09 2018-08-08 東亞合成株式会社 Active energy ray-curable adhesive composition for plastic film or sheet
JP6826530B2 (en) * 2015-06-23 2021-02-03 株式会社クラレ Adhesives, Adhesives, and How to Make Adhesives
KR102631774B1 (en) * 2016-06-21 2024-01-30 가부시키가이샤 아데카 Curable composition, method for producing cured product, and cured product of same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015143352A (en) * 2013-12-25 2015-08-06 東亞合成株式会社 Photocurable adhesive composition, polarizing plate and method for manufacturing the same, optical member, and liquid crystal display device
JP2017149135A (en) * 2016-02-25 2017-08-31 協立化学産業株式会社 Method for producing layered body
JP2017179202A (en) * 2016-03-31 2017-10-05 株式会社Adeka Curable composition, manufacturing method of cured article and the cured article
JP2017193597A (en) * 2016-04-18 2017-10-26 株式会社Adeka Curable composition
JP2018165330A (en) * 2017-03-28 2018-10-25 株式会社Adeka Curable composition
JP2019048929A (en) * 2017-09-08 2019-03-28 株式会社ダイセル Composition for fiber reinforced composite material, prepreg, and fiber reinforced composite material

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