WO2019017418A1 - Composition, adhesive including same, cured product of composition, and production method therefor - Google Patents

Composition, adhesive including same, cured product of composition, and production method therefor Download PDF

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Publication number
WO2019017418A1
WO2019017418A1 PCT/JP2018/027028 JP2018027028W WO2019017418A1 WO 2019017418 A1 WO2019017418 A1 WO 2019017418A1 JP 2018027028 W JP2018027028 W JP 2018027028W WO 2019017418 A1 WO2019017418 A1 WO 2019017418A1
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Prior art keywords
composition
compound
cured product
mass
parts
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PCT/JP2018/027028
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French (fr)
Japanese (ja)
Inventor
尭大 井上
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株式会社Adeka
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Priority to JP2019530585A priority Critical patent/JPWO2019017418A1/en
Publication of WO2019017418A1 publication Critical patent/WO2019017418A1/en

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds

Definitions

  • the present invention relates to a composition, an adhesive containing the same, a cured product of the composition and a method for producing the same, and more particularly, a composition suitable for an adhesive having excellent adhesion and adhesion, and an adhesive containing the same
  • the present invention relates to a cured product of a composition and a method for producing the same.
  • Patent Document 1 proposes an adhesive excellent in antistatic performance and excellent in adhesion between an optical laminate, in particular, a polarizing plate and a glass substrate even under high temperature and high humidity conditions. And according to patent document 1, while this adhesive does not produce foaming and peeling between an adhesive layer and a glass substrate, it can prevent the contamination of adherends, such as a high-priced liquid crystal module, etc. . Moreover, the method of using an adhesive sheet as another adhesion method of members is also known.
  • Patent No. 5649275 gazette
  • the pressure-sensitive adhesive sheet has an advantage that the positional deviation is small when bonding the adherend.
  • the pressure-sensitive adhesive sheet has a problem that the adhesion is lowered when placed in an environment of high temperature and high humidity.
  • the curable adhesive since the curable adhesive has fluidity compared to the pressure-sensitive adhesive sheet, when the adherend is bonded to the curable adhesive under pressure, positional displacement of the adherend occurs. there is a possibility.
  • a method of using the curable adhesive a method of reducing the flowability by starting curing of the curable adhesive before laminating the adherends may be considered.
  • the time to reach the desired fluidity may limit the step of bonding the adherends.
  • the object of the present invention is to have adhesion easiness that can bond adherends with little positional deviation, and adhesion that exhibits high adhesion even when placed under high temperature and high humidity environment. It is an object of the present invention to provide a composition suitable for an adhesive, an adhesive containing the same, a cured product of the composition and a method for producing the same.
  • the present inventor is capable of two different curings of light curing and heat curing, thereby using a composition that can be cured in two stages of semi curing and main curing. As a result, it has been found that the above-mentioned problems can be solved, and the present invention has been completed.
  • the composition of the present invention comprises a cyclic ether compound having a cyclic ether group, a radical polymerizable compound having a radical polymerizable group, a photo radical initiator capable of polymerizing the radical polymerizable groups, and the cyclic ether. And a thermal polymerization initiator capable of polymerizing groups with one another.
  • the thermal polymerization initiator preferably includes an anionic polymerization initiator, and the anionic polymerization initiator is at least one selected from the group consisting of a curing agent and a curing catalyst.
  • the curing agent preferably includes dicyandiamide, and the curing catalyst preferably includes an imidazole compound.
  • the content of the radically polymerizable compound is 10 parts by mass or more and 90 parts by mass or less with respect to a total of 100 parts by mass of the cyclic ether compound and the radically polymerizable compound. Is preferred.
  • the adhesive of the present invention is characterized by containing the composition of the present invention.
  • the cured product of the present invention is characterized in that it is a cured product of the composition of the present invention.
  • one having a storage elastic modulus at a temperature of 25 ° C. of 1.0 ⁇ 10 3 Pa or more and less than 1.0 ⁇ 10 5 Pa is preferable because of excellent adhesion easiness, and others the embodiment is preferable because the 1.0 ⁇ 10 5 Pa or more 1.0 ⁇ 10 10 Pa or less of those excellent adhesion.
  • the method for producing a cured product of the present invention at least one of the step of polymerizing radical polymerizable groups contained in the composition by light irradiation and the step of polymerizing cyclic ether groups contained in the composition by heat treatment It is a manufacturing method of hardened material which has a process, and The composition is characterized in that it is a composition of the present invention.
  • adhesion having adhesion easiness that can bond adherends with little positional deviation, and adhesion showing high adhesion even when placed under high temperature and high humidity environment A composition suitable for the agent, an adhesive containing the same, a cured product of the composition, and a method for producing the same can be provided.
  • composition the adhesive, the cured product and the method for producing the cured product of the present invention will be described in detail.
  • the composition of the present invention comprises a cyclic ether compound having a cyclic ether group, a radical polymerizable compound having a radical polymerizable group, a photo radical initiator capable of polymerizing radical polymerizable groups, and a cyclic ether group. And a possible thermal polymerization initiator.
  • the composition of the present invention is capable of two different curing processes of light curing and heat curing, and by combining the two curing processes, it can be cured in two stages of semi curing and main curing. For this reason, the composition of the present invention can be used as an adhesive excellent in ease of adhesion and adhesion. The reason is presumed as follows.
  • the cured product in the semi-cured state is in a state in which the flowability is lower than that of the composition, when the adherend is pressed and bonded, positional displacement of the adherend is unlikely to occur.
  • the cured product in the semi-cured state has tackiness because it contains, for example, a cyclic ether compound or a radically polymerizable compound before polymerization.
  • the adherend is a resin material
  • the cured product in the semi-cured state can dissolve the adherend surface by the compound before polymerization.
  • cured material of a semi-hardened state can bond together a to-be-adhered body stably.
  • the composition of the present invention can be bonded to the adherend with less displacement using the cured product in this semi-cured state.
  • the composition of this invention can obtain the hardened
  • the composition of the present invention can have easy adhesion and adhesion to an adherend having a light shielding portion.
  • the composition of the present invention is one having a cyclic ether compound, a radically polymerizable compound, a photo radical initiator and a thermal polymerization initiator.
  • a cyclic ether compound As described above, the composition of the present invention is one having a cyclic ether compound, a radically polymerizable compound, a photo radical initiator and a thermal polymerization initiator.
  • each component of the composition of this invention is demonstrated.
  • the cyclic ether compound is a compound having a cyclic ether group.
  • the cyclic ether group may be any one having at least one ether bond in the ring structure, and examples thereof include an epoxy group and an oxetanyl group. That is, as a cyclic ether compound, the epoxy compound which has an epoxy group, the oxetane compound which has oxetanyl group can be mentioned.
  • the number of contained cyclic ether groups can be appropriately set according to the desired adhesiveness and the like.
  • the number of cyclic ethers contained may be 1 or more per one cyclic ether compound, but can be 2 or more and 10 or less, preferably 2 or more and 5 or less, and particularly preferably 2 or more and 3 or less Is preferred.
  • a composition using such a cyclic ether compound exhibits excellent ease of adhesion and adhesiveness when used as an adhesive.
  • composition of the present invention it is preferable to include an epoxy compound as the cyclic ether compound.
  • an epoxy compound as the cyclic ether compound.
  • Such cyclic ether compounds have excellent curability.
  • the compound which contains an epoxy group and other cyclic ether groups, such as oxetanyl group, in 1 molecule shall be contained in an epoxy compound.
  • the glycidyl ether type compound which has glycidyl ether group, and the epoxy cycloalkyl type compound which has an epoxy cycloalkyl group can be mentioned.
  • a glycidyl ether type compound is preferably contained as the epoxy compound.
  • the glycidyl ether type compound has excellent curability, so the composition exhibits excellent adhesion.
  • composition of the present invention it is preferable to include both a glycidyl ether type compound and an epoxy cycloalkyl type compound as the epoxy compound.
  • a glycidyl ether type compound can improve the dispersibility or solubility in a composition by being used together with an epoxy cycloalkyl type compound, and as a result, a cured product having not only easy adhesion and adhesiveness but also excellent transparency Because you can get
  • the content of the glycidyl ether type compound is 30 parts by mass or more in 100 parts by mass of the cyclic ether compound from the viewpoint of improving the adhesion of the composition.
  • 80 parts by mass or more is preferable, and 90 parts by mass or more is particularly preferable.
  • the content of the epoxy cycloalkyl type compound is 30 parts by mass or more in 100 parts by mass of the cyclic ether compound from the viewpoint of improving the dispersion stability of the composition.
  • 80 parts by mass or more is preferable, and 90 parts by mass or more is particularly preferable.
  • the content of the glycidyl ether type compound can be 1 part by mass to 99 parts by mass with respect to 100 parts by mass of the glycidyl ether type compound and the epoxy cycloalkyl type compound, and 10 parts by mass It is preferable that it is a part or more and 90 mass parts or less, and it is preferable that it is 20 mass parts or more and 80 mass parts or less. By using such a composition, excellent coatability, adhesion and adhesiveness are exhibited.
  • the compound which contains both a glycidyl ether group and an epoxy cycloalkyl group in 1 molecule shall be included in a glycidyl ether type compound.
  • the glycidyl ether type compound may be any one having a glycidyl ether structure, such as a glycidyl ether of an aliphatic alcohol, a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof. It can be mentioned.
  • glycidyl ether type compound allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12 to 13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, neopentyl glycol Glycidyl ethers of polyhydric alcohols such as diglycidyl ethers, propylene glycol and trimethylo
  • glycidyl ether type compound a compound having at least one aromatic ring can also be used.
  • glycidyl ether type compounds having an aromatic ring include polyglycidyl ethers of polyhydric phenols or alkylene oxide adducts thereof, such as bisphenol A, bisphenol F, or glycidyl ether compounds of compounds obtained by further adding an alkylene oxide thereto. And epoxy novolac resins.
  • epoxy cycloalkyl type compound polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring and a hydroxyl group directly bonded to the alicyclic ring, or cyclohexene or cyclopentene ring-containing compound with an oxidizing agent
  • examples thereof include cyclohexene oxide and cyclopentene oxide-containing compounds obtained by epoxidation.
  • epoxy cycloalkyl type compound for example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexane carboxylate , 6-Methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate 3,4-Epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane- Metadioxane Bis (3,4-epoxycyclohexylmethyl) a
  • compounds other than glycidyl ether type compounds and epoxy cycloalkyl type compounds can also be used as the epoxy compound.
  • compounds other than such glycidyl ether type compounds and epoxy cycloalkyl type compounds for example, 1,2-epoxy-4- (2-oxiranyl) cyclohexane of 2,2-bis (hydroxymethyl) -1-butanol An additive etc. can be mentioned.
  • UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200 (all manufactured by Union Carbide Corporation), Celoxide 2021, Celoxide 2021 P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 2000, Celoxide 3000, Cyclomer A 200, Cyclomer M 100, Cyclomer M 101, Epolide GT-301, Epolide GT-302, Epolide 401, Epolide 403, ETHB, Epolide HD 300, EHPE-3150, ETHB, Epoblend (above, made by Daicel Chemical Industries, Ltd.), Epicoat 801, Epicoat 828 (above, made by Yuka Shell Epoxy Co., Ltd.), PY- 06, 0163, DY-022 (all manufactured by Ciba Specialty Chemicals), KRM-2720, EP-4100, EP-4000, EP-4080, EP-4088S, EP-4900, EPR-2000,
  • the following compounds can be mentioned, for example.
  • a compound having both a cyclic ether group and a radically polymerizable group such as 4-hydroxybutyl acrylate glycidyl ether does not correspond to a cyclic ether compound, but corresponds to a radically polymerizable compound. It shall be.
  • the molecular weight of the cyclic ether compound is not particularly limited as long as desired adhesiveness and the like can be obtained, and for example, 50 or more and 2,000,000 or less can do.
  • the cyclic ether compound preferably contains a low molecular weight compound from the viewpoint of ease of application and adhesion of the composition. Moreover, since the low molecular weight compound is excellent in dispersibility or solubility in the composition, a cured product excellent in transparency can be obtained.
  • the cyclic ether compound preferably also contains a high molecular weight compound from the viewpoint of ease of adhesion of the composition and suppression of dissolution of the adherend.
  • a composition is because when the adherend contains an organic material, the composition is excellent in the suppression of dissolution of the adherend and the suppression of white turbidity thereby.
  • the cyclic ether compound is a compound of a low molecular weight compound and a high molecular weight compound from the viewpoint of the balance of ease of application of the composition, ease of adhesion and suppression of dissolution of adherends. It is preferable to include both. Moreover, it is because dispersion
  • the molecular weight of the low molecular weight compound may be any as long as desired coatability and the like can be obtained, and can be, for example, 1,000 or less, preferably 50 or more and 500 or less, and more preferably 50 or more and 300 or less. It is preferable that it is the following.
  • the molecular weight of the high molecular weight compound may be any as long as desired adhesion and the like can be obtained, and can be, for example, larger than 1,000, preferably 1,000 or more and 5,000 or less. Especially, it is preferable that they are 1,500 or more and 3,000 or less.
  • molecular weight shows a weight average molecular weight (Mw), when a compound is a polymer.
  • the weight average molecular weight can be determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).
  • the weight average molecular weight is, for example, GPC (LC-2000 plus series) manufactured by JASCO Corporation, the elution solvent is tetrahydrofuran, and polystyrene standards for calibration curve are 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 (TSKgel standard polystyrene manufactured by Tosoh Corp.), and the measurement column is KF It can obtain and measure as -804, KF-803, and KF-802 (made by Showa Denko KK). Also, the measurement temperature can be 40 ° C., and the flow rate can be 1.0 mL / min.
  • GPC LC-2000 plus series
  • the elution solvent is tetrahydrofuran
  • polystyrene standards for calibration curve are Mw 1,110,000, 707,000, 397,000, 189,000, 98,900, 37,200, 13,700, 9,490
  • the content of the low molecular weight compound in the cyclic ether compound is not particularly limited as long as desired adhesiveness and the like can be obtained, for example, adhesion ease It adjusts suitably from a viewpoint of balance, such as transparency and transparency.
  • the content of the low molecular weight compound is, for example, 40 parts by mass or more and 90 parts by mass or less in 100 parts by mass of the cyclic ether compound. Among these, 45 parts by mass or more and 80 parts by mass or less are preferable.
  • the content of the low molecular weight compound is, for example, preferably 50 parts by mass or more in 100 parts by mass of the cyclic ether compound.
  • 70 parts by mass or more is preferable, 90 parts by mass or more is preferable, and 100 parts by mass, that is, it is preferable that only a low molecular weight compound is contained as a cyclic ether compound.
  • the cyclic ether compound may include a compound which is liquid at room temperature (hereinafter, may be simply referred to as “liquid compound”). It is preferable to include a compound which is solid at room temperature (hereinafter, may be simply referred to as "solid compound”).
  • the solid compound may be one having a softening point or a melting point (a softening point when both a softening point and a melting point are present) of 30 ° C. or more.
  • the liquid compound may be one having a softening point or a melting point (if the softening point and the melting point are both, the softening point) is less than 30 ° C.
  • the softening point or melting point (if the softening point and the melting point are both, the softening point) of the solid compound is preferably 35 ° C. or more and 180 ° C. or less, and more preferably 40 ° C. or more and 100 ° C. or less
  • the temperature is preferably 42 ° C. or more and 80 ° C. or less, and particularly preferably 45 ° C. or more and 70 ° C. or less.
  • the content of the solid compound may be any as long as desired adhesiveness can be obtained, but 10 parts by mass or more in 100 parts by mass of the total of the solid compound and the liquid compound It is preferable that it is 70 mass parts or less, and it is preferable that it is 20 mass parts or more and 60 mass parts or less.
  • content of a cyclic ether compound is not specifically limited if desired adhesiveness etc. are obtained as one embodiment of the composition of this invention,
  • solid content 100 mass of a composition is used.
  • the amount may be 10 parts by mass or more and 95 parts by mass or less, preferably 30 parts by mass or more and 85 parts by mass or less, and particularly preferably 40 parts by mass or more and 60 parts by mass or less.
  • solid content contains all the components other than a solvent.
  • the content is on a mass basis, and cyclic ether compounds, radically polymerizable compounds, photo radical initiators and thermal polymerization initiators are, for example, at 25 ° C. Even in liquid form, it is included in the solid content.
  • the radically polymerizable compound is one having a radically polymerizable group.
  • the radically polymerizable group may be any group as long as it can be polymerized by radical polymerization, and examples thereof include ethylenically unsaturated double bond groups such as methacryl group, acryl group and allyl group, among which methacryl group or acryl group It is preferable that it is an acryl group, that is, the radically polymerizable compound is an acrylate. It is because a radically polymerizable compound has little influence of oxygen inhibition by a radically polymerizable group being these functional groups, and a composition exhibits the outstanding adhesiveness.
  • the number of radically polymerizable groups in the radically polymerizable compound can be appropriately set according to the desired adhesiveness and the like.
  • the number of radically polymerizable groups contained may be 1 or more per molecule of radically polymerizable compound, but can be 2 or more and 50 or less.
  • a composition containing such a radically polymerizable compound exhibits excellent ease of adhesion and adhesiveness when used as an adhesive.
  • the radically polymerizable compound examples include compounds having a urethane bond such as urethane methacrylate and urethane acrylate, and compounds having no urethane bond such as methacrylic monomer and acrylic monomer (hereinafter referred to simply as "acrylate monomer”) Can be mentioned.
  • the radically polymerizable compound may include at least one of a compound having a urethane bond and a compound having no urethane bond, and in particular, it may include both a compound having a urethane bond and a compound having no urethane bond. preferable.
  • a composition is because it exhibits excellent adhesion and adhesiveness when used as an adhesive.
  • the content of the compound having no urethane bond is, for example, a compound having no urethane bond and a compound having a urethane bond It is preferable that it is 20 mass parts or more and 60 mass parts or less with respect to a total of 100 mass parts, and it is preferable that it is 30 mass parts or more and 60 mass parts or less especially. Such a composition is because it exhibits excellent adhesion and adhesiveness.
  • Examples of the compound having a urethane bond include, as urethane (meth) acrylate, polycarbonate urethane (meth) acrylate, polyester urethane (meth) acrylate, polyether urethane (meth) acrylate, caprolactone urethane (meth) acrylate and the like These can be obtained by the reaction of an isocyanate compound obtained by reacting a polyol and a diisocyanate with a (meth) acrylate monomer having a hydroxyl group.
  • polyols examples include polycarbonate diols, polyester polyols, polyether polyols, and polycaprolactone polyols.
  • (meth) acrylate includes the meaning of both an acrylate and a methacrylate.
  • (meth) acrylic both meaning of acrylic and methacrylic is included.
  • the weight average molecular weight (Mw) of the compound having a urethane bond is not particularly limited as long as desired adhesiveness and the like can be obtained, but can be 1,000 or more and 200,000 or less. However, it is preferably 2,000 or more and 30,000 or less, and particularly preferably 2,000 or more and 20,000 or less. Such a composition is because it has excellent adhesion and adhesiveness when used as an adhesive.
  • the number of radically polymerizable functional groups contained in the compound having a urethane bond is not particularly limited as long as desired adhesiveness and the like can be obtained, but it is 1 or more and 20 or less in one molecule. Among them, it is preferably 1 or more and 10 or less, and particularly preferably 1 or more and 3 or less. Such a composition is because it has excellent adhesion and adhesiveness when used as an adhesive.
  • the compound having no urethane bond is not particularly limited as long as desired adhesiveness and the like can be obtained, and a monofunctional compound having one radically polymerizable functional group and a polyfunctional compound having two or more groups are used. be able to.
  • the compound having no urethane bond preferably contains a monofunctional compound. Such a composition is because it has excellent adhesion and adhesiveness when used as an adhesive.
  • Examples of monofunctional compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate And stearyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, polyoxyalkylene modified (meth) acrylate, (meth) acrylic Acid 2-hydroxyethyl
  • a compound having a cyclic ether group such as tetrahydrofurfuryl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether can also be used.
  • the monofunctional compound may contain only one type, and for example, two or more types may be used in combination.
  • the monofunctional compound preferably contains a compound having a cyclic ether group, a compound having a hydroxyl group such as (meth) acrylic acid hydroxyalkyl ester, and the like.
  • a composition is because it exhibits excellent adhesiveness when used as an adhesive.
  • the content of the compound having a cyclic ether group is not particularly limited as long as desired adhesiveness and the like can be obtained, and for example, it is 50 parts by mass or more with respect to 100 parts by mass of the monofunctional compound. In particular, it is preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more. Within this range, the composition exhibits excellent adhesion when used as an adhesive.
  • the content of the compound having a hydroxyl group such as the above (meth) acrylic acid hydroxyalkyl ester, and the total content in the case of including both the compound having a hydroxyl group and the compound having a cyclic ether group are each cyclic ether. It can be made similar to the content of the compound having a group.
  • the monofunctional compound preferably includes a bridged carbocyclic compound having a bridged carbocyclic group.
  • the composition exhibits excellent adhesiveness when used as an adhesive.
  • the bridging carbon ring is a structure in which two or more hydrocarbon rings share a part of the ring structure.
  • bridged carbocyclic compound examples include compounds having an isobornyl group such as (meth) acrylic acid isobornyl, etc., an adamantyl group such as 1-adamantyl (meth) acrylic acid and 2-methyl-2-adamantyl (meth) acrylic acid.
  • an isobornyl group such as (meth) acrylic acid isobornyl, etc.
  • an adamantyl group such as 1-adamantyl (meth) acrylic acid and 2-methyl-2-adamantyl (meth) acrylic acid.
  • Compounds, dicyclopentadiene and the like can be mentioned.
  • the content of the crosslinked carbocyclic compound is not particularly limited as long as desired adhesiveness and the like can be obtained, and preferably 50 parts by mass or less with respect to 100 parts by mass of the monofunctional compound, for example.
  • the amount is preferably 10 parts by mass or more and 40 parts by mass or less, and particularly preferably 20 parts by mass or more and 30 parts by mass or less. Within this range, the composition exhibits excellent adhesion when used as an adhesive.
  • polyfunctional compound examples include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neo Pentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified phosphoric acid di (meth) Acrylate, di (acryloxyethyl) isocyanurate, allylated cyclohexyl di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) a Lilate, propionic acid modified dipentaeryth
  • the molecular weight of the compound not having a urethane bond can be 5,000 or less, preferably 100 or more and 1,000 or less, and particularly preferably 100 or more and 500 or less.
  • a composition having such a composition exerts excellent ease of adhesion and adhesiveness when used as an adhesive.
  • the molecular weight of the radically polymerizable compound is not particularly limited as long as desired adhesiveness and the like can be obtained, and is, for example, 50 or more and 200,000 or less. be able to.
  • the radically polymerizable compound preferably contains a low molecular weight compound from the viewpoint of ease of application and adhesion of the composition. In one embodiment of the composition of the present invention, the radically polymerizable compound preferably contains a high molecular weight compound from the viewpoint of ease of adhesion of the composition and suppression of dissolution of the adherend.
  • a composition is because when the adherend contains an organic material, the composition is excellent in the suppression of dissolution of the adherend and the suppression of white turbidity thereby.
  • the radically polymerizable compound is 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 ease of adhesion and the suppression of dissolution of adherends. It is preferable to include both of them.
  • the molecular weight of the low molecular weight compound may be any as long as desired coatability and the like can be obtained, and can be, for example, 2,000 or less, preferably 50 or more and 1,000 or less, and more preferably 50 or more. It is preferable that it is 300 or less.
  • the molecular weight of the high molecular weight compound may be any as long as desired adhesion and the like can be obtained, and can be, for example, larger than 2,000, and preferably 2,500 or more and 20,000 or less. Especially, it is preferable that they are 2,500 or more and 10,000 or less.
  • the content of the low molecular weight compound contained in the radically polymerizable compound is not particularly limited as long as desired adhesiveness and the like can be obtained, and for example, the total of 100 parts by mass of the low molecular weight compound and the high molecular weight compound On the other hand, it can be 10 parts by mass or more and 90 parts by mass or less, preferably 30 parts by mass or more and 70 parts by mass or less, and particularly preferably 40 parts by mass or more and 60 parts by mass or less.
  • Such a composition is because when the adherend contains an organic material, the composition is excellent in the suppression of dissolution of the adherend and the suppression of white turbidity thereby. In addition, such a composition exhibits excellent ease of application and adhesion.
  • the content of the radically polymerizable compound is not particularly limited as long as desired adhesiveness and the like can be obtained, and, for example, cyclic ether compounds and radically polymerizable
  • the amount can be 1 to 99 parts by mass, preferably 10 to 90 parts by mass, and more preferably 40 to 60 parts by mass with respect to 100 parts by mass of the total of the compounds. Is preferred.
  • the content of the radically polymerizable compound is in the range described above, when it is used as an adhesive, excellent adhesion easiness and adhesiveness are exhibited.
  • the content of the radically polymerizable compound can be 5 parts by mass to 95 parts by mass or less with respect to 100 parts by mass of the solid content of the composition, and 30 parts by mass
  • the content is preferably 80 parts by mass or less, and more preferably 40 parts by mass or more and 60 parts by mass or less.
  • Such a composition is because it has excellent adhesion and adhesiveness when used as an adhesive.
  • the photoradical initiator is capable of polymerizing radically polymerizable groups.
  • the photo radical initiator may contain only one type, or two or more types may be used in combination.
  • composition of the present invention specifically, conventionally known compounds can be used as the photo radical initiator, and examples thereof include benzophenone, phenylbiphenyl ketone, 1-hydroxy-cyclohexyl-phenyl ketone, 1 -Hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morpholine-2- (4'-methylmercapto) benzoylpropane, Thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoyl Lopan, 2-hydroxy-2- (4'-isopropyl
  • N-1414, N-1717, N-1919, PZ-408, NCI-831, NCI-930 made by ADEKA Corporation
  • the content of the photo radical initiator is not particularly limited as long as desired adhesiveness and the like can be obtained, but, for example, 100 mass of radical polymerizable compound
  • the amount can be 1 part by mass or more and 20 parts by mass or less, preferably 2 parts by mass or more and 15 parts by mass or less, and particularly preferably 2 parts by mass or more and 12 parts by mass or less. It is because the composition of such composition has the outstanding ease of adhesion and adhesiveness, when it uses as an adhesive agent.
  • the thermal polymerization initiator may be any one capable of initiating polymerization of cyclic ether groups by heating, and mention may be made of cationic polymerization initiator, anionic polymerization initiator, etc. Can.
  • the thermal polymerization initiator may contain only one type, or two or more types may be used in combination.
  • the thermal polymerization initiator preferably comprises an anionic polymerization initiator.
  • the anionic polymerization initiator is less in inhibition of curing due to the influence of an amine compound and the like contained in the adherend, and is capable of stably polymerizing cyclic ether groups.
  • Anionic polymerization initiator As an anionic polymerization initiator, what is necessary is just to be able to polymerize cyclic ether groups by anionic polymerization, for example, a curing agent, a curing catalyst, etc. can be mentioned.
  • cyclic ether compounds can be cross-linked by being covalently bonded to a cyclic ether group, and, for example, dicyandiamide, modified polyamines, hydrazides, 4,4'-diaminodiphenyl Sulfone, guanamines, melamine and the like can be mentioned. Among them, dicyandiamide is preferably contained.
  • a curing agent is capable of efficiently polymerizing cyclic ether groups with one another, and it is easy to reduce the content of the curing agent. These curing agents may be used alone or in combination of two or more.
  • the commercial products of the dicyandiamide are not limited to those containing only dicyandiamide, and those containing dicyandiamide and other components can also be used.
  • Examples of the commercially available products include DICY7, DICY15, DICY50 (above, manufactured by Mitsubishi Chemical Co., Ltd.), Amicure CG-NA, Amicure Cg-325 G, Amicure CG-1200 G, Dicyanex1400 F (above, made by Air Products Co., Ltd.), EH-3636 AS manufactured by ADEKA EH-4351S, EH-5910, and the like.
  • denaturation thing of polyamines As said modification
  • the polyamines used for the modified polyamine are not particularly limited, but, for example, fats such as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, 1,2-diaminopropane, polyoxypropylene diamine, polyoxypropylene triamine etc.
  • Aliphatic polyamine isophoronediamine, mensenediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl Alicyclic polyamines such as -2,4,8,10-tetraoxaspiro (5.5) undecane; m-phenylenediamine, p-phenylenediamine, tolylene-2,4-diamine, tolylene-2,6 Mononuclear polyamines such as diamine, mesitylene-2,4-diamine, mesitylene-2, 6-diamine, 3,5-diethyl tolylene-2,4-diamine, 3,5-diethyl tolylene-2, 6-diamine And aromatic polyamines such as biphenylenediamine, 4,4-diaminodip
  • the epoxy addition modified product can be produced by subjecting the above-mentioned polyamines and an epoxy compound to an addition reaction according to a conventional method.
  • the epoxy compound mentioned at the time of explanation of a cyclic ether compound can be used, for example.
  • the above-mentioned amidated modified product can be produced by reacting the above-mentioned polyamines with carboxylic acids such as adipic acid, sebacic acid, phthalic acid, isophthalic acid and dimer acid according to a conventional method.
  • carboxylic acids such as adipic acid, sebacic acid, phthalic acid, isophthalic acid and dimer acid according to a conventional method.
  • the Mannich modified product usually comprises the above polyamines, aldehydes such as formaldehyde, and phenols having at least one aldehyde forming reactive site in the core of phenol, cresol, xylenol, tert-butylphenol, resorcin, etc. It can be produced by reaction according to the method.
  • hydrazides examples include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide and the like.
  • a curing catalyst there can be mentioned a catalyst which generates an acidic substance or an alkaline substance which causes cyclic ether groups to react with each other by the action of heat or energy ray and promotes the polymerization reaction of cyclic ether groups.
  • phosphine compounds such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecyl Imidazoles such as imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-aminopropylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole Imidazole salts which are salts of the above imidazoles with trimellitic acid, isocyanuric acid, boron and the like; amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; 3- ( Ureas such as 2,4-dichlorophen
  • the curing catalyst preferably contains, among others, imidazoles. This is because the curing catalyst can polymerize cyclic ether groups at a low temperature by using it together with a curing agent such as dicyandiamide.
  • the anionic polymerization initiator may be used alone or in combination of two or more, and may include, for example, at least one selected from the group of curing agents and curing catalysts, among which curing agents and curing It is preferable to contain both of the catalysts, and in particular, it is preferable to contain dicyandiamide as a curing agent and to contain imidazoles as a curing catalyst.
  • Such compositions can polymerize cyclic ethers at low temperatures.
  • a cured product having excellent transparency is easy to manufacture, and further, the curing speed is excellent.
  • the polymerization can be efficiently accelerated by, for example, lowering the curing temperature and improving the curing rate.
  • suppression of the content of the anionic polymerization initiator, reduction of the ratio of remaining unreacted, and the like become easy, and the composition becomes easy to produce a cured product excellent in transparency.
  • anionic polymerization initiators are usually solid at around room temperature, and may be contained in a dispersed state in the composition.
  • the above initiator can efficiently polymerize cyclic ether groups, and the content can be easily reduced.
  • the composition is excellent in light transmittance, and for example, the polymerization of radical polymerizable groups by light irradiation becomes easy.
  • such a composition has a small amount of non-reacted anionic polymerization initiator, and it becomes easy to obtain a cured product with high transparency. From these facts, it becomes easy to obtain a cured product which is excellent in ease of adhesion and adhesion and further excellent in transparency.
  • the content of the curing agent is particularly limited as long as desired adhesiveness and the like can be obtained.
  • it can be 5 parts by mass or more and 95 parts by mass or less, preferably 40 parts by mass or more and 95 parts by mass or less, with respect to 100 parts by mass in total of the curing agent and the curing catalyst, and 50 parts by mass It is preferable that it is a part or more and 95 mass parts or less, Especially, it is preferable that it is 85 mass parts or more and 95 mass parts or less.
  • the content of the curing agent is preferably 30 parts by mass or more and 70 parts by mass or less in 100 parts by mass in total of the curing agent and the curing catalyst, from the viewpoint of easy lowering of the curing temperature.
  • the content is preferably 40 parts by mass or more and 60 parts by mass or less, and particularly preferably 45 parts by mass or more and 55 parts by mass or less.
  • the content of the anionic polymerization initiator is not particularly limited as long as desired adhesiveness and the like can be obtained, and for example, 100 parts by mass of a cyclic ether compound On the other hand, it can be 0.1 to 20 parts by mass, preferably 1 to 15 parts by mass, and more preferably 1 to 5 parts by mass, The content is more preferably 1.0 parts by mass or more and 2.0 parts by mass or less, and still more preferably 1.1 parts by mass or more and 1.4 parts by mass or less.
  • a composition is because it has excellent adhesion and adhesiveness when used as an adhesive.
  • the cationic polymerization initiator is not particularly limited as long as it is a compound capable of generating a cationic species or a Lewis acid upon heating, and a conventionally known compound can be used.
  • an onium salt initiator is used be able to.
  • onium salt initiator for example, sulfonium such as aryldialkylsulfonium hexafluoroantimonate, aryldialkylsulfonium hexafluorophosphate, diarylalkylsulfonium hexafluoroantimonate, aryldialkylsulfonium tetraperfluorophenyl borate and the like
  • sulfonium such as aryldialkylsulfonium hexafluoroantimonate, aryldialkylsulfonium hexafluorophosphate, diarylalkylsulfonium hexafluoroantimonate, aryldialkylsulfonium tetraperfluorophenyl borate and the like
  • iodonium salts such as diaryliodonium hexafluoroantimonate, diaryliodonium hexafluorophosphate and diaryl
  • a commercial item can also be used as a cationic polymerization initiator.
  • Adeka Opton CP-77 Adeka Opton CP-66 (made by Adeka), CI-2639, CI-2624 (made by Nippon Soda Co., Ltd.), Sun Aid SI-60 L, Sun Aid SI-80 L and San Aid SI-100 L (San Shin Chemical Industry Co., Ltd.) Company) and the like.
  • the content of the cationic polymerization initiator relative to 100 parts by mass of the cyclic ether compound is not particularly limited as long as desired adhesiveness and the like can be obtained, and can be the same as the anionic polymerization initiator.
  • composition of the present invention has a cyclic ether compound, a radically polymerizable compound, a photo radical initiator and a thermal polymerization initiator, and as one embodiment thereof, contains other components as necessary. It may be one.
  • Such other components can include, for example, solvents capable of dissolving or dispersing the above-mentioned components.
  • the solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Ethyl acetate, methanol, ethanol, isopropanol and the like can be mentioned.
  • a thiol compound as an embodiment of the composition of the present invention from the viewpoint of being able to impart excellent adhesion and transparency to the composition of the present invention .
  • Any thiol compound may be used as long as it can impart excellent adhesion and transparency to the cured product of the composition of the present invention, and tetraethylene glycol bis (3-mercaptopropionate), 1,4 -Bifunctional thiol compounds such as -bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, 1,2 3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), Trifunctional thiol compounds such as trimethylol ethane tris (3-mercaptobutyrate), pentaeryth Examples include tetrafunctional thiol compounds such as tol tetrakis (3
  • thiol compound for example, Karenz MT (registered trademark) BD-1 (trade name, bifunctional thiol compound, 1,4-bis (3-mercaptobutyryloxy) butane, Showa Denko KK), Karens MT (registered trademark) NR-1 (trade name, trifunctional thiol compound, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H) , 3H, 5H) -trione, Showa Denko KK, Karenz MT (registered trademark) PE-1 (trade name, tetrafunctional thiol compound, pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko KK) , EGMP-4 (trade name, bifunctional thiol compound, tetraethylene glycol bis (3-mercaptopropionate), SC Organic Chemical Co., Ltd.), TMMP (com
  • the content of the thiol compound can be 0.1 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the solid content of the composition, and 1 part by mass or more
  • the amount is preferably 10 parts by mass or less, and more preferably 5 parts by mass or more and 10 parts by mass or less.
  • inorganic fillers As other components, if necessary, inorganic fillers, organic fillers, pigments, silane coupling agents, colorants such as dyes, photosensitizers, antifoaming agents, thickeners, thixo agents, surfactants, Various resin additives such as leveling agents, flame retardants, plasticizers, stabilizers, polymerization inhibitors, ultraviolet light absorbers, antioxidants, antistatic agents, flow control agents, adhesion promoters and the like can be included.
  • the total content of the other components is preferably 30 parts by mass or less in 100 parts by mass of the solid content of the composition.
  • the method for producing the composition of the present invention is not particularly limited as long as the above components can be uniformly mixed.
  • a thermal polymerization initiator is used.
  • a method of adding and mixing an optical radical initiator is used.
  • the method of using a well-known mixing apparatus can be employ
  • composition of the present invention when a high melting point compound and a low melting point compound are contained as cyclic ether compounds, the low melting point compound and the high melting point compound are mixed, and after being liquid at room temperature, radically polymerizable
  • a high melting point compound and a low melting point compound are contained as cyclic ether compounds
  • the low melting point compound and the high melting point compound are mixed, and after being liquid at room temperature, radically polymerizable
  • the method of adding and mixing other components, such as a compound can be used.
  • composition of the present invention is not particularly limited as long as it is used for forming a cured product, and in addition to the resist material of the printed wiring board, resist ink, pigment resist ink for car filters, semiconductor Insulating varnishes, insulation sheets, laminated plates, plasmas in various coating fields such as sealants, inks, plastic coatings, paper printing, film coatings, glass coatings, shatterproof coatings, furniture coatings, FRPs, linings, and also in the electronics sector Display panels, display media such as display elements, retardation plates, polarizing plates, light polarizing prisms, optical anisotropic bodies such as various light filters, adhesives, insulating materials, structural materials, optical waveguide cladding, etc. can be mentioned. .
  • composition of the present invention is preferably used in an adhesive from the viewpoint that the effect of being curable in two steps of semi-curing and main curing can be exhibited more effectively. That is, the adhesive of the present invention comprises the composition of the present invention.
  • Specific applications of the adhesive of the present invention include optical materials represented by glasses and imaging lenses, applications of electronic materials represented by laminates and printed substrates, and automotive applications represented by head-up displays and car navigation It can be used in various applications such as equipment and display panels represented by organic EL and liquid crystal.
  • the adhesive is preferably used in applications where transparency is required, and is particularly preferably used in applications such as optical materials, in-vehicle devices, display panels and the like.
  • the adherend with the adhesive of the present invention may be an inorganic material, but is preferably an organic material.
  • the adherend is an organic material
  • the cured product in the semi-cured state of the composition of the present invention can dissolve the surface of the adherend and it becomes easy to bond the adherends.
  • organic materials as adherends include cellulose esters such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose, etc .; polyamide; polyimide; polyurethane; epoxy resin; polycarbonate ; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polybutylene terephthalate, etc.
  • cellulose esters such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose, etc .
  • polyamide polyimide
  • polyurethane epoxy resin
  • polycarbonate polyesters such as polyethylene
  • Vinyl compounds such as polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylic acid ester; polycarbonate; polysulfone; polyether sulfone; polyether ketone; And polymeric materials such as polyoxyethylene and norbornene resin.
  • the inorganic material as the adherend include glasses such as soda glass and quartz glass, metals, metal oxides and the like.
  • the cured product of the present invention is a cured product of the composition of the present invention described above. Therefore, it is easy to indicate the semi-cured state and the main cured state.
  • the cured product of the present invention is a cured product in a semi-cured state of the composition of the present invention, so that, for example, adhesion ease can be easily given to bond adherends with less positional deviation.
  • the cured product is a cured product in the main cured state of the composition of the present invention, for example, it is possible to easily impart excellent adhesion to an adherend.
  • the storage elastic modulus of the cured product of the present invention is usually higher than that of the above composition, and can be appropriately set according to the application of the cured product.
  • the storage elastic modulus can be, for example, 1.0 ⁇ 10 3 Pa or more at 25 ° C.
  • the cured product has excellent adhesion ease, it can be 1.0 ⁇ 10 3 Pa or more and less than 1.0 ⁇ 10 5 Pa.
  • the adherend when the cured product according to one embodiment of the present invention is a cured product having reduced fluidity as compared to the composition of the present invention, the adherend can be pressure-bonded to be bonded. There is little misalignment of In addition, by setting the storage elastic modulus in the above range, tackiness can be exhibited at around room temperature, and the adherend can be easily bonded.
  • the cured product of such storage modulus can be obtained by semi-curing the composition of the present invention, for example, a compound of only one of the radically polymerizable compound and the cyclic ether compound contained in the composition of the present invention Can be easily obtained, for example, by using a polymer as a cured product in a semi-cured state by polymerization.
  • the storage elastic modulus is 1.0 ⁇ 10 5 Pa or more at 25 ° C. 0 ⁇ may be 10 10 Pa or less, inter alia, preferably not more than 1.0 ⁇ 10 5 Pa or more 1.0 ⁇ 10 8 Pa, in particular, 1.0 ⁇ 10 5 Pa or more 1.0 ⁇ 10 It is preferable that it is 6 Pa or less. It is because the hardened
  • the cured product according to one embodiment of the present invention can stably maintain the adhesion state with the adherend at room temperature.
  • the cured product of such storage elastic modulus is obtained, for example, by polymerizing both the radically polymerizable compound and the cyclic ether compound contained in the composition of the present invention by the main curing of the composition of the present invention It is because it can be easily obtained by setting it as the hardened
  • storage elastic modulus can measure the sample for evaluation using a dynamic-viscoelasticity measuring apparatus.
  • the thickness of the evaluation sample can be, for example, 50 ⁇ m.
  • the measurement conditions of the storage elastic modulus are 8 mm parallel plate, sample diameter 8 mm, thickness of sample for evaluation (gap of stage and parallel plate) 50 ⁇ m, frequency 5 Hz, swing angle 0.5% It can be done.
  • a dynamic viscoelasticity measuring apparatus a dynamic viscoelasticity measuring apparatus MCR-302 manufactured by Anton Paar can be used.
  • the method of measuring the storage elastic modulus of the prepared sample for evaluation is to hold the composition in parallel plates so that the film thickness (gap) becomes 50 ⁇ m. Then, the composition may be cured under predetermined curing conditions while being held between parallel plates, and then the storage elastic modulus of the obtained cured product may be measured under the above-described measurement conditions.
  • the thickness of the cured product is, for example, different depending on the size of the adherend when the cured product is used as an adhesive layer to adhere adherends to each other, but is, for example, 0.1 ⁇ m or more and 1 mm or less be able to.
  • the method for producing the cured product of the present invention is not particularly limited as long as the composition of the present invention can be cured.
  • a method of polymerizing the cyclic ether compound and the radically polymerizable compound contained in the composition can be used.
  • a method of polymerizing either one of a cyclic ether compound and a radically polymerizable compound That is, the method of semi-curing the composition of the present invention can be used.
  • a method of polymerizing both of a cyclic ether compound and a radically polymerizable compound that is, the composition of the present invention as another embodiment.
  • a method of curing can be used, and among them, a method of sequentially polymerizing both of the cyclic ether compound and the radically polymerizable compound contained in the composition can be preferably used.
  • the method of polymerizing the cyclic ether compound in the composition of the present invention may include the step of polymerizing the cyclic ether groups contained in the composition by heat treatment.
  • the method of polymerizing the radically polymerizable compound in the composition of the present invention may include the step of polymerizing the radically polymerizable groups contained in the composition by light irradiation.
  • the method for producing a cured product of the present invention comprises the steps of polymerizing radical polymerizable groups contained in the composition of the present invention by light irradiation and steps of polymerizing cyclic ether groups contained in the composition of the present invention by heat treatment (I) a mode including only one of (i) polymerizing radically polymerizable groups with light and polymerizing cyclic ether groups with heat treatment (first embodiment) Form (a second embodiment) including two steps of (form) and (ii) a step of polymerizing radically polymerizable groups with light and a step of polymerizing cyclic ether groups by heat treatment (second embodiment) It can be divided.
  • cured material of this invention is divided into each form, and is demonstrated.
  • the first embodiment of the method for producing a cured product of the present invention comprises only one of the steps of polymerizing radically polymerizable groups with light and polymerizing cyclic ether groups with heat treatment. It is According to the first embodiment, the cured product in the semi-cured state can be formed by performing only one of the above steps. Therefore, in the first embodiment, when the adherend is pressurized and attached, a cured product with less positional deviation of the adherend can be obtained. Moreover, in 1st Embodiment, tackiness is shown at room temperature vicinity, and the hardened
  • Step of polymerizing radically polymerizable groups This step is a step of polymerizing the radically polymerizable groups contained in the composition of the present invention by light irradiation.
  • the light to be irradiated can be appropriately set according to the type of photo radical initiator, and examples include ultraviolet light, electron beam, X-ray, radiation, high frequency and the like.
  • a light source of light a well-known light source can be used according to the kind of light.
  • an ultraviolet light source an ultraviolet laser, a mercury lamp, a xenon laser, a metal halide lamp, sunlight, etc. may be mentioned.
  • the total light intensity of the irradiated is light, as long as it is obtained the desired curing conditions, for example, be a 100 mJ / cm 2 or more 2,000 mJ / cm 2 or less.
  • Step of polymerizing cyclic ether groups This step is a step of polymerizing cyclic ether groups contained in the composition of the present invention by heat treatment.
  • the heating temperature is appropriately set according to the thickness of the coating film or cured product of the composition to be treated, the polymerization initiation temperature of the thermal polymerization initiator, etc., and is, for example, 50 ° C. or more and 250 ° C. or less In particular, it is preferably 100 ° C. or more and 200 ° C. or less, and particularly preferably 100 ° C. or more and 150 ° C. or less.
  • heating temperature shall show the surface temperature of the composition or hardened
  • the heating time can be 10 minutes or more and 2 hours or less.
  • heating time shows the time which a composition or hardened
  • the production method of the present invention may have other steps as necessary.
  • a step of applying the composition of the present invention a step of polymerizing radically polymerizable groups or cyclic After the process of polymerizing ether groups, the process etc. which bond a to-be-adhered body to hardened
  • the step of applying the composition of the present invention is a step of applying the composition prior to the step of polymerizing radically polymerizable groups and the step of polymerizing cyclic ether groups.
  • the coating method include known methods such as a die coater, a roll coater, a curtain coater, various types of printing, and immersion.
  • the application target of the composition of the present invention can be an adherend adhered by the composition of the present invention.
  • a material which comprises such a to-be-adhered body an inorganic material, an organic material, etc. can be mentioned.
  • an inorganic material and an organic material the thing similar to what was demonstrated in detail by description of the composition of this invention can be used specifically.
  • the step of bonding is a step of bonding an adherend to a cured product after the step of polymerizing radically polymerizable groups or the step of polymerizing cyclic ether groups. By performing this step at the above timing, it is possible to manufacture a cured product capable of bonding the adherend with less positional deviation.
  • any method may be used as long as the adherends can be bonded to the cured product with little positional deviation, and the adherend is pressed after being brought into contact with the cured product. Known methods such as can be used.
  • the cured product produced according to the first embodiment is a cured product in a semi-cured state.
  • the storage elastic modulus and the like of the cured product can be the same as the preferred range from the viewpoint of excellent adhesion as described above.
  • the second embodiment of the method for producing a cured product of the present invention includes both steps of polymerizing radically polymerizable groups with light and polymerizing cyclic ether groups with heat. According to the second embodiment, by including both steps of the above steps, first, one of the steps of polymerizing the radical polymerizable groups and polymerizing the cyclic ether groups is carried out, A cured product in a semi-cured state can be formed. In addition, after one process is performed, the other process can be performed to form a cured product in the main curing state.
  • a cured product in the main curing state can be obtained through two-stage curing processing of semi-curing and main curing. Therefore, in the second embodiment, the adherend is attached to the cured product, for example, between the step of polymerizing the radically polymerizable groups and the step of polymerizing the cyclic ether groups. It is possible to produce a cured product in which the adherends are bonded together with little positional deviation and stably bonded.
  • cured material of this form is demonstrated.
  • the step of polymerizing radical polymerizable groups with light and the step of polymerizing cyclic ether groups with heat treatment are the same as those described in the first embodiment.
  • the order of implementation of the step of polymerizing radically polymerizable groups with each other and the step of polymerizing cyclic ether groups with heat treatment may be to simultaneously perform both steps. It is preferable that the step of polymerizing radically polymerizable groups and the step of polymerizing cyclic ether groups are sequentially performed, and in particular, after carrying out the step of polymerizing radically polymerizable groups, a cyclic ether group It is preferable to carry out the step of polymerizing each other. This is because the composition of the present invention can effectively exhibit the effect of being able to obtain a cured product in the main curing state through the two-step curing process of semi-curing and main curing.
  • the cured product after the execution of one of the polymerization steps to be carried out first is usually either one of a polymer of a radically polymerizable compound and a polymer of a cyclic ether compound. It may be substantially free of the polymer of the other compound.
  • the second embodiment may have other steps as necessary.
  • a step of applying the composition of the present invention a step of polymerizing radically polymerizable groups and cyclic groups
  • the process etc. which bond a to-be-adhered body to hardened
  • the application method and the like in the applying step and the bonding method and the like in the bonding step can be the same as the contents of the description of the first embodiment.
  • the cured product produced according to the second embodiment is a cured product in the main curing state.
  • the composition, the adhesive and the cured product of the present invention have been described in detail using the preferred embodiments, but the present invention is not limited to the above embodiments. Further, the manufacturing method of the present invention is not limited to the first embodiment and the second embodiment described above.
  • the above embodiment is an exemplification, and it has substantially the same configuration as the technical idea described in the claims of the present invention, and any one having the same function and effect can be used. It is included in the technical scope of the invention.
  • Examples 1 to 29 and Comparative Examples 1 to 5 A cyclic ether compound, a radically polymerizable compound, a photo radical initiator, a thermal polymerization initiator and a thiol compound were compounded according to the formulations in Tables 1 to 5 below to obtain a composition. Each component is as follows. Using the composition obtained, 1. Adhesion after main curing, Transparency after main curing, 3. Adhesion after wet heat test, 4. Transparency after wet heat test5. The tackiness was evaluated. The compounding amounts in Tables 1 to 5 represent parts by mass of each component. Also, "-" in the table indicates one that has not been evaluated or can not be evaluated.
  • Cyclic ether compound Epoxy compounds other than glycidyl ether type compounds and epoxychloroalkyl type compounds (EHPE-3150 manufactured by Daicel Corporation, high molecular weight compounds, solid compounds, softening point 70 ° C to 90 ° C)
  • A-2 Glycidyl ether type compound (EPPN-201 manufactured by Nippon Kayaku Co., Ltd., high molecular weight compound, solid compound, softening point 65 ° C.
  • A-3 Glycidyl ether type compound (Mitsubishi Chemical Corporation JER 1007, high molecular weight compound, weight average molecular weight 2,900, solid compound, softening point 128 ° C.)
  • A-4 Glycidyl ether type compound (Mitsubishi Chemical Corporation JER 1009, high molecular weight compound, weight average molecular weight 3,800, solid compound, softening point 144 ° C.)
  • A-5 Epoxy chloralkyl type compound (Celoxide 2021 P, manufactured by Daicel Corporation, molecular weight 252, liquid compound)
  • A-6 Glycidyl ether type compound (ED-523T manufactured by ADEKA Co., Ltd., low molecular weight compound, liquid compound)
  • A-7 Glycidyl ether type compound (EP-4100E manufactured by ADEKA Co., Ltd., low molecular weight compound, liquid compound)
  • A-8 Glycidyl ether type compound (EP-4080E manufactured by ADEKA Co., Ltd., low
  • A-10 Glycidyl ether type compound (NC-2000-L, manufactured by Nippon Kayaku Co., Ltd., high molecular weight compound, solid compound, softening point 47 ° C.-57 ° C.)
  • B-1 Urethane acrylate (UN-9000 PEP, manufactured by Rygi Kogyo Co., Ltd., weight average molecular weight (Mw) 5,000)
  • B-2 Urethane Acrylate (UN-9200A, manufactured by KONAMI KOGYO CO., LTD., Weight average molecular weight 15,000)
  • B-3 4-hydroxybutyl acrylate glycidyl ether (monofunctional acrylate monomer, molecular weight 200)
  • B-4 4-hydroxybutyl acrylate (monofunctional acrylate monomer, molecular weight 144)
  • B-5 Acryloyl morpholine (monofunctional acrylate monomer, molecular weight 141)
  • B-6 Tetrahydrofurfuryl methacrylate (monofunctional acrylate monomer, molecular weight 170)
  • B-7 Isobornyl acrylate (monofunctional acrylate monomer, molecular weight 208)
  • D-1 Dicyandiamide (DICY) (EH-3636AS manufactured by ADEKA Corporation)
  • D-2 Dicyandiamide (DICY) (EH-4351S manufactured by ADEKA Corporation)
  • D-3 2-ethyl-4-methylimidazole
  • D-4 2-undecylimidazole
  • D-5 2-heptadecylimidazole
  • D-6 50% by mass of dicyandiamide (DICY) 50% by mass of imidazoles (( Adeka Hardener EH-5910 manufactured by Adeka Co., Ltd.
  • a 90 ° peel test was conducted using Sample 1 for evaluation of adhesion after main curing, and evaluation was made according to the following criteria.
  • the 90 ° peel test was performed by peeling 90 ° at a tensile speed of 50 mm / min using a compact table-top load tester MODEL-FTN1-13A (manufactured by Aiko Engineering Co., Ltd.).
  • the sample for evaluation 1 was subjected to the heat and humidity test, and thereafter evaluated in the same manner as the adhesion after the main curing.
  • the moist heat test was carried out by maintaining the environment at 85 ° C. and 85 RH% for 120 hours. Evaluation criteria are as follows. Same as adhesion after main curing.
  • the sample for evaluation 1 and the sample for evaluation 2 were subjected to a heat-of-moisture test, and then evaluated in the same manner as the transparency after main curing.
  • the moist heat test was carried out by maintaining the environment at 85 ° C. and 85 RH% for 120 hours. Evaluation criteria are as follows. Same as transparency after main curing.
  • Tack property The storage elastic modulus of the sample for evaluation of semi-curing and the sample for full-curing evaluation manufactured using each composition was measured and judged based on the following criteria.
  • the storage elastic modulus was measured using a dynamic viscoelasticity measuring device for the evaluation sample for semi-curing and the sample for main curing.
  • the film thickness of each sample was 50 ⁇ m. More specifically, the measurement conditions of storage modulus are 8 mm parallel plate, sample diameter 8 mm, film thickness of evaluation sample (gap between stage and parallel plate) 50 ⁇ m, frequency 5 Hz, swing angle 0.5%, The temperature was 25 ° C.
  • a dynamic viscoelasticity measuring device a dynamic viscoelasticity measuring device MCR-302 manufactured by Anton Paar was used.
  • the semi-cured evaluation sample is preferably B (having tackiness).
  • A tacky
  • C fluid
  • the sample for the main curing evaluation is photo-curing A (no tackiness).
  • B taciness
  • C fluid
  • the following method was used to measure the semi-cured evaluation sample.
  • (1) The compositions obtained in Examples and Comparative Examples were sandwiched by parallel plates such that the film thickness (gap) was 50 ⁇ m.
  • (3) The storage elastic modulus was measured on the said measurement conditions with respect to the sample for semi-hardening evaluation obtained by (2).
  • the measurement method of the sample for this curing evaluation is that UV irradiation is performed at 1000 mJ / cm 2 , the temperature rising rate is raised from 25 ° C. to 120 ° C. at 5 ° C./min, and the temperature is maintained for 30 minutes after reaching 120 ° C. Then, it is cooled from 120 ° C. to 25 ° C. at a temperature decrease rate of 5 ° C./min, and the storage elastic modulus is measured with respect to the sample for main curing evaluation reaching 25 ° C. The method was used.
  • compositions of the examples can form a cured product in a semi-cured state having tackiness by curing treatment (light irradiation treatment in this embodiment). It has been confirmed that it can be adjusted.
  • composition of the example has low tackiness due to the additional curing treatment (heat treatment in this example), and the main curing shows high adhesion even when placed under high temperature and high humidity environment. It was confirmed that a cured product of the state was obtained.
  • the composition of the present invention can be used, for example, as an adhesive excellent in ease of adhesion and adhesion.
  • the composition of the present invention is also useful, for example, for adhesion of an adherend having a light shielding portion, since a cured product in a semi-cured state and a main cured state can be formed in the order of photocuring and thermal curing. It could be confirmed.
  • Example 4 From the results of Example 4 and Example 5, it was confirmed that the adhesiveness is improved by using a cyclic ether compound having a high molecular weight.

Abstract

Provided are a composition suitable for an adhesive, an adhesive including the same, a cured product of the composition, and a production method therefor. The composition contains: a cyclic ether compound having a cyclic ether group; a radical-polymerisable compound having a radical-polymerisable group; a photo-radical initiator capable of polymerising the radical-polymerisable groups; and a thermal polymerisation initiator capable of polymerising the cyclic ether groups. The thermal polymerisation initiator preferably includes an anionic polymerisation initiator. The anionic polymerisation initiator preferably includes at least one selected from the group consisting of a curing agent and a curing catalyst.

Description

組成物、これを含む接着剤、組成物の硬化物およびその製造方法Composition, adhesive containing the same, cured product of the composition and method for producing the same
　本発明は、組成物、これを含む接着剤、組成物の硬化物およびその製造方法に関し、詳しくは、接着容易性および接着性に優れた接着剤に適した組成物、これを含む接着剤、組成物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 of the composition and a method for producing the same, and more particularly, a composition suitable for an adhesive having excellent adhesion and adhesion, and an adhesive containing the same The present invention relates to a cured product of a composition and a method for producing the same.
　部材同士の接着方法としては、例えば、光硬化または熱硬化により硬化する硬化性接着剤を用いる方法が知られている。例えば、特許文献１では、電防止性能に優れ、高温、高湿の条件下においても、光学積層体、特に偏光板とガラス基板との接着性に優れた接着剤が提案されている。そして、特許文献１によれば、この接着剤は、粘着剤層とガラス基板との間に発泡や剥離が生じない上に、高額な液晶モジュール等の被着体の汚染を防止することができる。また、部材同士の他の接着方法としては、粘着シートを用いる方法も知られている。 As a method of bonding members to each other, for example, a method using a curable adhesive which is cured by light curing or heat curing is known. For example, Patent Document 1 proposes an adhesive excellent in antistatic performance and excellent in adhesion between an optical laminate, in particular, a polarizing plate and a glass substrate even under high temperature and high humidity conditions. And according to patent document 1, while this adhesive does not produce foaming and peeling between an adhesive layer and a glass substrate, it can prevent the contamination of adherends, such as a high-priced liquid crystal module, etc. . Moreover, the method of using an adhesive sheet as another adhesion method of members is also known.
特許第５６４９２７５号公報Patent No. 5649275 gazette
　粘着シートは、被着体を接着する際に、位置ずれが少ないといった利点がある。しかしながら、粘着シートは、高温度および高湿度の環境下に置かれた場合に密着力が低下するといった問題がある。これに対して、硬化性接着剤は、粘着シートと比較して流動性を有するため、被着体を硬化性接着剤に対して加圧して貼り合わせる際に、被着体の位置ずれが生じる可能性がある。 The pressure-sensitive adhesive sheet has an advantage that the positional deviation is small when bonding the adherend. However, the pressure-sensitive adhesive sheet has a problem that the adhesion is lowered when placed in an environment of high temperature and high humidity. On the other hand, since the curable adhesive has fluidity compared to the pressure-sensitive adhesive sheet, when the adherend is bonded to the curable adhesive under pressure, positional displacement of the adherend occurs. there is a possibility.
　このような問題に対しては、硬化性接着剤の使用法として、被着体を貼り合わせる前に、硬化性接着剤の硬化を開始することで流動性を低下させる方法も考えられる。しかしながら、この方法では、所望の流動性となるまでの時間により、被着体を貼り合わせる工程に制約が生じる場合がある。 With respect to such a problem, as a method of using the curable adhesive, a method of reducing the flowability by starting curing of the curable adhesive before laminating the adherends may be considered. However, in this method, the time to reach the desired fluidity may limit the step of bonding the adherends.
　そこで、本発明の目的は、被着体を位置ずれ少なく貼り合わせることができる接着容易性と、高温度および高湿度の環境下に置かれた場合でも高い密着力を示す接着性と、を有する、接着剤に適した組成物、これを含む接着剤、組成物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 object of the present invention is to have adhesion easiness that can bond adherends with little positional deviation, and adhesion that exhibits high adhesion even when placed under high temperature and high humidity environment. It is an object of the present invention to provide a composition suitable for an adhesive, an adhesive containing the same, a cured product of the composition and a method for producing the same.
　本発明者は、上記課題を解消するために鋭意検討した結果、光硬化および熱硬化の２つの異なる硬化が可能であり、それにより半硬化および本硬化の２段階で硬化可能な組成物を用いることで、上記課題を解消することができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventor is capable of two different curings of light curing and heat curing, thereby using a composition that can be cured in two stages of semi curing and main curing. As a result, it has been found that the above-mentioned problems can be solved, and the present invention has been completed.
　すなわち、本発明の組成物は、環状エーテル基を有する環状エーテル化合物と、ラジカル重合性基を有するラジカル重合性化合物と、前記ラジカル重合性基同士を重合可能な光ラジカル開始剤と、前記環状エーテル基同士を重合可能な熱重合開始剤と、を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 comprises a cyclic ether compound having a cyclic ether group, a radical polymerizable compound having a radical polymerizable group, a photo radical initiator capable of polymerizing the radical polymerizable groups, and the cyclic ether. And a thermal polymerization initiator capable of polymerizing groups with one another.
　本発明の組成物の一実施形態としては、前記熱重合開始剤は、アニオン重合開始剤を含むことが好ましく、前記アニオン重合開始剤は、硬化剤および硬化触媒からなる群から選択される少なくとも一種を含むことが好ましく、前記硬化剤は、ジシアンジアミドを含み、前記硬化触媒は、イミダゾール化合物を含むことが好ましい。また、本発明の組成物の一実施形態としては、前記ラジカル重合性化合物の含有量は、前記環状エーテル化合物および前記ラジカル重合性化合物の合計１００質量部に対して１０質量部以上９０質量部以下であることが好ましい。 In one embodiment of the composition of the present invention, the thermal polymerization initiator preferably includes an anionic polymerization initiator, and the anionic polymerization initiator is at least one selected from the group consisting of a curing agent and a curing catalyst. The curing agent preferably includes dicyandiamide, and the curing catalyst preferably includes an imidazole compound. In one embodiment of the composition of the present invention, the content of the radically polymerizable compound is 10 parts by mass or more and 90 parts by mass or less with respect to a total of 100 parts by mass of the cyclic ether compound and the radically polymerizable compound. Is preferred.
　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。 The adhesive of the present invention is characterized by containing the composition of the present invention.
　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。 The cured product of the present invention is characterized in that it is a cured product of the composition of the present invention.
　本発明の硬化物の一実施形態としては、温度２５℃における貯蔵弾性率が、１．０×１０３Ｐａ以上１．０×１０５Ｐａ未満のものは接着容易性に優れるため好ましく、他の実施形態としては、１．０×１０５Ｐａ以上１．０×１０１０Ｐａ以下のものは接着性に優れるため好ましい。 As one embodiment of the cured product of the present invention, one having a storage elastic modulus at a temperature of 25 ° C. of 1.0 × 10 3 Pa or more and less than 1.0 × 10 5 Pa is preferable because of excellent adhesion easiness, and others the embodiment is preferable because the 1.0 × 10 5 Pa or more 1.0 × 10 10 Pa or less of those excellent adhesion.
　本発明の硬化物の製造方法は、組成物に含まれるラジカル重合性基同士を光照射により重合する工程、および組成物に含まれる環状エーテル基同士を加熱処理により重合する工程のうち少なくとも一方の工程を有する硬化物の製造方法であって、
　前記組成物が、本発明の組成物であることを特徴とするものである。 In the method for producing a cured product of the present invention, at least one of the step of polymerizing radical polymerizable groups contained in the composition by light irradiation and the step of polymerizing cyclic ether groups contained in the composition by heat treatment It is a manufacturing method of hardened material which has a process, and
The composition is characterized in that it is a composition of the present invention.
　本発明によれば、被着体を位置ずれ少なく貼り合わせることができる接着容易性と、高温度および高湿度の環境下に置かれた場合でも高い密着力を示す接着性と、を有する、接着剤に適した組成物、これを含む接着剤、組成物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, adhesion having adhesion easiness that can bond adherends with little positional deviation, and adhesion showing high adhesion even when placed under high temperature and high humidity environment A composition suitable for the agent, an adhesive containing the same, a cured product of the composition, and a method for producing the same can be provided.
　以下、本発明の組成物、接着剤、硬化物および硬化物の製造方法について詳細に説明する。 Hereinafter, the composition, the adhesive, the cured product and the method for producing the cured product of the present invention 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、環状エーテル基を有する環状エーテル化合物と、ラジカル重合性基を有するラジカル重合性化合物と、ラジカル重合性基同士を重合可能な光ラジカル開始剤と、環状エーテル基同士を重合可能な熱重合開始剤と、を含有するものである。本発明の組成物は、光硬化および熱硬化の２つの異なる硬化処理が可能であり、この２つの硬化処理を組み合わせることで半硬化および本硬化の２段階で硬化できる。このため、本発明の組成物は、接着容易性および接着性に優れた接着剤として用いることができる。その理由は、以下のように推察される。 <Composition>
First, the composition of the present invention will be described. The composition of the present invention comprises a cyclic ether compound having a cyclic ether group, a radical polymerizable compound having a radical polymerizable group, a photo radical initiator capable of polymerizing radical polymerizable groups, and a cyclic ether group. And a possible thermal polymerization initiator. The composition of the present invention is capable of two different curing processes of light curing and heat curing, and by combining the two curing processes, it can be cured in two stages of semi curing and main curing. For this reason, the composition of the present invention can be used as an adhesive excellent in ease of adhesion and adhesion. The reason is presumed as follows.
　すなわち、半硬化状態の硬化物は、組成物よりも流動性が低下した状態であるため、被着体を加圧して貼り合わせる際に、被着体の位置ずれが生じにくい。また、半硬化状態の硬化物は、例えば、重合前の環状エーテル化合物またはラジカル重合性化合物を含むため、タック性を有する。ここで、被着体が樹脂材料である場合、半硬化状態の硬化物は、重合前の化合物により被着体表面を溶解することができる。このため、半硬化状態の硬化物は、被着体を安定的に貼り合わせることができる。このような理由から、本発明の組成物は、この半硬化状態の硬化物を用いて、被着体を位置ずれ少なく貼り合わせることができる。 That is, since the cured product in the semi-cured state is in a state in which the flowability is lower than that of the composition, when the adherend is pressed and bonded, positional displacement of the adherend is unlikely to occur. In addition, the cured product in the semi-cured state has tackiness because it contains, for example, a cyclic ether compound or a radically polymerizable compound before polymerization. Here, when the adherend is a resin material, the cured product in the semi-cured state can dissolve the adherend surface by the compound before polymerization. For this reason, the hardened | cured material of a semi-hardened state can bond together a to-be-adhered body stably. For these reasons, the composition of the present invention can be bonded to the adherend with less displacement using the cured product in this semi-cured state.
　また、本発明の組成物は、半硬化状態の硬化物を形成した後、本硬化状態の硬化物を得ることができる。本発明の組成物は、環状エーテル化合物を含むため、本発明の組成物の硬化物は、高温度および高湿度の環境下に置かれた場合でも高い密着力を有する。以上より、本発明の組成物は、被着体を位置ずれ少なく貼り合わせることができる接着容易性と、高温度および高湿度の環境下に置かれた場合でも高い密着力を示す接着性と、を発揮するのである。 Moreover, the composition of this invention can obtain the hardened | cured material of this hardening state, after forming the hardened | cured material of a semi-hardened state. Since the composition of the present invention contains a cyclic ether compound, the cured product of the composition of the present invention has high adhesion even when placed in a high temperature and high humidity environment. From the above, the composition of the present invention has adhesion ease that can bond adherends with little positional deviation, and adhesion showing high adhesion even when placed under high temperature and high humidity environment, To exert
　なお、光照射により硬化する従来の接着剤は、被着体が遮光部分を含む場合に未硬化部分が生じ、被着体との間で十分な密着力を発揮できない場合がある。これに対して、本発明の組成物は、例えば、光照射により形成された半硬化状態の硬化物に対して被着体を貼り合わせ、次いで、熱硬化により本硬化状態とすることで、被着体が遮光部分を有する場合でも、硬化物が被着体との間で高い密着力を発揮することができる。このように、本発明の組成物は、遮光部分を有する被着体に対しても、接着容易性および接着性を有することができるのである。 In addition, when the to-be-adhered body contains a light-shielding part, the conventional adhesive agent hardened | cured by light irradiation may produce an unhardened part, and may not exhibit sufficient adhesive force with a to-be-adhered body. On the other hand, in the composition of the present invention, an adherend is attached to a cured product in a semi-cured state formed by light irradiation, for example, and then the cured product is brought into a main curing state by heat curing. Even when the adherend has a light shielding portion, the cured product can exhibit high adhesion to the adherend. Thus, the composition of the present invention can have easy adhesion and adhesion to an adherend having a light shielding portion.
　本発明の組成物は、上述のとおり、環状エーテル化合物、ラジカル重合性化合物、光ラジカル開始剤および熱重合開始剤を有するものである。以下、本発明の組成物の各成分について説明する。 As described above, the composition of the present invention is one having a cyclic ether compound, a radically polymerizable compound, a photo radical initiator and a thermal polymerization initiator. Hereinafter, each component of the composition of this invention is demonstrated.
１．環状エーテル化合物
　環状エーテル化合物とは、環状エーテル基を有する化合物である。環状エーテル基としては、エーテル結合を環構造の中に少なくとも１つ有するものであればよく、エポキシ基、オキセタニル基等を挙げることができる。すなわち、環状エーテル化合物としては、エポキシ基を有するエポキシ化合物、オキセタニル基を有するオキセタン化合物を挙げることができる。 1. Cyclic Ether Compound The cyclic ether compound is a compound having a cyclic ether group. The cyclic ether group may be any one having at least one ether bond in the ring structure, and examples thereof include an epoxy group and an oxetanyl group. That is, as a cyclic ether compound, the epoxy compound which has an epoxy group, the oxetane compound which has oxetanyl group can be mentioned.
　環状エーテル基の含有数としては、所望の接着性等に応じて適宜設定することができる。環状エーテルの含有数は、環状エーテル化合物１分子当たり１以上であればよいが、２以上１０以下とすることができ、なかでも、２以上５以下であることが好ましく、特に、２以上３以下であることが好ましい。このような環状エーテル化合物を用いた組成物は、接着剤として用いた場合、優れた接着容易性および接着性を発揮するからである。 The number of contained cyclic ether groups can be appropriately set according to the desired adhesiveness and the like. The number of cyclic ethers contained may be 1 or more per one cyclic ether compound, but can be 2 or more and 10 or less, preferably 2 or more and 5 or less, and particularly preferably 2 or more and 3 or less Is preferred. A composition using such a cyclic ether compound exhibits excellent ease of adhesion and adhesiveness when used as an adhesive.
　本発明の組成物の一実施形態としては、環状エーテル化合物として、エポキシ化合物を含むことが好ましい。このような環状エーテル化合物は、優れた硬化性を有するからである。なお、１分子中にエポキシ基と、オキセタニル基等のその他の環状エーテル基と、を含む化合物は、エポキシ化合物に含まれるものとする。 In one embodiment of the composition of the present invention, it is preferable to include an epoxy compound as the cyclic ether compound. Such cyclic ether compounds have excellent curability. In addition, the compound which contains an epoxy group and other cyclic ether groups, such as oxetanyl group, in 1 molecule shall be contained in an epoxy compound.
　エポキシ化合物としては、グリシジルエーテル基を有するグリシジルエーテル型化合物、エポキシシクロアルキル基を有するエポキシシクロアルキル型化合物を挙げることができる。本発明の組成物の一実施形態としては、エポキシ化合物として、グリシジルエーテル型化合物を含むことが好ましい。グリシジルエーテル型化合物は、優れた硬化性を有するため、組成物は優れた接着性を発揮するからである。 As an epoxy compound, the glycidyl ether type compound which has glycidyl ether group, and the epoxy cycloalkyl type compound which has an epoxy cycloalkyl group can be mentioned. In one embodiment of the composition of the present invention, a glycidyl ether type compound is preferably contained as the epoxy compound. The glycidyl ether type compound has excellent curability, so the composition exhibits excellent adhesion.
　本発明の組成物の一実施形態としては、エポキシ化合物として、グリシジルエーテル型化合物およびエポキシシクロアルキル型化合物の両者を含むことが好ましい。グリシジルエーテル型化合物は、エポキシシクロアルキル型化合物と共に用いられることで、組成物中への分散性または溶解性等を向上できる結果、接着容易性および接着性のみならず、透明性に優れた硬化物を得ることができるからである。 In one embodiment of the composition of the present invention, it is preferable to include both a glycidyl ether type compound and an epoxy cycloalkyl type compound as the epoxy compound. A glycidyl ether type compound can improve the dispersibility or solubility in a composition by being used together with an epoxy cycloalkyl type compound, and as a result, a cured product having not only easy adhesion and adhesiveness but also excellent transparency Because you can get
　本発明の組成物の一実施形態としては、グリシジルエーテル型化合物の含有量は、組成物の接着性を向上する観点からは、環状エーテル化合物１００質量部中に、３０質量部以上であることが好ましく、なかでも、８０質量部以上であることが好ましく、特に、９０質量部以上であることが好ましい。 In one embodiment of the composition of the present invention, the content of the glycidyl ether type compound is 30 parts by mass or more in 100 parts by mass of the cyclic ether compound from the viewpoint of improving the adhesion of the composition. Among them, 80 parts by mass or more is preferable, and 90 parts by mass or more is particularly preferable.
　また、本発明の組成物の一実施形態としては、エポキシシクロアルキル型化合物の含有量は、組成物の分散安定性を向上する観点からは、環状エーテル化合物１００質量部中に、３０質量部以上であることが好ましく、なかでも、８０質量部以上であることが好ましく、特に、９０質量部以上であることが好ましい。 In one embodiment of the composition of the present invention, the content of the epoxy cycloalkyl type compound is 30 parts by mass or more in 100 parts by mass of the cyclic ether compound from the viewpoint of improving the dispersion stability of the composition. Among them, 80 parts by mass or more is preferable, and 90 parts by mass or more is particularly preferable.
　上記化合物の両者を含む場合、グリシジルエーテル型化合物の含有量は、グリシジルエーテル型化合物およびエポキシシクロアルキル型化合物１００質量部に対して、１質量部以上９９質量部以下とすることができ、１０質量部以上９０質量部以下であることが好ましく、２０質量部以上８０質量部以下であることが好ましい。かかる組成とすることで、優れた塗工容易性、接着容易性および接着性を発揮するからである。なお、１分子中にグリシジルエーテル基およびエポキシシクロアルキル基の両者を含む化合物は、グリシジルエーテル型化合物に含めるものとする。 When both of the above compounds are contained, the content of the glycidyl ether type compound can be 1 part by mass to 99 parts by mass with respect to 100 parts by mass of the glycidyl ether type compound and the epoxy cycloalkyl type compound, and 10 parts by mass It is preferable that it is a part or more and 90 mass parts or less, and it is preferable that it is 20 mass parts or more and 80 mass parts or less. By using such a composition, excellent coatability, adhesion and adhesiveness are exhibited. In addition, the compound which contains both a glycidyl ether group and an epoxy cycloalkyl group in 1 molecule shall be included in a glycidyl ether type compound.
　本発明の組成物においては、グリシジルエーテル型化合物は、グリシジルエーテル構造を有するものであればよく、脂肪族アルコールのグリシジルエーテル化物、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を挙げることができる。 In the composition of the present invention, the glycidyl ether type compound may be any one having a glycidyl ether structure, such as a glycidyl ether of an aliphatic alcohol, a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof. It can be mentioned.
　グリシジルエーテル型化合物としては、より具体的には、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、グリセリンのトリグリシジルエーテル、トリメチロールプロパンのトリグリシジルエーテル、ソルビトールのテトラグリシジルエーテル、ジペンタエリスリトールのヘキサグリシジルエーテル、ポリエチレングリコールのジグリシジルエーテル、ポリプロピレングリコールのジグリシジルエーテル、ネオペンチルグリコールの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、水素添加ビスフェノールＡジグリシジルエーテルが挙げられる。さらに、脂肪族高級アルコールのモノグリシジルエーテルやエポキシ化ポリブタジエン等を挙げることができる。 More specifically, as the glycidyl ether type compound, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12 to 13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, neopentyl glycol Glycidyl ethers of polyhydric alcohols such as diglycidyl ethers, propylene glycol and trimethylo Trimethylolpropane, polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as glycerin, hydrogenated bisphenol A, diglycidyl ether. Furthermore, monoglycidyl ethers of aliphatic higher alcohols, epoxidized polybutadiene and the like can be mentioned.
　上記グリシジルエーテル型化合物としては、少なくとも１個の芳香族環を有する化合物も用いることができる。芳香族環を有するグリシジルエーテル型化合物としては、例えば、多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ポリグリシジルエーテル、例えばビスフェノールＡ、ビスフェノールＦ、またはこれらに、さらにアルキレンオキサイドを付加した化合物のグリシジルエーテル化物、エポキシノボラック樹脂等を挙げることができる。 As the above glycidyl ether type compound, a compound having at least one aromatic ring can also be used. Examples of glycidyl ether type compounds having an aromatic ring include polyglycidyl ethers of polyhydric phenols or alkylene oxide adducts thereof, such as bisphenol A, bisphenol F, or glycidyl ether compounds of compounds obtained by further adding an alkylene oxide thereto. And epoxy novolac resins.
　上記エポキシシクロアルキル型化合物の具体例としては、少なくとも１個の脂環を有し、脂環に直接ヒドロキシル基が結合した多価アルコールのポリグリシジルエーテル化物またはシクロヘキセンやシクロペンテン環含有化合物を酸化剤でエポキシ化することによって得られるシクロヘキセンオキサイドやシクロペンテンオキサイド含有化合物が挙げられる。 As a specific example of the epoxy cycloalkyl type compound, polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring and a hydroxyl group directly bonded to the alicyclic ring, or cyclohexene or cyclopentene ring-containing compound with an oxidizing agent Examples thereof include cyclohexene oxide and cyclopentene oxide-containing compounds obtained by epoxidation.
　エポキシシクロアルキル型化合物としては、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サンカルボキシレート、３，４－エポキシ－１－メチルシクロヘキシル－３，４－エポキシ－１－メチルヘキサンカルボキシレート、６－メチル－３，４－エポキシシクロヘキシルメチル－６－メチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシ－３－メチルシクロヘキシルメチル－３，４－エポキシ－３－メチルシクロヘキサンカルボキシレート、３，４－エポキシ－５－メチルシクロヘキシルメチル－３，４－エポキシ－５－メチルシクロヘキサンカルボキシレート、２－（３，４－エポキシシクロヘキシル－５，５－スピロ－３，４－エポキシ）シクロヘキサン－メタジオキサン、ビス（３，４－エポキシシクロヘキシルメチル）アジペート、メチレンビス（３，４－エポキシシクロヘキサン）、プロパン－２，２－ジイル－ビス（３，４－エポキシシクロヘキサン）、２，２－ビス（３，４－エポキシシクロヘキシル）プロパン、ジシクロペンタジエンジエポキサイド、エチレンビス（３，４－エポキシシクロヘキサンカルボキシレート）、エポキシヘキサヒドロフタル酸ジオクチル、エポキシヘキサヒドロフタル酸ジ－２－エチルヘキシル、１－エポキシエチル－３，４－エポキシシクロヘキサン、１，２－エポキシ－２－エポキシエチルシクロヘキサン、α－ピネンオキシド、ε－カプロラクトン変性３’，４’－エポキシシクロへキシルメチル　３，４－エポキシシクロヘキサンカルボキシレート等が挙げられる。 As an epoxy cycloalkyl type compound, for example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexane carboxylate , 6-Methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate 3,4-Epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane- Metadioxane Bis (3,4-epoxycyclohexylmethyl) adipate, methylene bis (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, α-pinene oxide, ε-caprolactone modified 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, etc.
　本発明の組成物の一実施形態としては、上記エポキシ化合物として、グリシジルエーテル型化合物およびエポキシシクロアルキル型化合物以外の化合物も用いることができる。このような、グリシジルエーテル型化合物およびエポキシシクロアルキル型化合物以外の化合物としては、例えば、２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物等を挙げることができる。 In one embodiment of the composition of the present invention, compounds other than glycidyl ether type compounds and epoxy cycloalkyl type compounds can also be used as the epoxy compound. As compounds other than such glycidyl ether type compounds and epoxy cycloalkyl type compounds, for example, 1,2-epoxy-4- (2-oxiranyl) cyclohexane of 2,2-bis (hydroxymethyl) -1-butanol An additive etc. can be mentioned.
　エポキシ化合物として好適に使用できる市販品としては、ＵＶＲ－６１００、ＵＶＲ－６１０５、ＵＶＲ－６１１０、ＵＶＲ－６１２８、ＵＶＲ－６２００（以上、ユニオンカーバイド社製）、セロキサイド２０２１、セロキサイド２０２１Ｐ、セロキサイド２０８１、セロキサイド２０８３、セロキサイド２０８５、セロキサイド２０００、セロキサイド３０００、サイクロマーＡ２００、サイクロマーＭ１００、サイクロマーＭ１０１、エポリードＧＴ－３０１、エポリードＧＴ－３０２、エポリード４０１、エポリード４０３、ＥＴＨＢ、エポリードＨＤ３００、ＥＨＰＥ－３１５０、ＥＴＨＢ、エポブレンド（以上、ダイセル化学工業（株）製）、エピコート８０１、エピコート８２８（以上、油化シェルエポキシ社製）、ＰＹ－３０６、０１６３、ＤＹ－０２２（以上、チバ・スペシャルティ・ケミカルズ社製）、ＫＲＭ－２７２０、ＥＰ－４１００、ＥＰ－４０００、ＥＰ－４０８０、ＥＰ－４０８８Ｓ、ＥＰ－４９００、ＥＰＲ－２０００、ＥＰＲ－４０３０、ＥＤ－５０５、ＥＤ－５０６、ＫＲＭ－２１１０、ＫＲＭ－２１９９（以上、（株）ＡＤＥＫＡ製）、エポライトＭ－１２３０、エポライトＥＨＤＧ－Ｌ、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、エポライト４０００、エポライト３００２、エポライトＦＲ－１５００（以上、共栄社化学（株）製）、サントートＳＴ００００、ＹＤ－７１６、ＹＨ－３００、ＰＧ－２０２、ＰＧ－２０７、ＹＤ－１７２、ＹＤＰＮ６３８（以上、東都化成（株）製）、ＪＥＲ８２７、ＪＥＲ８２８、ＪＥＲ８３４、ＪＥＲ１００１、ＪＥＲ１００２、ＪＥＲ１００３、ＪＥＲ１０５５、ＪＥＲ１００７、ＪＥＲ１００９、ＪＥＲ１０１０（以上、ジャパンエポキシレジン（株）製）、ＢＲＥＮ－Ｓ、ＥＰＰＮ－２０１、ＥＰＰＮ－５０１Ｎ、ＥＯＣＮ－１０２０、ＧＡＮ、ＧＯＴ、ＮＣ－２０００Ｌ、ＮＣ－３０００（以上、日本化薬（株）社製）等を挙げることができる。 Commercially available products which can be suitably used as an epoxy compound include UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200 (all manufactured by Union Carbide Corporation), Celoxide 2021, Celoxide 2021 P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 2000, Celoxide 3000, Cyclomer A 200, Cyclomer M 100, Cyclomer M 101, Epolide GT-301, Epolide GT-302, Epolide 401, Epolide 403, ETHB, Epolide HD 300, EHPE-3150, ETHB, Epoblend (above, made by Daicel Chemical Industries, Ltd.), Epicoat 801, Epicoat 828 (above, made by Yuka Shell Epoxy Co., Ltd.), PY- 06, 0163, DY-022 (all manufactured by Ciba Specialty Chemicals), KRM-2720, EP-4100, EP-4000, EP-4080, EP-4088S, EP-4900, EPR-2000, EPR-4030 , ED-505, ED-506, KRM-2110, KRM-2199 (all, made by ADEKA), Epolight M-1230, Epolight EHDG-L, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P EPOLITE 200P, EPOLITE 400P, EPOLITE 1500 NP, EPOLITE 1600, EPOLITE 80 MF, EPOLITE 100 MF, EPOLITE 4000, EPOLITE 3002, EPOLITE FR-1500 (all manufactured by Kyoeisha Chemical Co., Ltd.) , Suntote ST0000, YD-716, YH-300, PG-202, PG-207, YD-172, YDPN 638 (all manufactured by Toto Kasei Co., Ltd.), JER 827, JER 828, JER 834, JER 1001, JER 1002, JER 1003, JER 1055, JER1007, JER1009, JER1010 (above, Japan Epoxy Resins Co., Ltd.), BREN-S, EPPN-201, EPPN-501N, EOCN-1020, GAN, GOT, NC-2000L, NC-3000 (above, Nippon Kayaku) Co., Ltd., etc. can be mentioned.
　また、上記オキセタン化合物の具体例としては、例えば、以下の化合物を挙げることができる。３－エチル－３－ヒドロキシメチルオキセタン、３－（メタ）アリルオキシメチル－３－エチルオキセタン、（３－エチル－３－オキセタニルメトキシ）メチルベンゼン、４－フルオロ－［１－（３－エチル－３－オキセタニルメトキシ）メチル］ベンゼン、４－メトキシ－［１－（３－エチル－３－オキセタニルメトキシ）メチル］ベンゼン、［１－（３－エチル－３－オキセタニルメトキシ）エチル］フェニルエーテル、イソブトキシメチル（３－エチル－３－オキセタニルメチル）エーテル、イソボルニルオキシエチル（３－エチル－３－オキセタニルメチル）エーテル、イソボルニル（３－エチル－３－オキセタニルメチル）エーテル、２－エチルヘキシル（３－エチル－３－オキセタニルメチル）エーテル、エチルジエチレングリコール（３－エチル－３－オキセタニルメチル）エーテル、ジシクロペンタジエン（３－エチル－３－オキセタニルメチル）エーテル、ジシクロペンテニルオキシエチル（３－エチル－３－オキセタニルメチル）エーテル、ジシクロペンテニル（３－エチル－３－オキセタニルメチル）エーテル、テトラヒドロフルフリル（３－エチル－３－オキセタニルメチル）エーテル、テトラブロモフェニル（３－エチル－３－オキセタニルメチル）エーテル、２－テトラブロモフェノキシエチル（３－エチル－３－オキセタニルメチル）エーテル、トリブロモフェニル（３－エチル－３－オキセタニルメチル）エーテル、２－トリブロモフェノキシエチル（３－エチル－３－オキセタニルメチル）エーテル、２－ヒドロキシエチル（３－エチル－３－オキセタニルメチル）エーテル、２－ヒドロキシプロピル（３－エチル－３－オキセタニルメチル）エーテル、ブトキシエチル（３－エチル－３－オキセタニルメチル）エーテル、ペンタクロロフェニル（３－エチル－３－オキセタニルメチル）エーテル、ペンタブロモフェニル（３－エチル－３－オキセタニルメチル）エーテル、ボルニル（３－エチル－３－オキセタニルメチル）エーテル、３，７－ビス（３－オキセタニル）－５－オキサ－ノナン、３，３’－（１，３－（２－メチレニル）プロパンジイルビス（オキシメチレン））ビス－（３－エチルオキセタン）、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、ジシクロペンテニルビス（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、トリシクロデカンジイルジメチレン（３－エチル－３－オキセタニルメチル）エーテル、トリメチロールプロパントリス（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、ペンタエリスリトールトリス（３－エチル－３－オキセタニルメチル）エーテル、ペンタエリスリトールテトラキス（３－エチル－３－オキセタニルメチル）エーテル、ポ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、ジペンタエリスリトールヘキサキス（３－エチル－３－オキセタニルメチル）エーテル、ジペンタエリスリトールペンタキス（３－エチル－３－オキセタニルメチル）エーテル、ジペンタエリスリトールテトラキス（３－エチル－３－オキセタニルメチル）エーテル、カプロラクトン変性ジペンタエリスリトールヘキサキス（３－エチル－３－オキセタニルメチル）エーテル、カプロラクトン変性ジペンタエリスリトールペンタキス（３－エチル－３－オキセタニルメチル）エーテル、ジトリメチロールプロパンテトラキス（３－エチル－３－オキセタニルメチル）エーテル、ＥＯ変性ビスフェノールＡビス（３－エチル－３－オキセタニルメチル）エーテル、ＰＯ変性ビスフェノールＡビス（３－エチル－３－オキセタニルメチル）エーテル、ＥＯ変性水添ビスフェノールＡビス（３－エチル－３－オキセタニルメチル）エーテル、ＰＯ変性水添ビスフェノールＡビス（３－エチル－３－オキセタニルメチル）エーテル、ＥＯ変性ビスフェノールＦ（３－エチル－３－オキセタニルメチル）エーテル等を挙げることができる。 Moreover, as a specific example of the said oxetane compound, the following compounds can be mentioned, for example. 3-ethyl-3-hydroxymethyl oxetane, 3- (meth) allyloxymethyl-3-ethyl oxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3 -Oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl- 3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl ( 3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether Ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl) -3- Xetanyl methyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromo Phenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 '-(1 , 3- (2-Methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-Ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-biphenyl [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol Bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane Tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-Echi -3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-) Oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone modified dipentaerythritol hexakis (3-ethyl- 3-oxetanylmethyl) ether, caprolactone modified with dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3- Ethyl-3-oxetanylmethyl) ether, EO modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, etc. Can.
　なお、本発明の組成物においては、４－ヒドロキシブチルアクリレートグリシジルエーテルのような環状エーテル基およびラジカル重合性基の両者を有する化合物は、環状エーテル化合物には該当せず、ラジカル重合性化合物に該当するものとする。 In the composition of the present invention, a compound having both a cyclic ether group and a radically polymerizable group such as 4-hydroxybutyl acrylate glycidyl ether does not correspond to a cyclic ether compound, but corresponds to a radically polymerizable compound. It shall be.
　本発明の組成物の一実施形態としては、環状エーテル化合物の分子量は、所望の接着性等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、５０以上２，０００，０００以下とすることができる。 In one embodiment of the composition of the present invention, the molecular weight of the cyclic ether compound is not particularly limited as long as desired adhesiveness and the like can be obtained, and for example, 50 or more and 2,000,000 or less can do.
　本発明の組成物の一実施形態としては、環状エーテル化合物は、組成物の塗工容易性および接着容易性等の観点からは、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。 In one embodiment of the composition of the present invention, the cyclic ether compound preferably contains a low molecular weight compound from the viewpoint of ease of application and adhesion of the composition. Moreover, since the low molecular weight compound is excellent in dispersibility or solubility in the composition, a cured product excellent in transparency can be obtained.
　また、本発明の組成物の一実施形態としては、環状エーテル化合物は、組成物の接着容易性および被着体の溶解抑制等の観点からは、高分子量化合物を含むことも好ましい。このような組成物は、被着体が有機材料を含む場合に、被着体の溶解抑制およびそれによる白濁抑制に優れるからである。 In one embodiment of the composition of the present invention, the cyclic ether compound preferably also contains a high molecular weight compound from the viewpoint of ease of adhesion of the composition and suppression of dissolution of the adherend. Such a composition is because when the adherend contains an organic material, the composition is excellent in the suppression of dissolution of the adherend and the suppression of white turbidity thereby.
　本発明の組成物の一実施形態としては、環状エーテル化合物は、組成物の塗工容易性、接着容易性および被着体の溶解抑制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、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。 In one embodiment of the composition of the present invention, the cyclic ether compound is a compound of a low molecular weight compound and a high molecular weight compound from the viewpoint of the balance of ease of application of the composition, ease of adhesion and suppression of dissolution of adherends. It is preferable to include both. Moreover, it is because dispersion | distribution or solubility in a composition can be improved by using a high molecular weight compound with a low molecular weight compound, and the hardened | cured material excellent in 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。 The molecular weight of the low molecular weight compound may be any as long as desired coatability and the like can be obtained, and can be, for example, 1,000 or less, preferably 50 or more and 500 or less, and more preferably 50 or more and 300 or less. It is preferable that it is the following.
　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５，０００以下であることが好ましく、なかでも、１，５００以上３，０００以下であることが好ましい。 The molecular weight of the high molecular weight compound may be any as long as desired adhesion and the like can be obtained, and can be, for example, larger than 1,000, preferably 1,000 or more and 5,000 or less. Especially, it is preferable that they are 1,500 or more and 3,000 or less.
　なお、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。また、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。 In addition, molecular weight shows a weight average molecular weight (Mw), when a compound is a polymer. The weight average molecular weight can be determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).
　重量平均分子量は、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。 The weight average molecular weight is, for example, GPC (LC-2000 plus series) manufactured by JASCO Corporation, the elution solvent is tetrahydrofuran, and polystyrene standards for calibration curve are 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 (TSKgel standard polystyrene manufactured by Tosoh Corp.), and the measurement column is KF It can obtain and measure as -804, KF-803, and KF-802 (made by Showa Denko KK). Also, the measurement temperature can be 40 ° C., and the flow rate can be 1.0 mL / min.
　本発明の組成物の一実施形態としては、環状エーテル化合物における、低分子量化合物の含有量は、所望の接着性等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、接着容易性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。接着容易性および透明性等のバランスに優れたものとする観点からは、低分子量化合物の含有量は、例えば、環状エーテル化合物１００質量部中に、４０質量部以上９０質量部以下であることが好ましく、なかでも、４５質量部以上８０質量部以下であることが好ましい。また、組成物の塗工容易性および接着容易性等の観点からは、低分子量化合物の含有量としては、例えば、環状エーテル化合物１００質量部中に、５０質量部以上であることが好ましく、なかでも、７０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、１００質量部であること、すなわち、環状エーテル化合物として、低分子量化合物のみを含むことが好ましい。 In one embodiment of the composition of the present invention, the content of the low molecular weight compound in the cyclic ether compound is not particularly limited as long as desired adhesiveness and the like can be obtained, for example, adhesion ease It adjusts suitably from a viewpoint of balance, such as transparency and transparency. From the viewpoint of achieving an excellent balance of adhesion ease and transparency, the content of the low molecular weight compound is, for example, 40 parts by mass or more and 90 parts by mass or less in 100 parts by mass of the cyclic ether compound. Among these, 45 parts by mass or more and 80 parts by mass or less are preferable. In addition, from the viewpoint of easiness of coating and adhesion of the composition, the content of the low molecular weight compound is, for example, preferably 50 parts by mass or more in 100 parts by mass of the cyclic ether compound. However, 70 parts by mass or more is preferable, 90 parts by mass or more is preferable, and 100 parts by mass, that is, it is preferable that only a low molecular weight compound is contained as a cyclic ether compound.
　本発明の組成物の一実施形態としては、上記環状エーテル化合物は、室温で液体である化合物（以下、単に、「液体化合物」と称する場合がある。）を含むものであってもよいが、室温で固体である化合物（以下、単に、「固体化合物」と称する場合がある。）を含むことが好ましい。固体化合物としては、軟化点または融点（軟化点および融点の両者を有する場合には、軟化点）が３０℃以上であるものとすることができる。液体化合物としては、軟化点または融点（軟化点および融点の両者を有する場合には、軟化点）が３０℃未満であるものとすることができる。固体化合物を含むことにより、本発明の一実施形態に係る組成物は、優れた接着性を発揮可能となるからである。 In one embodiment of the composition of the present invention, the cyclic ether compound may include a compound which is liquid at room temperature (hereinafter, may be simply referred to as “liquid compound”). It is preferable to include a compound which is solid at room temperature (hereinafter, may be simply referred to as "solid compound"). The solid compound may be one having a softening point or a melting point (a softening point when both a softening point and a melting point are present) of 30 ° C. or more. The liquid compound may be one having a softening point or a melting point (if the softening point and the melting point are both, the softening point) is less than 30 ° C. By including the solid compound, the composition according to the embodiment of the present invention can exhibit excellent adhesion.
　固体化合物の軟化点または融点（軟化点および融点の両者を有する場合には、軟化点）としては、３５℃以上１８０℃以下であることが好ましく、なかでも、４０℃以上１００℃以下であることが好ましく、特に、４２℃以上８０℃以下であることが好ましく、なかでも特に、４５℃以上７０℃以下であることが好ましい。軟化点または融点が上述の範囲であることで、接着性に優れると共に、固体状化合物を、室温で液状である液状化合物と混合する場合、例えば、固体状化合物を軟化点以上に加熱することで両者を相溶性よく混合することが容易となる等、本発明の一実施形態に係る組成物の製造が容易になるからである。また、本発明の一実施形態に係る組成物は、塗布性に優れたものとなるからである。なお、軟化点は、ＪＩＳ　Ｋ７２３４（環球法）に準拠した方法により求められるものである。 The softening point or melting point (if the softening point and the melting point are both, the softening point) of the solid compound is preferably 35 ° C. or more and 180 ° C. or less, and more preferably 40 ° C. or more and 100 ° C. or less In particular, the temperature is preferably 42 ° C. or more and 80 ° C. or less, and particularly preferably 45 ° C. or more and 70 ° C. or less. When mixing a solid compound with a liquid compound that is liquid at room temperature while having excellent adhesion as the softening point or melting point is in the above range, for example, by heating the solid compound to the softening point or higher This is because, for example, it becomes easy to mix the two with good compatibility, and the manufacture of the composition according to one embodiment of the present invention becomes easy. Moreover, it is because the composition concerning one Embodiment of this invention becomes the thing excellent in applicability. In addition, a softening point is calculated | required by the method based on JISK7234 (ring and ball method).
　本発明の組成物の一実施形態としては、固体化合物の含有量は、所望の接着性が得られるものであればよいが、固体化合物および液体化合物の合計１００質量部中に、１０質量部以上７０質量部以下であることが好ましく、２０質量部以上６０質量部以下であることが好ましい。固体状化合物の含有量を上述の範囲とすることで、本発明の一実施形態に係る組成物の製造容易性および塗工容易性、接着容易性および被着体の溶解抑制のバランスを優れたものとすることができるからである。 In one embodiment of the composition of the present invention, the content of the solid compound may be any as long as desired adhesiveness can be obtained, but 10 parts by mass or more in 100 parts by mass of the total of the solid compound and the liquid compound It is preferable that it is 70 mass parts or less, and it is preferable that it is 20 mass parts or more and 60 mass parts or less. By setting the content of the solid compound in the above-mentioned range, the balance between the easiness of production of the composition according to an embodiment of the present invention and the easiness of coating, adhesion ease and suppression of dissolution of adherends is excellent. It is because it can be
　本発明の組成物の一実施形態としては、環状エーテル化合物の含有量は、所望の接着性等が得られるものであれば特に限定されるものではないが、例えば、組成物の固形分１００質量部中に１０質量部以上９５質量部以下とすることができ、３０質量部以上８５質量部以下であることが好ましく、なかでも、４０質量部以上６０質量部以下であることが好ましい。環状エーテル化合物の含有量が上述の範囲内であることで、優れた接着容易性および接着性を発揮するからである。なお、固形分とは、溶剤以外の全ての成分を含むものである。なお、本発明の組成物においては、特に断りがない場合には、含有量は質量基準であり、環状エーテル化合物、ラジカル重合性化合物、光ラジカル開始剤および熱重合開始剤は、例えば２５℃で液状であっても、固形分に含まれる。 Although content of a cyclic ether compound is not specifically limited if desired adhesiveness etc. are obtained as one embodiment of the composition of this invention, For example, solid content 100 mass of a composition is used. The amount may be 10 parts by mass or more and 95 parts by mass or less, preferably 30 parts by mass or more and 85 parts by mass or less, and particularly preferably 40 parts by mass or more and 60 parts by mass or less. When the content of the cyclic ether compound is in the above-mentioned range, excellent adhesion easiness and adhesiveness are exhibited. In addition, solid content contains all the components other than a solvent. In the composition of the present invention, unless otherwise specified, the content is on a mass basis, and cyclic ether compounds, radically polymerizable compounds, photo radical initiators and thermal polymerization initiators are, for example, at 25 ° C. Even in liquid form, it is included in the solid content.
２．ラジカル重合性化合物
　ラジカル重合性化合物とは、ラジカル重合性基を有するものである。ラジカル重合性基としては、ラジカル重合により重合可能なものであればよく、メタクリル基、アクリル基、アリル基等のエチレン性不飽和二重結合基を挙げることができ、なかでもメタクリル基またはアクリル基であることが好ましく、なかでもアクリル基であること、すなわち、ラジカル重合性化合物がアクリレートであることが好ましい。ラジカル重合性基がこれらの官能基であることで、ラジカル重合性化合物は、酸素阻害の影響が少なく、組成物は、優れた接着性を発揮するからである。 2. Radically Polymerizable Compound The radically polymerizable compound is one having a radically polymerizable group. The radically polymerizable group may be any group as long as it can be polymerized by radical polymerization, and examples thereof include ethylenically unsaturated double bond groups such as methacryl group, acryl group and allyl group, among which methacryl group or acryl group It is preferable that it is an acryl group, that is, the radically polymerizable compound is an acrylate. It is because a radically polymerizable compound has little influence of oxygen inhibition by a radically polymerizable group being these functional groups, and a composition exhibits the outstanding adhesiveness.
　本発明の組成物の一実施形態としては、ラジカル重合性化合物におけるラジカル重合性基の含有数は、所望の接着性等に応じて適宜設定することができる。ラジカル重合性基の含有数は、ラジカル重合性化合物１分子当たり１以上であればよいが、２以上５０以下とすることができる。このようなラジカル重合性化合物を含む組成物は、接着剤として用いた場合、優れた接着容易性および接着性を発揮するからである。 As one embodiment of the composition of the present invention, the number of radically polymerizable groups in the radically polymerizable compound can be appropriately set according to the desired adhesiveness and the like. The number of radically polymerizable groups contained may be 1 or more per molecule of radically polymerizable compound, but can be 2 or more and 50 or less. A composition containing such a radically polymerizable compound exhibits excellent ease of adhesion and adhesiveness when used as an adhesive.
　ラジカル重合性化合物としては、具体的には、ウレタンメタクリレート、ウレタンアクリレート等のウレタン結合を有する化合物、メタクリルモノマー、アクリルモノマー等のウレタン結合を有しない化合物（以下、単に、「アクリレートモノマー」と称する場合がある。）を挙げることができる。 Specific examples of the radically polymerizable compound include compounds having a urethane bond such as urethane methacrylate and urethane acrylate, and compounds having no urethane bond such as methacrylic monomer and acrylic monomer (hereinafter referred to simply as "acrylate monomer") Can be mentioned.
　ラジカル重合性化合物は、ウレタン結合を有する化合物およびウレタン結合を有しない化合物の少なくとも一方を含むものとすることができ、なかでも、ウレタン結合を有する化合物およびウレタン結合を有しない化合物の両者を含むものであることが好ましい。このような組成物は、接着剤として用いた場合、優れた接着容易性および接着性を発揮するからである。 The radically polymerizable compound may include at least one of a compound having a urethane bond and a compound having no urethane bond, and in particular, it may include both a compound having a urethane bond and a compound having no urethane bond. preferable. Such a composition is because it exhibits excellent adhesion and adhesiveness when used as an adhesive.
　ラジカル重合性化合物が、ウレタン結合を有する化合物およびウレタン結合を有しない化合物の両者を含むものである場合、ウレタン結合を有しない化合物の含有量は、例えば、ウレタン結合を有しない化合物およびウレタン結合を有する化合物の合計１００質量部に対して、２０質量部以上６０質量部以下であることが好ましく、なかでも３０質量部以上６０質量部以下であることが好ましい。このような組成物は、優れた接着容易性および接着性を発揮するからである。 When the radically polymerizable compound contains both a compound having a urethane bond and a compound having no urethane bond, the content of the compound having no urethane bond is, for example, a compound having no urethane bond and a compound having a urethane bond It is preferable that it is 20 mass parts or more and 60 mass parts or less with respect to a total of 100 mass parts, and it is preferable that it is 30 mass parts or more and 60 mass parts or less especially. Such a composition is because it exhibits excellent adhesion and adhesiveness.
　ウレタン結合を有する化合物としては、例えば、ウレタン（メタ）アクリレートとして、ポリカーボネート系ウレタン（メタ）アクリレート、ポリエステル系ウレタン（メタ）アクリレート、ポリエーテル系ウレタン（メタ）アクリレート、カプロラクトン系ウレタン（メタ）アクリレート等が挙げられ、これらは、ポリオールとジイソシアネートとを反応させて得られるイソシアネート化合物と、水酸基を有する（メタ）アクリレートモノマーとの反応により得ることができる。 Examples of the compound having a urethane bond include, as urethane (meth) acrylate, polycarbonate urethane (meth) acrylate, polyester urethane (meth) acrylate, polyether urethane (meth) acrylate, caprolactone urethane (meth) acrylate and the like These can be obtained by the reaction of an isocyanate compound obtained by reacting a polyol and a diisocyanate with a (meth) acrylate monomer having a hydroxyl group.
　上記ポリオールとしては、ポリカーボネートジオール、ポリエステルポリオール、ポリエーテルポリオール、ポリカプロラクトンポリオールが挙げられる。 Examples of the polyols include polycarbonate diols, polyester polyols, polyether polyols, and polycaprolactone polyols.
　上記水酸基を有するアクリレートモノマーとしては、アクリル酸、ヒドロキシエチルアクリレート等が挙げられる。なお、（メタ）アクリレートは、アクリレートおよびメタクリレートの両者の意を含むものである。また、以下、（メタ）アクリルについても、アクリルおよびメタクリルの両方の意を含むものである。 As an acrylate monomer which has the said hydroxyl group, acrylic acid, hydroxyethyl acrylate, etc. are mentioned. In addition, (meth) acrylate includes the meaning of both an acrylate and a methacrylate. In addition, hereinafter, with respect to (meth) acrylic, both meaning of acrylic and methacrylic is included.
　ウレタン結合を有する化合物の市販品としては、例えば、アートレジンＵＮ－３３３、ＵＮ－３５０、ＵＮ－３５２、ＵＮ－３５３、ＵＮ－１２５５、ＵＮ－２６００、ＵＮ－２７００、ＵＮ－５５００、ＵＮ－５５９０、ＵＮ－５５０７、ＵＮ－６０６０ＰＴＭ、ＵＮ－６２００、ＵＮ－６２０２、ＵＮ－６３０３、ＵＮ－６３０４、ＵＮ－６３０５、ＵＮ－７６００、ＵＮ－７７００、ＵＮ－９０００ＰＥＰ、ＵＮ－９２００Ａ、ＵＮ－３３２０ＨＡ、ＵＮ－３３２０ＨＣ、ＵＮ－３３２０ＨＳ、ＵＮ－９０４、ＵＮ－９０６Ｓ、ＵＮ－９０１Ｔ、ＵＮ－９０５、ＵＮ－９５２（以上、根上工業（株）製）、ＥＢＥＣＲＹＬ２３０、ＥＢＥＣＲＹＬ２７０、ＥＢＥＣＲＹＬ４８５８、ＥＢＥＣＲＹＬ８８０７、ＥＢＥＣＲＹＬ９２６０、ＥＢＥＣＲＹＬ９２７０（以上、ダイセル・オルネクス（株）製）、Ｕ－４ＨＡ、Ｕ－６ＨＡ、Ｕ－６ＬＰＡ、ＵＡ－１１００Ｈ、ＵＡ－２００ＰＡ、ＵＡ－４２００、ＵＡ－１２２Ｐ、ＵＡ－５３Ｈ、ＮＫエステルＡＢＥ－３００、Ａ９３００、Ａ－ＬＥＮ－１０、ＮＫエステルＡＭＰ－１０Ｇ、Ａ－ＴＭＭ－３ＬＭ－Ｎ、Ａ－ＤＰＨ、Ａ－ＴＭＭＴ（以上、新中村化学工業（株））等が挙げられる。 As a commercial item of the compound which has a urethane bond, for example, art resin UN-333, UN-350, UN-352, UN-353, UN-1255, UN-2600, UN-2700, UN-5500, UN-5590. , UN-5507, UN-6060PTM, UN-6200, UN-6202, UN-6303, UN-6304, UN-6305, UN-7600, UN-7700, UN-9000PEP, UN-9200A, UN-3320HA, UN -3320HC, UN-3320HS, UN-904, UN-906S, UN-901T, UN-905, UN-952 (above, made by Kegami Kogyo Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8807, EBECRYL9260 EBECRYL 9270 (manufactured by Daicel Ornex Co., Ltd.), U-4HA, U-6HA, U-6LPA, UA-1100H, UA-200PA, UA-4200, UA-122P, UA-53H, NK ester ABE-300 A9300, A-LEN-10, NK ester AMP-10G, A-TMM-3LM-N, A-DPH, A-TMMT (all from Shin-Nakamura Chemical Co., Ltd.) and the like.
　ウレタン結合を有する化合物の重量平均分子量（Ｍｗ）は、所望の接着性等が得られるものであれば特に限定されるものではないが、１，０００以上２００，０００以下とすることができ、なかでも、２，０００以上３０，０００以下であることが好ましく、特に、２，０００以上２０，０００以下であることが好ましい。このような組成物は、接着剤として用いた場合、優れた接着容易性および接着性を有するからである。 The weight average molecular weight (Mw) of the compound having a urethane bond is not particularly limited as long as desired adhesiveness and the like can be obtained, but can be 1,000 or more and 200,000 or less. However, it is preferably 2,000 or more and 30,000 or less, and particularly preferably 2,000 or more and 20,000 or less. Such a composition is because it has excellent adhesion and adhesiveness when used as an adhesive.
　ウレタン結合を有する化合物に含まれるラジカル重合性官能基の含有数としては、所望の接着性等が得られるものであれば特に限定されるものではないが、１分子中に１以上２０以下とすることができ、なかでも、１以上１０以下であることが好ましく、特に、１以上３以下であることが好ましい。このような組成物は、接着剤として用いた場合、優れた接着容易性および接着性を有するからである。 The number of radically polymerizable functional groups contained in the compound having a urethane bond is not particularly limited as long as desired adhesiveness and the like can be obtained, but it is 1 or more and 20 or less in one molecule. Among them, it is preferably 1 or more and 10 or less, and particularly preferably 1 or more and 3 or less. Such a composition is because it has excellent adhesion and adhesiveness when used as an adhesive.
　ウレタン結合を有しない化合物としては、所望の接着性等が得られるものであれば特に限定されるものではなく、ラジカル重合性官能基を１つ有する単官能化合物、２以上有する多官能化合物を用いることができる。 The compound having no urethane bond is not particularly limited as long as desired adhesiveness and the like can be obtained, and a monofunctional compound having one radically polymerizable functional group and a polyfunctional compound having two or more groups are used. be able to.
　ウレタン結合を有しない化合物は、単官能化合物を含むことが好ましい。このような組成物は、接着剤として用いた場合、優れた接着容易性および接着性を有するからである。 The compound having no urethane bond preferably contains a monofunctional compound. Such a composition is because it has excellent adhesion and adhesiveness when used as an adhesive.
　単官能化合物としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸ミリスチル、（メタ）アクリル酸パルミチルおよび（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）アクリル酸イソボルニル、（メタ）アクリル酸フェノキシエチル、（メタ）アクリル酸ベンジル、ポリオキシアルキレン変性（メタ）アクリレート、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、（メタ）アクリル酸４－ヒドロキシブチル等の（メタ）アクリル酸ヒドロキシアルキルエステル；アクリルアミド、メタクリルアミド、Ｎ－メチルアクリルアミド、Ｎ－メチルメタクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－メチロールメタクリルアミド等のアクリルアミド類；Ｎ－Ｎ－ジメチル（メタ）アクリルアミド、Ｎ－Ｎ－ジエチル（メタ）アクリルアミド、Ｎ－（メタ）アクリロイルモルフォリン、（メタ）アクリル酸Ｎ－Ｎ－ジエチルアミノエチル；アクリル酸、メタクリル酸、クロトン酸、マレイン酸、イタコン酸、シトラコン酸等のエチレン性不飽和カルボン酸等を挙げることができる。 Examples of monofunctional compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate And stearyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, polyoxyalkylene modified (meth) acrylate, (meth) acrylic Acid 2-hydroxyethyl, (meth) acid 2-hydroxypropyl methacrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate ) Acrylic acid hydroxyalkyl esters; Acrylamides such as acrylamide, methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide; N-N-dimethyl (meth) acrylamide, N- N-diethyl (meth) acrylamide, N- (meth) acryloyl morpholine, N-N-diethylaminoethyl (meth) acrylate; ethylenic such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid Such unsaturated carboxylic acid may be mentioned.
　単官能化合物としては、テトラヒドロフルフリル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートグリシジルエーテル等の環状エーテル基を有する化合物も用いることができる。本発明の組成物の一実施形態としては、単官能化合物は、１種類のみ含むものであってもよく、例えば、２種類以上を組み合わせて用いてもよい。 As a monofunctional compound, a compound having a cyclic ether group such as tetrahydrofurfuryl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether can also be used. In one embodiment of the composition of the present invention, the monofunctional compound may contain only one type, and for example, two or more types may be used in combination.
　本発明の組成物の一実施形態としては、単官能化合物に、環状エーテル基を有する化合物、（メタ）アクリル酸ヒドロキシアルキルエステル等の水酸基を有する化合物等を含むことが好ましい。このような組成物は、接着剤として用いた場合、優れた接着性を発揮するからである。 In one embodiment of the composition of the present invention, the monofunctional compound preferably contains a compound having a cyclic ether group, a compound having a hydroxyl group such as (meth) acrylic acid hydroxyalkyl ester, and the like. Such a composition is because it exhibits excellent adhesiveness when used as an adhesive.
　環状エーテル基を有する化合物の含有量は、所望の接着性等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、単官能化合物１００質量部に対して、５０質量部以上であることが好ましく、なかでも６０質量部以上であることが好ましく、特に、７０質量部以上であることが好ましい。かかる範囲とすることで、組成物は、接着剤として用いた場合、優れた接着性を発揮するからである。 The content of the compound having a cyclic ether group is not particularly limited as long as desired adhesiveness and the like can be obtained, and for example, it is 50 parts by mass or more with respect to 100 parts by mass of the monofunctional compound. In particular, it is preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more. Within this range, the composition exhibits excellent adhesion when used as an adhesive.
　また、上記（メタ）アクリル酸ヒドロキシアルキルエステル等の水酸基を有する化合物の含有量、並びに水酸基を有する化合物および環状エーテル基を有する化合物の両者を含む場合の合計の含有量についても、それぞれ、環状エーテル基を有する化合物の含有量と同様とすることができる。 In addition, the content of the compound having a hydroxyl group such as the above (meth) acrylic acid hydroxyalkyl ester, and the total content in the case of including both the compound having a hydroxyl group and the compound having a cyclic ether group are each cyclic ether. It can be made similar to the content of the compound having a group.
　単官能化合物には、架橋炭素環基を有する架橋炭素環化合物を含むことが好ましい。単官能化合物に架橋炭素環化合物が含まれることで、組成物は、接着剤として用いた場合、優れた接着性を発揮するからである。ここで、架橋炭素環は、２以上の炭化水素環同士がその環構造の一部を共有する構造である。 The monofunctional compound preferably includes a bridged carbocyclic compound having a bridged carbocyclic group. When the cross-linked carbocyclic compound is contained in the monofunctional compound, the composition exhibits excellent adhesiveness when used as an adhesive. Here, the bridging carbon ring is a structure in which two or more hydrocarbon rings share a part of the ring structure.
　架橋炭素環化合物としては、例えば、（メタ）アクリル酸イソボルニル等のイソボルニル基を有する化合物、（メタ）アクリル酸１－アダマンチル、（メタ）アクリル酸２－メチル－２－アダマンチル等のアダマンチル基を有する化合物、ジシクロペンタジエン等を挙げることができる。 Examples of the bridged carbocyclic compound include compounds having an isobornyl group such as (meth) acrylic acid isobornyl, etc., an adamantyl group such as 1-adamantyl (meth) acrylic acid and 2-methyl-2-adamantyl (meth) acrylic acid. Compounds, dicyclopentadiene and the like can be mentioned.
　架橋炭素環化合物の含有量は、所望の接着性等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、単官能化合物１００質量部に対して、５０質量部以下であることが好ましく、なかでも１０質量部以上４０質量部以下であることが好ましく、特に、２０質量部以上３０質量部以下であることが好ましい。かかる範囲とすることで、組成物は、接着剤として用いた場合、優れた接着性を発揮するからである。 The content of the crosslinked carbocyclic compound is not particularly limited as long as desired adhesiveness and the like can be obtained, and preferably 50 parts by mass or less with respect to 100 parts by mass of the monofunctional compound, for example. Among them, the amount is preferably 10 parts by mass or more and 40 parts by mass or less, and particularly preferably 20 parts by mass or more and 30 parts by mass or less. Within this range, the composition exhibits excellent adhesion when used as an adhesive.
　上記多官能化合物としては、例えば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、ネオペンチルグリコールジ（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、ネオペンチルグリコールアジペートジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、カプロラクトン変性ジシクロペンテニルジ（メタ）アクリレート、エチレンオキシド変性リン酸ジ（メタ）アクリレート、ジ（アクリロキシエチル）イソシアヌレート、アリル化シクロヘキシルジ（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トリ（メタ）アクリレート、プロピオン酸変性ジペンタエリスリトールトリ（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、プロピレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート、ビス（アクリロキシエチル）ヒドロキシエチルイソシアヌレート、イソシアヌル酸エチレンオキサイド変性ジアクリレート、イソシアヌル酸エチレンオキサイド変性トリアクリレート、ε―カプロラクトン変性トリス（アクリロキシエチル）イソシアヌレート、ジグリセリンテトラ（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、プロピオン酸変性ジペンタエリスリトールペンタ（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、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート等を挙げることができる。これら多官能化合物は、１種類のみ含むものであってもよく、例えば、２種類以上を組み合わせて用いてもよい。 Examples of the polyfunctional compound include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neo Pentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified phosphoric acid di (meth) Acrylate, di (acryloxyethyl) isocyanurate, allylated cyclohexyl di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) a Lilate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, bis (acryloxyethyl) hydroxy Ethyl isocyanurate, ethylene oxide modified with isocyanurate ethylene oxide, triacrylate with isocyanuric acid, ε-caprolactone modified tris (acryloxyethyl) isocyanurate, diglycerin tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, propion Acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate And caprolactone modified dipentaerythritol hexa (meth) acrylate. These polyfunctional compounds may contain only one type, and, for example, two or more types may be used in combination.
　ウレタン結合を有しない化合物の分子量は、５，０００以下とすることができ、なかでも、１００以上１，０００以下であることが好ましく、特に、１００以上５００以下であることが好ましい。このような組成を有する組成物は、接着剤として用いた場合、優れた接着容易性および接着性を発揮するからである。 The molecular weight of the compound not having a urethane bond can be 5,000 or less, preferably 100 or more and 1,000 or less, and particularly preferably 100 or more and 500 or less. A composition having such a composition exerts excellent ease of adhesion and adhesiveness when used as an adhesive.
　本発明の組成物の一実施形態としては、ラジカル重合性化合物の分子量は、所望の接着性等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、５０以上２００，０００以下とすることができる。 In one embodiment of the composition of the present invention, the molecular weight of the radically polymerizable compound is not particularly limited as long as desired adhesiveness and the like can be obtained, and is, for example, 50 or more and 200,000 or less. be able to.
　本発明の組成物の一実施形態としては、ラジカル重合性化合物は、組成物の塗工容易性および接着容易性等の観点からは、低分子量化合物を含むことが好ましい。また、本発明の組成物の一実施形態としては、ラジカル重合性化合物は、組成物の接着容易性および被着体の溶解抑制等の観点からは、高分子量化合物を含むことが好ましい。このような組成物は、被着体が有機材料を含む場合に、被着体の溶解抑制およびそれによる白濁抑制に優れるからである。 In one embodiment of the composition of the present invention, the radically polymerizable compound preferably contains a low molecular weight compound from the viewpoint of ease of application and adhesion of the composition. In one embodiment of the composition of the present invention, the radically polymerizable compound preferably contains a high molecular weight compound from the viewpoint of ease of adhesion of the composition and suppression of dissolution of the adherend. Such a composition is because when the adherend contains an organic material, the composition is excellent in the suppression of dissolution of the adherend and the suppression of white turbidity thereby.
　本発明の組成物の一実施形態としては、ラジカル重合性化合物は、組成物の塗工容易性、接着容易性および被着体の溶解抑制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。 In one embodiment of the composition of the present invention, the radically polymerizable compound is 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 ease of adhesion and the suppression of dissolution of adherends. It is preferable to include both of them.
　低分子量化合物の分子量は、所望の塗工性等が得られるものであればよく、例えば、２，０００以下とすることができ、５０以上１，０００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。 The molecular weight of the low molecular weight compound may be any as long as desired coatability and the like can be obtained, and can be, for example, 2,000 or less, preferably 50 or more and 1,000 or less, and more preferably 50 or more. It is preferable that it is 300 or less.
　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、２，０００より大きいものとすることができ、２，５００以上２０，０００以下であることが好ましく、なかでも、２，５００以上１０，０００以下であることが好ましい。 The molecular weight of the high molecular weight compound may be any as long as desired adhesion and the like can be obtained, and can be, for example, larger than 2,000, and preferably 2,500 or more and 20,000 or less. Especially, it is preferable that they are 2,500 or more and 10,000 or less.
　ラジカル重合性化合物に含まれる低分子量化合物の含有量は、所望の接着性等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、低分子量化合物および高分子量化合物の合計１００質量部に対して、１０質量部以上９０質量部以下とすることができ、３０質量部以上７０質量部以下であることが好ましく、なかでも４０質量部以上６０質量部以下であることが好ましい。このような組成物は、被着体が有機材料を含む場合に、被着体の溶解抑制およびそれによる白濁抑制に優れるからである。また、このような組成物は、優れた塗工容易性および接着容易性を発揮するからである。 The content of the low molecular weight compound contained in the radically polymerizable compound is not particularly limited as long as desired adhesiveness and the like can be obtained, and for example, the total of 100 parts by mass of the low molecular weight compound and the high molecular weight compound On the other hand, it can be 10 parts by mass or more and 90 parts by mass or less, preferably 30 parts by mass or more and 70 parts by mass or less, and particularly preferably 40 parts by mass or more and 60 parts by mass or less. Such a composition is because when the adherend contains an organic material, the composition is excellent in the suppression of dissolution of the adherend and the suppression of white turbidity thereby. In addition, such a composition exhibits excellent ease of application and adhesion.
　本発明の組成物の一実施形態としては、ラジカル重合性化合物の含有量は、所望の接着性等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、環状エーテル化合物およびラジカル重合性化合物の合計１００質量部に対して１質量部以上９９質量部以下とすることができ、１０質量部以上９０質量部以下であることが好ましく、なかでも、４０質量部以上６０質量部以下であることが好ましい。ラジカル重合性化合物の含有量を上述の範囲内とすることで、接着剤として用いた場合、優れた接着容易性および接着性を発揮するからである。 In one embodiment of the composition of the present invention, the content of the radically polymerizable compound is not particularly limited as long as desired adhesiveness and the like can be obtained, and, for example, cyclic ether compounds and radically polymerizable The amount can be 1 to 99 parts by mass, preferably 10 to 90 parts by mass, and more preferably 40 to 60 parts by mass with respect to 100 parts by mass of the total of the compounds. Is preferred. When the content of the radically polymerizable compound is in the range described above, when it is used as an adhesive, excellent adhesion easiness and adhesiveness are exhibited.
　本発明の組成物の一実施形態としては、ラジカル重合性化合物の含有量は、組成物の固形分１００質量部に対して、５質量部上９５質量部以下とすることができ、３０質量部以上８０質量部以下であることが好ましく、なかでも、４０質量部以上６０質量部以下であることが好ましい。このような組成物は、接着剤として用いた場合、優れた接着容易性および接着性を有するからである。 As one embodiment of the composition of the present invention, the content of the radically polymerizable compound can be 5 parts by mass to 95 parts by mass or less with respect to 100 parts by mass of the solid content of the composition, and 30 parts by mass The content is preferably 80 parts by mass or less, and more preferably 40 parts by mass or more and 60 parts by mass or less. Such a composition is because it has excellent adhesion and adhesiveness when used as an adhesive.
３．光ラジカル開始剤
　本発明の組成物において、光ラジカル開始剤は、ラジカル重合性基同士を重合可能なものである。本発明の組成物一実施形態としては、光ラジカル開始剤は、１種類のみを含むものであってもよく、２種類以上を組み合わせて用いてもよい。本発明の組成物においては、光ラジカル開始剤としては、具体的には、従来既知の化合物を用いることが可能であり、例えば、ベンゾフェノン、フェニルビフェニルケトン、１－ヒドロキシ－シクロヘキシル－フェニルケトン、１－ヒドロキシ－１－ベンゾイルシクロヘキサン、ベンゾイン、ベンジルジメチルケタール、１－ベンジル－１－ジメチルアミノ－１－（４’－モルホリノベンゾイル）プロパン、２－モルホリル－２－（４’－メチルメルカプト）ベンゾイルプロパン、チオキサントン、１－クロル－４－プロポキシチオキサントン、イソプロピルチオキサントン、ジエチルチオキサントン、エチルアントラキノン、４－ベンゾイル－４’－メチルジフェニルスルフィド、ベンゾインブチルエーテル、２－ヒドロキシ－２－ベンゾイルプロパン、２－ヒドロキシ－２－（４’－イソプロピル）ベンゾイルプロパン、４－ブチルベンゾイルトリクロロメタン、４－フェノキシベンゾイルジクロロメタン、ベンゾイル蟻酸メチル、１，７－ビス（９’－アクリジニル）ヘプタン、９－ｎ－ブチル－３，６－ビス（２’－モルホリノイソブチロイル）カルバゾール、２－メチル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－フェニル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－ナフチル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２，２－ビス（２－クロロフェニル）－４，５，４’，５’－テトラフェニル－１－２’－ビイミダゾール、４、４－アゾビスイソブチロニトリル、トリフェニルホスフィン、カンファーキノン、過酸化ベンゾイル、１．２－オクタンジオン，１－［４－（フェニルチオ）－，２－（Ｏ－ベンゾイルオキシム）］、エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（０－アセチルオキシム）等が挙げられる。 3. Photoradical initiator In the composition of the present invention, the photoradical initiator is capable of polymerizing radically polymerizable groups. In one embodiment of the composition of the present invention, the photo radical initiator may contain only one type, or two or more types may be used in combination. In the composition of the present invention, specifically, conventionally known compounds can be used as the photo radical initiator, and examples thereof include benzophenone, phenylbiphenyl ketone, 1-hydroxy-cyclohexyl-phenyl ketone, 1 -Hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morpholine-2- (4'-methylmercapto) benzoylpropane, Thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoyl Lopan, 2-hydroxy-2- (4'-isopropyl) benzoylpropane, 4-butyl benzoyl trichloromethane, 4-phenoxy benzoyl dichloromethane, methyl benzoyl formate, 1,7-bis (9'-acridinyl) heptane, 9-n -Butyl-3,6-bis (2'-morpholinoisobutyryl) carbazole, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine, 2,2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1-2 '-Biimidazole, 4, 4-azobisisobutyronitrile, triphenylphosphine, camphorquinone, benzoyl peroxide 1.2-Octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Yl]-, 1- (0-acetyl oxime) and the like.
　光ラジカル開始剤の市販品としては、Ｎ－１４１４、Ｎ－１７１７、Ｎ－１９１９、ＰＺ－４０８、ＮＣＩ－８３１、ＮＣＩ－９３０（（株）ＡＤＥＫＡ社製）、ＩＲＧＡＣＵＲＥ３６９、ＩＲＧＡＣＵＲＥ９０７、ＩＲＧＡＣＵＲＥＯＸＥ０１、ＩＲＧＡＣＵＲＥＯＸＥ０２（ＢＡＳＦ（株）社製）等が挙げられる。 As a commercial item of a photo radical initiator, N-1414, N-1717, N-1919, PZ-408, NCI-831, NCI-930 (made by ADEKA Corporation), IRGACURE369, IRGACURE907, IRGACUREOXE01, IRGACUREOXE02 ( BASF Corporation) and the like.
　本発明の組成物の一実施形態としては、光ラジカル開始剤の含有量は、所望の接着性等が得られるものであれば特に限定されるものではないが、例えば、ラジカル重合性化合物１００質量部に対して、１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、２質量部以上１２質量部以下であることが好ましい。このような組成の組成物は、接着剤として用いた場合、優れた接着容易性および接着性を有するからである。 In one embodiment of the composition of the present invention, the content of the photo radical initiator is not particularly limited as long as desired adhesiveness and the like can be obtained, but, for example, 100 mass of radical polymerizable compound The amount can be 1 part by mass or more and 20 parts by mass or less, preferably 2 parts by mass or more and 15 parts by mass or less, and particularly preferably 2 parts by mass or more and 12 parts by mass or less. It is because the composition of such composition has the outstanding ease of adhesion and adhesiveness, when it uses as an adhesive agent.
４．熱重合開始剤
　本発明の組成物において、熱重合開始剤は、加熱することにより、環状エーテル基同士の重合を開始できるものであればよく、カチオン重合開始剤およびアニオン重合開始剤等を挙げることができる。本発明の組成物の一実施形態としては、熱重合開始剤は、１種類のみを含むものであってもよく、２種類以上を組み合わせて用いてもよい。 4. Thermal polymerization initiator In the composition of the present invention, the thermal polymerization initiator may be any one capable of initiating polymerization of cyclic ether groups by heating, and mention may be made of cationic polymerization initiator, anionic polymerization initiator, etc. Can. In one embodiment of the composition of the present invention, the thermal polymerization initiator may contain only one type, or two or more types may be used in combination.
　本発明の組成物の一実施形態としては、熱重合開始剤は、アニオン重合開始剤を含むことが好ましい。アニオン重合開始剤は、被着体に含まれるアミン化合物等の影響による硬化阻害が少なく、環状エーテル基同士を安定的に重合できるからである。 In one embodiment of the composition of the present invention, the thermal polymerization initiator preferably comprises an anionic polymerization initiator. The anionic polymerization initiator is less in inhibition of curing due to the influence of an amine compound and the like contained in the adherend, and is capable of stably polymerizing cyclic ether groups.
４－１．アニオン重合開始剤
　アニオン重合開始剤としては、環状エーテル基同士をアニオン重合により重合可能なものであればよく、例えば、硬化剤、硬化触媒等を挙げることができる。 4-1. Anionic polymerization initiator As an anionic polymerization initiator, what is necessary is just to be able to polymerize cyclic ether groups by anionic polymerization, for example, a curing agent, a curing catalyst, etc. can be mentioned.
　硬化剤としては、例えば、環状エーテル基と共有結合により結合することで、環状エーテル化合物同士を架橋するものとすることができ、例えば、ジシアンジアミド、変性ポリアミン、ヒドラジド類、４，４’－ジアミノジフェニルスルホン、グアナミン類およびメラミン等を挙げることができる。なかでも、ジシアンジアミドを含むことが好ましい。このような硬化剤は、環状エーテル基同士を効率的に重合可能であり、硬化剤の含有量の低減が容易だからである。これらの硬化剤は、単独で使用しても良いし、２種類以上を併用してもよい。 As the curing agent, for example, cyclic ether compounds can be cross-linked by being covalently bonded to a cyclic ether group, and, for example, dicyandiamide, modified polyamines, hydrazides, 4,4'-diaminodiphenyl Sulfone, guanamines, melamine and the like can be mentioned. Among them, dicyandiamide is preferably contained. Such a curing agent is capable of efficiently polymerizing cyclic ether groups with one another, and it is easy to reduce the content of the curing agent. These curing agents may be used alone or in combination of two or more.
　上記ジシアンジアミドの市販品としては、ジシアンジアミドのみを含むものに限らず、ジシアンジアミドと他の成分を含むものも用いることができる。 The commercial products of the dicyandiamide are not limited to those containing only dicyandiamide, and those containing dicyandiamide and other components can also be used.
　上記市販品としては、例えば、ＤＩＣＹ７、ＤＩＣＹ１５，ＤＩＣＹ５０（以上、三菱化学社製）、ＡｍｉｃｕｒｅＣＧ－ＮＡ、ＡｍｉｃｕｒｅＣｇ－３２５Ｇ、ＡｍｉｃｕｒｅＣＧ－１２００Ｇ，Ｄｉｃｙａｎｅｘ１４００Ｆ（以上、エアープロダクツ社製）、ＡＤＥＫＡ社製ＥＨ－３６３６ＡＳ、ＥＨ－４３５１Ｓ、ＥＨ－５９１０等が挙げられる。 Examples of the commercially available products include DICY7, DICY15, DICY50 (above, manufactured by Mitsubishi Chemical Co., Ltd.), Amicure CG-NA, Amicure Cg-325 G, Amicure CG-1200 G, Dicyanex1400 F (above, made by Air Products Co., Ltd.), EH-3636 AS manufactured by ADEKA EH-4351S, EH-5910, and the like.
　上記変性ポリアミンとしては、ポリアミン類のエポキシ付加変性物、アミド化変性物、マンニッヒ変性物等が挙げられる。変性ポリアミンに用いられるポリアミン類としては、特に制限はないが、例えば、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、１，２－ジアミノプロパン、ポリオキシプロピレンジアミン、ポリオキシプロピレントリアミン等の脂肪族ポリアミン；イソホロンジアミン、メンセンジアミン、ビス（４－アミノ－３－メチルジシクロヘキシル）メタン、ジアミノジシクロヘキシルメタン、ビス（アミノメチル）シクロヘキサン、Ｎ－アミノエチルピペラジン、３，９－ビス（３－アミノプロピル）－２，４，８，１０－テトラオキサスピロ（５．５）ウンデカン等の脂環式ポリアミン；ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、トリレン－２，４－ジアミン、トリレン－２，６－ジアミン、メシチレン－２，４－ジアミン、メシチレン－２，６－ジアミン、３，５－ジエチルトリレン－２，４－ジアミン、３，５－ジエチルトリレン－２，６－ジアミン等の単核ポリアミン；ビフェニレンジアミン、４，４－ジアミノジフェニルメタン、２，５－ナフチレンジアミン、２，６－ナフチレンジアミン等の芳香族ポリアミン；後述するイミダゾール類が挙げられる。 As said modification | denaturation polyamine, the epoxy addition modification | denaturation thing of polyamines, an amidification modification | denaturation thing, a Mannich modification etc. are mentioned. The polyamines used for the modified polyamine are not particularly limited, but, for example, fats such as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, 1,2-diaminopropane, polyoxypropylene diamine, polyoxypropylene triamine etc. Aliphatic polyamine; isophoronediamine, mensenediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl Alicyclic polyamines such as -2,4,8,10-tetraoxaspiro (5.5) undecane; m-phenylenediamine, p-phenylenediamine, tolylene-2,4-diamine, tolylene-2,6 Mononuclear polyamines such as diamine, mesitylene-2,4-diamine, mesitylene-2, 6-diamine, 3,5-diethyl tolylene-2,4-diamine, 3,5-diethyl tolylene-2, 6-diamine And aromatic polyamines such as biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, 2,6-naphthylenediamine, etc .; and imidazoles described later.
　上記エポキシ付加変性物は、上記ポリアミン類と、エポキシ化合物とを、常法によって付加反応させることによって製造することができる。 The epoxy addition modified product can be produced by subjecting the above-mentioned polyamines and an epoxy compound to an addition reaction according to a conventional method.
　上記エポキシ付加変性物に用いられる上記エポキシ化合物としては、例えば、環状エーテル化合物の説明の際に挙げたエポキシ化合物を用いることができる。 As the above-mentioned epoxy compound used for the above-mentioned epoxy addition modification thing, the epoxy compound mentioned at the time of explanation of a cyclic ether compound can be used, for example.
　上記アミド化変性物は、上記ポリアミン類と、アジピン酸、セバシン酸、フタル酸、イソフタル酸、ダイマー酸等のカルボン酸類とを、常法によって反応させることによって製造することができる。 The above-mentioned amidated modified product can be produced by reacting the above-mentioned polyamines with carboxylic acids such as adipic acid, sebacic acid, phthalic acid, isophthalic acid and dimer acid according to a conventional method.
　上記マンニッヒ化変性物は、上記ポリアミン類と、ホルムアルデヒド等のアルデヒド類、およびフェノール、クレゾール、キシレノール、第三ブチルフェノール、レゾルシン等の核に少なくとも一個のアルデヒド化反応性箇所を有するフェノール類とを、常法によって反応させることによって製造することができる。 The Mannich modified product usually comprises the above polyamines, aldehydes such as formaldehyde, and phenols having at least one aldehyde forming reactive site in the core of phenol, cresol, xylenol, tert-butylphenol, resorcin, etc. It can be produced by reaction according to the method.
　上記ヒドラジド類としては、シュウ酸ジヒドラジド、マロン酸ジヒドラジド、コハク酸ジヒドラジド、グルタル酸ジヒドラジド、アジピン酸ジヒドラジド、スベリン酸ジヒドラジド、アゼライン酸ジヒドラジド、セバシン酸ジヒドラジド、フタル酸ジヒドラジド等が挙げられる。 Examples of the hydrazides include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide and the like.
　硬化触媒としては、熱またはエネルギー線等の作用により環状エーテル基同士を反応させる酸性物質若しくはアルカリ性物質を発生し、環状エーテル基同士の重合反応等を促進するものを挙げることができる。例えば、トリフェニルホスフィン等のホスフィン化合物；テトラフェニルホスフォニウムブロマイド等のホスホニウム塩；２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、２－イソプロピルイミダゾール、２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、２－アミノプロピルイミダゾール、１，２－ジメチルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－ベンジル－２－フェニルイミダゾール等のイミダゾール類；上記イミダゾール類と、トリメリット酸、イソシアヌル酸、硼素等との塩であるイミダゾール塩類；ベンジルジメチルアミン、２，４，６－トリス（ジメチルアミノメチル）フェノール等のアミン類；３－（３，４－ジクロロフェニル）－１，１－ジメチルウレア、イソホロンジイソシアネート－ジメチルウレア、トリレンジイソシアネート－ジメチルウレア等のウレア類；トリメチルアンモニウムクロライド等の４級アンモニウム塩類；および、三フッ化硼素と、アミン類やエーテル化合物等との錯化合物等を挙げることができる。これらの硬化触媒は、単独で使用してもよいし、２種類以上を併用してもよい。 As a curing catalyst, there can be mentioned a catalyst which generates an acidic substance or an alkaline substance which causes cyclic ether groups to react with each other by the action of heat or energy ray and promotes the polymerization reaction of cyclic ether groups. For example, phosphine compounds such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecyl Imidazoles such as imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-aminopropylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole Imidazole salts which are salts of the above imidazoles with trimellitic acid, isocyanuric acid, boron and the like; amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; 3- ( Ureas such as 2,4-dichlorophenyl) -1,1-dimethylurea, isophorone diisocyanate-dimethylurea, tolylene diisocyanate-dimethylurea; quaternary ammonium salts such as trimethyl ammonium chloride; and boron trifluoride and amines And complex compounds with ether compounds and the like. These curing catalysts may be used alone or in combination of two or more.
　硬化触媒は、なかでも、イミダゾール類を含むことが好ましい。硬化触媒は、例えば、ジシアンジアミド等の硬化剤と共に用いることで、低温度で環状エーテル基同士を重合可能だからである。 The curing catalyst preferably contains, among others, imidazoles. This is because the curing catalyst can polymerize cyclic ether groups at a low temperature by using it together with a curing agent such as dicyandiamide.
　アニオン重合開始剤は、１種類または２種類以上を組み合わせて用いることができ、例えば、硬化剤および硬化触媒の群から選択される少なくとも１種を含むものとすることができ、なかでも、硬化剤および硬化触媒の両者を含むことが好ましく、特に、硬化剤としてジシアンジアミドを含み、硬化触媒としてイミダゾール類を含むことが好ましい。このような組成物は、低温で環状エーテルを重合することができる。また、透明性に優れた硬化物が製造容易となり、さらに、硬化速度に優れたものとなるからである。 The anionic polymerization initiator may be used alone or in combination of two or more, and may include, for example, at least one selected from the group of curing agents and curing catalysts, among which curing agents and curing It is preferable to contain both of the catalysts, and in particular, it is preferable to contain dicyandiamide as a curing agent and to contain imidazoles as a curing catalyst. Such compositions can polymerize cyclic ethers at low temperatures. In addition, a cured product having excellent transparency is easy to manufacture, and further, the curing speed is excellent.
　なお、透明性に優れた硬化物が製造容易となる理由については、明確ではないが、以下のように推察される。すなわち、硬化温度の低下、硬化速度の向上等により、効率的に重合を促進可能等になる。その結果、アニオン重合開始剤の含有量の抑制、未反応のまま残存する割合の低下等が容易となり、組成物は、透明性に優れた硬化物の製造が容易になるのである。 In addition, although it is not clear about the reason which the hardened | cured material excellent in transparency becomes easy to manufacture, it is guessed as follows. That is, the polymerization can be efficiently accelerated by, for example, lowering the curing temperature and improving the curing rate. As a result, suppression of the content of the anionic polymerization initiator, reduction of the ratio of remaining unreacted, and the like become easy, and the composition becomes easy to produce a cured product excellent in transparency.
　より具体的には、アニオン重合開始剤は、通常、室温付近で固体状であるものが多く、組成物中に分散状態で含まれることがある。しかしながら、上記の開始剤は、環状エーテル基同士を効率的に重合可能であり、含有量の低減が容易である。その結果、組成物は、光透過性に優れ、例えば、光照射によるラジカル重合性基同士の重合が容易となる。また、このような組成物は、アニオン重合開始剤の未反応物の残渣が少なく、透明性の高い硬化物を得ることが容易となる。このようなことから、接着容易性および接着性に優れ、さらに透明性に優れた硬化物を得ることが容易となる。 More specifically, many anionic polymerization initiators are usually solid at around room temperature, and may be contained in a dispersed state in the composition. However, the above initiator can efficiently polymerize cyclic ether groups, and the content can be easily reduced. As a result, the composition is excellent in light transmittance, and for example, the polymerization of radical polymerizable groups by light irradiation becomes easy. In addition, such a composition has a small amount of non-reacted anionic polymerization initiator, and it becomes easy to obtain a cured product with high transparency. From these facts, it becomes easy to obtain a cured product which is excellent in ease of adhesion and adhesion and further excellent in transparency.
　本発明の組成物の一実施形態として、アニオン重合開始剤が硬化剤および硬化触媒の両者を含む場合、硬化剤の含有量は、所望の接着性等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、硬化剤および硬化触媒の合計１００質量部に対して、５質量部以上９５質量部以下とすることができ、４０質量部以上９５質量部以下であることが好ましく、５０質量部以上９５質量部以下であることが好ましく、なかでも８５質量部以上９５質量部以下であることが好ましい。このような組成物は、接着剤として用いた場合、接着容易性および接着性に優れ、さらに透明性に優れた硬化物を得ることが容易となるからである。 In one embodiment of the composition of the present invention, when the anionic polymerization initiator contains both a curing agent and a curing catalyst, the content of the curing agent is particularly limited as long as desired adhesiveness and the like can be obtained. For example, it can be 5 parts by mass or more and 95 parts by mass or less, preferably 40 parts by mass or more and 95 parts by mass or less, with respect to 100 parts by mass in total of the curing agent and the curing catalyst, and 50 parts by mass It is preferable that it is a part or more and 95 mass parts or less, Especially, it is preferable that it is 85 mass parts or more and 95 mass parts or less. When such a composition is used as an adhesive, it is easy to obtain a cured product which is excellent in ease of adhesion and adhesion and further excellent in transparency.
　また、上記硬化剤の含有量は、硬化温度低下が容易であるとの観点からは、硬化剤および硬化触媒の合計１００質量部中に、３０質量部以上７０質量部以下であることが好ましく、４０質量部以上６０質量部以下であることが好ましく、特に、４５質量部以上５５質量部以下であることが好ましい。 In addition, the content of the curing agent is preferably 30 parts by mass or more and 70 parts by mass or less in 100 parts by mass in total of the curing agent and the curing catalyst, from the viewpoint of easy lowering of the curing temperature. The content is preferably 40 parts by mass or more and 60 parts by mass or less, and particularly preferably 45 parts by mass or more and 55 parts by mass or less.
　本発明の組成物の一実施形態としては、アニオン重合開始剤の含有量は、所望の接着性等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、環状エーテル化合物１００質量部に対して、０．１質量部以上２０質量部以下とすることができ、１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、１質量部以上５質量部以下であることが好ましく、１．０質量部以上２．０質量部以下であることがより好ましく、１．１質量部以上１．４質量部以下であることがさらに好ましい。このような組成物は、接着剤として用いた場合、優れた接着容易性および接着性を有するからである。 In one embodiment of the composition of the present invention, the content of the anionic polymerization initiator is not particularly limited as long as desired adhesiveness and the like can be obtained, and for example, 100 parts by mass of a cyclic ether compound On the other hand, it can be 0.1 to 20 parts by mass, preferably 1 to 15 parts by mass, and more preferably 1 to 5 parts by mass, The content is more preferably 1.0 parts by mass or more and 2.0 parts by mass or less, and still more preferably 1.1 parts by mass or more and 1.4 parts by mass or less. Such a composition is because it has excellent adhesion and adhesiveness when used as an adhesive.
４－２．カチオン重合開始剤
　カチオン重合開始剤は加熱によりカチオン種またはルイス酸を発生する化合物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、オニウム塩系開始剤を使用することができる。 4-2. Cationic Polymerization Initiator The cationic polymerization initiator is not particularly limited as long as it is a compound capable of generating a cationic species or a Lewis acid upon heating, and a conventionally known compound can be used. For example, an onium salt initiator is used be able to.
　オニウム塩系開始剤としては、例えば、アリールジアルキルスルホニウムヘキサフルオロアンチモン酸塩、アリールジアルキルスルホニウムヘキサフルオロリン酸塩、ジアリールアルキルスルホニウムヘキサフルオロアンチモン酸塩、アリールジアルキルスルホニウムテトラパーフルオロフェニルホウ酸塩等のスルホニウム塩系、ジアリールヨードニウムヘキサフルオロアンチモン酸塩、ジアリールヨードニウムヘキサフルオロリン酸塩およびジアリールヨードニウムテトラパーフルオロフェニルホウ酸塩等のヨードニウム塩系等が挙げられる。これらは市場にて容易に入手することができる。 As the onium salt initiator, for example, sulfonium such as aryldialkylsulfonium hexafluoroantimonate, aryldialkylsulfonium hexafluorophosphate, diarylalkylsulfonium hexafluoroantimonate, aryldialkylsulfonium tetraperfluorophenyl borate and the like Examples thereof include salts, iodonium salts such as diaryliodonium hexafluoroantimonate, diaryliodonium hexafluorophosphate and diaryliodonium tetraperfluorophenyl borate. These are readily available in the market.
　カチオン重合開始剤としては、市販品を用いることもできる。例えば、アデカオプトンＣＰ－７７、アデカオプトンＣＰ－６６（ＡＤＥＫＡ社製）、ＣＩ－２６３９、ＣＩ－２６２４（日本曹達社製）、サンエイドＳＩ－６０Ｌ、サンエイドＳＩ－８０ＬおよびサンエイドＳＩ－１００Ｌ（三新化学工業社製）等が挙げられる。 A commercial item can also be used as a cationic polymerization initiator. For example, Adeka Opton CP-77, Adeka Opton CP-66 (made by Adeka), CI-2639, CI-2624 (made by Nippon Soda Co., Ltd.), Sun Aid SI-60 L, Sun Aid SI-80 L and San Aid SI-100 L (San Shin Chemical Industry Co., Ltd.) Company) and the like.
　カチオン重合開始剤の環状エーテル化合物１００質量部に対する含有量は、所望の接着性等が得られるものであれば特に限定されるものではなく、アニオン重合開始剤と同様とすることができる。 The content of the cationic polymerization initiator relative to 100 parts by mass of the cyclic ether compound is not particularly limited as long as desired adhesiveness and the like can be obtained, and can be the same as the anionic polymerization initiator.
５．その他の成分
　本発明の組成物は、環状エーテル化合物、ラジカル重合性化合物、光ラジカル開始剤および熱重合開始剤を有するものであるが、その一実施形態として、必要に応じてその他の成分を含むものであってもよい。このようなその他の成分としては、例えば、上記各成分を溶解または分散可能な溶剤を含むことができる。 5. Other Components The composition of the present invention has a cyclic ether compound, a radically polymerizable compound, a photo radical initiator and a thermal polymerization initiator, and as one embodiment thereof, contains other components as necessary. It may be one. Such other components can include, for example, solvents capable of dissolving or dispersing the above-mentioned components.
　溶剤としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルセロソルブ、エチルセロソルブ、クロロホルム、塩化メチレン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、ベンゼン、トルエン、キシレン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、酢酸エチル、メタノール、エタノールおよびイソプロパノール等を挙げることができる。 Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Ethyl acetate, methanol, ethanol, isopropanol and the like can be mentioned.
　その他の成分としては、本発明の組成物に対して、優れた接着性および透明性を付与することができるという観点から、本発明の組成物の一実施形態として、チオール化合物を含むことが好ましい。 As another component, it is preferable to include a thiol compound as an embodiment of the composition of the present invention from the viewpoint of being able to impart excellent adhesion and transparency to the composition of the present invention .
　チオール化合物としては、本発明の組成物の硬化物に、優れた接着性および透明性を付与することができるものであればよく、テトラエチレングリコールビス（３－メルカプトプロピオネート）、１，４－ビス（３－メルカプトブチリルオキシ）ブタン等の２官能チオール化合物、トリメチロールプロパントリス（３－メルカプトプロピオネート）、トリス－［（３－メルカプトプロピオニルオキシ）－エチル］－イソシアヌレート、１，３，５－トリス（３－メルカプトブチリルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、トリメチロールプロパントリス（３－メルカプトブチレート）、トリメチロールエタントリス（３－メルカプトブチレート）等の３官能チオール化合物、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）等の４官能チオール化合物、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）等の６官能チオール化合物等が挙げられる。 Any thiol compound may be used as long as it can impart excellent adhesion and transparency to the cured product of the composition of the present invention, and tetraethylene glycol bis (3-mercaptopropionate), 1,4 -Bifunctional thiol compounds such as -bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, 1,2 3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), Trifunctional thiol compounds such as trimethylol ethane tris (3-mercaptobutyrate), pentaeryth Examples include tetrafunctional thiol compounds such as tol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate), and hexafunctional thiol compounds such as dipentaerythritol hexakis (3-mercaptopropionate). Be
　チオール化合物の市販品としては、例えば、カレンズＭＴ（登録商標）ＢＤ－１（商品名、２官能チオール化合物、１，４－ビス（３－メルカプトブチリルオキシ）ブタン、昭和電工（株））、カレンズＭＴ（登録商標）ＮＲ－１（商品名、３官能チオール化合物、１，３，５－トリス（３－メルカプトブチリルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、昭和電工（株））、カレンズＭＴ（登録商標）ＰＥ－１（商品名、４官能チオール化合物、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、昭和電工（株））、ＥＧＭＰ－４（商品名、２官能チオール化合物、テトラエチレングリコールビス（３－メルカプトプロピオネート）、ＳＣ有機化学（株））、ＴＭＭＰ（商品名、３官能チオール化合物、トリメチロールプロパン　トリス（３－メルカプトプロピオネート、ＳＣ有機化学（株））、ＴＥＭＰＩＣ（商品名、３官能チオール化合物、トリス－［（３－メルカプトプロピオニルオキシ）－エチル］－イソシアヌレート、ＳＣ有機化学（株））、ＰＥＭＰ（商品名、４官能チオール化合物、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ＳＣ有機化学（株））、ＤＰＭＰ（商品名、６官能チオール化合物、ジペンタエリスリトールヘキサキス、（３－メルカプトプロピオネート）、ＳＣ有機化学（株））等が挙げられる。 As a commercial item of the thiol compound, for example, Karenz MT (registered trademark) BD-1 (trade name, bifunctional thiol compound, 1,4-bis (3-mercaptobutyryloxy) butane, Showa Denko KK), Karens MT (registered trademark) NR-1 (trade name, trifunctional thiol compound, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H) , 3H, 5H) -trione, Showa Denko KK, Karenz MT (registered trademark) PE-1 (trade name, tetrafunctional thiol compound, pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko KK) , EGMP-4 (trade name, bifunctional thiol compound, tetraethylene glycol bis (3-mercaptopropionate), SC Organic Chemical Co., Ltd.), TMMP (commodity Trifunctional thiol compound, trimethylolpropane tris (3-mercaptopropionate, SC Organic Chemical Co., Ltd.), TEMPIC (trade name, trifunctional thiol compound, tris-[(3-mercaptopropionyloxy) -ethyl]- Isocyanurate, SC Organic Chemical Co., Ltd., PEMP (trade name, tetrafunctional thiol compound, pentaerythritol tetrakis (3-mercaptopropionate), SC Organic Chemical Co., Ltd.), DPMP (trade name, hexafunctional thiol compound) Dipentaerythritol hexakis, (3-mercaptopropionate), SC Organic Chemical Co., Ltd., and the like.
　本発明の組成物の一実施形態としては、チオール化合物の含有量は、組成物の固形分１００質量部中に、０．１質量部以上２０質量部以下とすることができ、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、５質量部以上１０質量部以下であることが好ましい。このような組成物は、接着剤として用いた場合、接着性および透明性に優れた硬化物を得ることが容易となるからである。 In one embodiment of the composition of the present invention, the content of the thiol compound can be 0.1 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the solid content of the composition, and 1 part by mass or more The amount is preferably 10 parts by mass or less, and more preferably 5 parts by mass or more and 10 parts by mass or less. When such a composition is used as an adhesive, it is easy to obtain a cured product having excellent adhesion and transparency.
　その他の成分としては、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、組成物の固形分１００質量部中に３０質量部以下が好ましい。 As other components, if necessary, inorganic fillers, organic fillers, pigments, silane coupling agents, colorants such as dyes, photosensitizers, antifoaming agents, thickeners, thixo agents, surfactants, Various resin additives such as leveling agents, flame retardants, plasticizers, stabilizers, polymerization inhibitors, ultraviolet light absorbers, antioxidants, antistatic agents, flow control agents, adhesion promoters and the like can be included. The total content of the other components is preferably 30 parts by mass or less in 100 parts by mass of the solid content of the composition.
＜組成物の製造方法＞
　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、環状エーテル化合物およびラジカル重合性化合物を混合した後、熱重合開始剤および光ラジカル開始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用いることができる。 <Method of producing composition>
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, after mixing a cyclic ether compound and a radically polymerizable compound, a thermal polymerization initiator is used. And a method of adding and mixing an optical radical initiator. In addition, about the mixing method, the method of using a well-known mixing apparatus can be employ | adopted, for example, the method of using 3 rolls, a sand mill, a ball mill etc. can be used.
　本発明の組成物の一実施形態として、環状エーテル化合物として、高融点化合物および低融点化合物を含む場合には、低融点化合物および高融点化合物を混合し、室温で液状とした後、ラジカル重合性化合物等の他の成分を添加し混合する方法を用いることができる。 In one embodiment of the composition of the present invention, when a high melting point compound and a low melting point compound are contained as cyclic ether compounds, the low melting point compound and the high melting point compound are mixed, and after being liquid at room temperature, radically polymerizable The method of adding and mixing other components, such as a compound, can be used.
＜用途＞
　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、プリント配線基板のレジスト材料の他、レジストインキ、カーフィルター用顔料レジストインキ、半導体封止剤、インキ、プラスチック塗料、紙印刷、フィルムコーティング、ガラスコーティング、飛散防止塗料、家具塗装等の種々のコーティング分野、ＦＲＰ、ライニング、さらにはエレクトロニクス分野における絶縁ワニス、絶縁シート、積層版、プラズマディスプレイパネル、ディスプレイ素子等の表示媒体や、位相差板、偏光板、光偏光プリズム、各種光フィルター等の光学異方体、接着剤、絶縁材、構造材、光導波路クラッド等を挙げることができる。 <Use>
The application of the composition of the present invention is not particularly limited as long as it is used for forming a cured product, and in addition to the resist material of the printed wiring board, resist ink, pigment resist ink for car filters, semiconductor Insulating varnishes, insulation sheets, laminated plates, plasmas in various coating fields such as sealants, inks, plastic coatings, paper printing, film coatings, glass coatings, shatterproof coatings, furniture coatings, FRPs, linings, and also in the electronics sector Display panels, display media such as display elements, retardation plates, polarizing plates, light polarizing prisms, optical anisotropic bodies such as various light filters, adhesives, insulating materials, structural materials, optical waveguide cladding, etc. can be mentioned. .
　本発明の組成物は、半硬化および本硬化の２段階で硬化可能であ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。すなわち、本発明の接着剤は、本発明の組成物を含むものである。 The composition of the present invention is preferably used in an adhesive from the viewpoint that the effect of being curable in two steps of semi-curing and main curing can be exhibited more effectively. That is, the adhesive of the present invention comprises the composition of the present invention.
　本発明の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。接着剤は、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。 Specific applications of the adhesive of the present invention include optical materials represented by glasses and imaging lenses, applications of electronic materials represented by laminates and printed substrates, and automotive applications represented by head-up displays and car navigation It can be used in various applications such as equipment and display panels represented by organic EL and liquid crystal. The adhesive is preferably used in applications where transparency is required, and is particularly preferably used in applications such as optical materials, in-vehicle devices, display panels and the like.
　本発明の接着剤による被着体は、無機材料であってもよいが、有機材料であることが好ましい。被着体が有機材料であることで、本発明の組成物の半硬化状態の硬化物は、被着体表面を溶解でき、被着体を貼り合わせることが容易となるからである。 The adherend with the adhesive of the present invention may be an inorganic material, but is preferably an organic material. When the adherend is an organic material, the cured product in the semi-cured state of the composition of the present invention can dissolve the surface of the adherend and it becomes easy to bond the adherends.
　被着体としての有機材料としては、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；エポキシ樹脂；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。被着体としての無機材料としては、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 organic materials as adherends include cellulose esters such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose, etc .; polyamide; polyimide; polyurethane; epoxy resin; polycarbonate ; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polybutylene terephthalate, etc. polystyrene Polyethylene, polypropylene, polymethylpentene, polytetrafluoroethylene, polyolefin such as cycloolefin polymer Vinyl compounds such as polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylic acid ester; polycarbonate; polysulfone; polyether sulfone; polyether ketone; And polymeric materials such as polyoxyethylene and norbornene resin. Examples of the inorganic material as the adherend include glasses such as soda glass and quartz glass, metals, metal oxides and the like.
＜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、上述の本発明の組成物の硬化物である。したがって、半硬化状態および本硬化状態を示すことが容易である。本発明の硬化物は、本発明の組成物の半硬化状態の硬化物であることで、例えば、被着体を位置ずれ少なく貼り合わせる接着容易性を容易に付与できる。また、その硬化物は、本発明の組成物の本硬化状態の硬化物であるので、例えば、被着体との間で優れた接着性を容易に付与できる。 <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 described above. Therefore, it is easy to indicate the semi-cured state and the main cured state. The cured product of the present invention is a cured product in a semi-cured state of the composition of the present invention, so that, for example, adhesion ease can be easily given to bond adherends with less positional deviation. In addition, since the cured product is a cured product in the main cured state of the composition of the present invention, for example, it is possible to easily impart excellent adhesion to an adherend.
　本発明の硬化物の貯蔵弾性率は、通常、上記組成物より貯蔵弾性率が高いものであり、硬化物の用途等に応じて適宜設定することができる。本発明の硬化物の一実施形態としては、貯蔵弾性率を２５℃において、例えば、１．０×１０３Ｐａ以上とすることができる。例えば、硬化物が優れた接着容易性を有するものとなるとの観点からは、１．０×１０３Ｐａ以上１．０×１０５Ｐａ未満とすることができる。貯蔵弾性率をかかる範囲とすることで、本発明の一実施形態の硬化物は、優れた接着容易性を発揮するからである。 The storage elastic modulus of the cured product of the present invention is usually higher than that of the above composition, and can be appropriately set according to the application of the cured product. In one embodiment of the cured product of the present invention, the storage elastic modulus can be, for example, 1.0 × 10 3 Pa or more at 25 ° C. For example, from the viewpoint that the cured product has excellent adhesion ease, it can be 1.0 × 10 3 Pa or more and less than 1.0 × 10 5 Pa. By setting the storage elastic modulus in such a range, the cured product of one embodiment of the present invention exhibits excellent adhesion ease.
　例えば、本発明の一実施形態に係る硬化物は、本発明の組成物と比較して流動性が低下した硬化物であることで、被着体を加圧して貼り合わせる際に、被着体の位置ずれが少ない。また、貯蔵弾性率を上記範囲とすることで、室温付近でタック性を示し、被着体を容易に貼り合わせることができる。 For example, when the cured product according to one embodiment of the present invention is a cured product having reduced fluidity as compared to the composition of the present invention, the adherend can be pressure-bonded to be bonded. There is little misalignment of In addition, by setting the storage elastic modulus in the above range, tackiness can be exhibited at around room temperature, and the adherend can be easily bonded.
　さらに、このような貯蔵弾性率の硬化物は、本発明の組成物を半硬化させることにより、例えば、本発明の組成物に含まれるラジカル重合性化合物および環状エーテル化合物のいずれか一方のみの化合物を重合した半硬化状態の硬化物とすること等で容易に得ることができる。 Furthermore, the cured product of such storage modulus can be obtained by semi-curing the composition of the present invention, for example, a compound of only one of the radically polymerizable compound and the cyclic ether compound contained in the composition of the present invention Can be easily obtained, for example, by using a polymer as a cured product in a semi-cured state by polymerization.
　また、本発明の硬化物の他の実施形態としては、硬化物が優れた接着性を有するものとなるとの観点からは、貯蔵弾性率を２５℃において、１．０×１０５Ｐａ以上１．０×１０１０Ｐａ以下としてもよく、なかでも、１．０×１０５Ｐａ以上１．０×１０８Ｐａ以下であることが好ましく、特に、１．０×１０５Ｐａ以上１．０×１０６Ｐａ以下であることが好ましい。貯蔵弾性率をかかる範囲とすることで、本発明の一実施形態の硬化物は、優れた接着性を発揮するからである。 In addition, as another embodiment of the cured product of the present invention, from the viewpoint that the cured product has excellent adhesiveness, the storage elastic modulus is 1.0 × 10 5 Pa or more at 25 ° C. 0 × may be 10 10 Pa or less, inter alia, preferably not more than 1.0 × 10 5 Pa or more 1.0 × 10 8 Pa, in particular, 1.0 × 10 5 Pa or more 1.0 × 10 It is preferable that it is 6 Pa or less. It is because the hardened | cured material of one Embodiment of this invention exhibits the outstanding adhesiveness by making storage elastic modulus into this range.
　例えば、本発明の一実施形態に係る硬化物は、室温で被着体との接着状態を安定的に保持可能となるからである。また、このような貯蔵弾性率の硬化物は、本発明の組成物を本硬化させることにより、例えば、本発明の組成物に含まれるラジカル重合性化合物および環状エーテル化合物の両者の化合物を重合した本硬化状態の硬化物とすること等で容易に得ることができるからである。 For example, the cured product according to one embodiment of the present invention can stably maintain the adhesion state with the adherend at room temperature. Moreover, the cured product of such storage elastic modulus is obtained, for example, by polymerizing both the radically polymerizable compound and the cyclic ether compound contained in the composition of the present invention by the main curing of the composition of the present invention It is because it can be easily obtained by setting it as the hardened | cured material of the main hardening state.
　なお、貯蔵弾性率は、評価用サンプルを動的粘弾性測定装置を用いて測定することができる。上記評価用サンプルの厚みは、例えば、５０μｍとすることができる。 In addition, storage elastic modulus can measure the sample for evaluation using a dynamic-viscoelasticity measuring apparatus. The thickness of the evaluation sample can be, for example, 50 μm.
　貯蔵弾性率の測定条件は、より具体的には、８ｍｍパラレルプレートを用い、サンプル直径８ｍｍ、評価用サンプルの膜厚（ステージおよびパラレルプレートのギャップ）５０μｍ、周波数を５Ｈｚ、振り角０．５％とすることができる。なお、動的粘弾性測定装置としては、Ａｎｔｏｎ　Ｐａａｒ社製の動的粘弾性測定装置ＭＣＲ－３０２を用いることができる。 More specifically, the measurement conditions of the storage elastic modulus are 8 mm parallel plate, sample diameter 8 mm, thickness of sample for evaluation (gap of stage and parallel plate) 50 μm, frequency 5 Hz, swing angle 0.5% It can be done. Incidentally, as the dynamic viscoelasticity measuring apparatus, a dynamic viscoelasticity measuring apparatus MCR-302 manufactured by Anton Paar can be used.
　作製した評価用サンプルについての貯蔵弾性率の測定方法は、例えば、組成物の硬化条件が判明している場合には、組成物を膜厚（ギャップ）が５０μｍとなるようにパラレルプレートで挟持し、次いで、パラレルプレートで挟持した状態で所定の硬化条件で組成物を硬化し、次いで、得られた硬化物の貯蔵弾性率を上述の測定条件で測定する方法を用いてもよい。 For example, when the curing condition of the composition is known, the method of measuring the storage elastic modulus of the prepared sample for evaluation is to hold the composition in parallel plates so that the film thickness (gap) becomes 50 μm. Then, the composition may be cured under predetermined curing conditions while being held between parallel plates, and then the storage elastic modulus of the obtained cured product may be measured under the above-described measurement conditions.
　硬化物の形状については、本発明の硬化物の用途等に応じて適宜設定することができる。硬化物の厚みは、例えば、硬化物が被着体同士を接着する接着層として用いられる場合には、被着体のサイズ等によって異なるものであるが、例えば、０．１μｍ以上１ｍｍ以下とすることができる。 About the shape of hardened | cured material, it can set suitably according to the use etc. of hardened | cured material of this invention. The thickness of the cured product is, for example, different depending on the size of the adherend when the cured product is used as an adhesive layer to adhere adherends to each other, but is, for example, 0.1 μm or more and 1 mm or less be able to.
　本発明の硬化物の製造方法としては、本発明の組成物を硬化させることができる方法であれば特に制限はない。本発明の製造方法の一実施形態としては、例えば、組成物に含まれる環状エーテル化合物およびラジカル重合性化合物をそれぞれ重合する方法を用いることができる。 The method for producing the cured product of the present invention is not particularly limited as long as the composition of the present invention can be cured. As one embodiment of the production method of the present invention, for example, a method of polymerizing the cyclic ether compound and the radically polymerizable compound contained in the composition can be used.
　例えば、接着容易性に優れた硬化物を得るとの観点からは、本発明の製造方法の一実施形態としては、例えば、環状エーテル化合物およびラジカル重合性化合物のいずれか一方の化合物を重合する方法、すなわち、本発明の組成物を半硬化する方法を用いることができる。 For example, from the viewpoint of obtaining a cured product excellent in adhesion ease, as one embodiment of the production method of the present invention, for example, a method of polymerizing either one of a cyclic ether compound and a radically polymerizable compound That is, the method of semi-curing the composition of the present invention can be used.
　また、接着性に優れた硬化物を得るとの観点からは、例えば、環状エーテル化合物およびラジカル重合性化合物の両者をそれぞれ重合する方法、すなわち、他の実施形態として、本発明の組成物を本硬化する方法を用いることができ、なかでも、組成物に含まれる環状エーテル化合物およびラジカル重合性化合物の両者を順次重合する方法を好ましく用いることができる。 Further, from the viewpoint of obtaining a cured product having excellent adhesion, for example, a method of polymerizing both of a cyclic ether compound and a radically polymerizable compound, that is, the composition of the present invention as another embodiment. A method of curing can be used, and among them, a method of sequentially polymerizing both of the cyclic ether compound and the radically polymerizable compound contained in the composition can be preferably used.
　本発明の組成物中の環状エーテル化合物を重合する方法としては、組成物に含まれる環状エーテル基同士を加熱処理により重合する工程を含むものとすることができる。 The method of polymerizing the cyclic ether compound in the composition of the present invention may include the step of polymerizing the cyclic ether groups contained in the composition by heat treatment.
　本発明の組成物中のラジカル重合性化合物を重合する方法としては、組成物に含まれるラジカル重合性基同士を光照射により重合する工程を含むものとすることができる。 The method of polymerizing the radically polymerizable compound in the composition of the present invention may include the step of polymerizing the radically polymerizable groups contained in the composition by light irradiation.
＜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、本発明の組成物に含まれるラジカル重合性基同士を光照射により重合する工程および本発明の組成物に含まれる環状エーテル基同士を加熱処理により重合する工程の少なくとも一方の工程を有するものであり、（ｉ）ラジカル重合性基同士を光照射により重合する工程および環状エーテル基同士を加熱処理により重合する工程のいずれか一方のみを含む形態（第１実施形態）と、（ｉｉ）ラジカル重合性基同士を光照射により重合する工程および環状エーテル基同士を加熱処理により重合する工程の両工程を含む形態（第２実施形態）と、の２つの形態に分けることができる。以下、本発明の硬化物の製造方法について、各形態に分けて説明する。 <Method of producing cured product>
Next, the method for producing the cured product of the present invention will be described.
The method for producing a cured product of the present invention comprises the steps of polymerizing radical polymerizable groups contained in the composition of the present invention by light irradiation and steps of polymerizing cyclic ether groups contained in the composition of the present invention by heat treatment (I) a mode including only one of (i) polymerizing radically polymerizable groups with light and polymerizing cyclic ether groups with heat treatment (first embodiment) Form (a second embodiment) including two steps of (form) and (ii) a step of polymerizing radically polymerizable groups with light and a step of polymerizing cyclic ether groups by heat treatment (second embodiment) It can be divided. Hereinafter, the manufacturing method of the hardened | cured material of this invention is divided into each form, and is demonstrated.
１．第１実施形態
　本発明の硬化物の製造方法の第１実施形態は、ラジカル重合性基同士を光照射により重合する工程および環状エーテル基同士を加熱処理により重合する工程のいずれか一方のみを含むものである。第１実施形態によれば、上記工程のいずれか一方の工程のみを行うことにより、半硬化状態の硬化物を形成できる。よって、第１実施形態は、被着体を加圧して貼り合わせる際に、被着体の位置ずれが少ない硬化物を得ることができる。また、第１実施形態においては、室温付近でタック性を示し、被着体を容易に貼り合わせることができる硬化物を得ることができる。以下、本形態の硬化物の製造方法に含まれる各工程について説明する。 1. First Embodiment The first embodiment of the method for producing a cured product of the present invention comprises only one of the steps of polymerizing radically polymerizable groups with light and polymerizing cyclic ether groups with heat treatment. It is According to the first embodiment, the cured product in the semi-cured state can be formed by performing only one of the above steps. Therefore, in the first embodiment, when the adherend is pressurized and attached, a cured product with less positional deviation of the adherend can be obtained. Moreover, in 1st Embodiment, tackiness is shown at room temperature vicinity, and the hardened | cured material which can bond an adherend easily can be obtained. Hereinafter, each process included in the manufacturing method of the hardened | cured material of this form is demonstrated.
１－１．実施工程
　本発明の硬化物の製造方法の第１実施形態は、上記ラジカル重合性基同士を光照射により重合する工程および上記環状エーテル基同士を加熱処理により重合する工程のいずれか一方の工程のみを含むものである。なかでも、ラジカル重合性基同士を光照射により重合する工程を含むものであることが好ましい。かかる工程は、半硬化状態を安定的に形成できるからである。 1-1. Implementation Steps In the first embodiment of the method for producing a cured product of the present invention, only one of the steps of polymerizing the above-mentioned radical polymerizable groups by light irradiation and of the above-mentioned process of polymerizing the above cyclic ether groups by heat treatment Is included. Among them, it is preferable to include a step of polymerizing radical polymerizable groups with each other by light irradiation. Such a step is because a semi-cured state can be stably formed.
１－２．ラジカル重合性基同士を重合する工程
　本工程は本発明の組成物に含まれるラジカル重合性基同士を光照射により重合する工程である。照射される光は、光ラジカル開始剤の種類に応じて適宜設定することができ、紫外線、電子線、Ｘ線、放射線、高周波等を挙げることができる。光の光源としては、光の種類に応じて公知の光源を用いることができる。例えば、紫外線の光源としては、紫外線レーザ、水銀ランプ、キセノンレーザ、メタルハライドランプおよび太陽光等が挙げられる。照射される光の合計光強度は、所望の硬化状態を得られるものであればよく、例えば、１００ｍＪ／ｃｍ２以上２，０００ｍＪ／ｃｍ２以下とすることができる。 1-2. Step of polymerizing radically polymerizable groups This step is a step of polymerizing the radically polymerizable groups contained in the composition of the present invention by light irradiation. The light to be irradiated can be appropriately set according to the type of photo radical initiator, and examples include ultraviolet light, electron beam, X-ray, radiation, high frequency and the like. As a light source of light, a well-known light source can be used according to the kind of light. For example, as an ultraviolet light source, an ultraviolet laser, a mercury lamp, a xenon laser, a metal halide lamp, sunlight, etc. may be mentioned. The total light intensity of the irradiated is light, as long as it is obtained the desired curing conditions, for example, be a 100 mJ / cm 2 or more 2,000 mJ / cm 2 or less.
１－３．環状エーテル基同士を重合する工程
　本工程は、本発明の組成物に含まれる環状エーテル基同士を加熱処理により重合する工程である。加熱温度は、処理対象となる組成物の塗膜または硬化物の厚み、熱重合開始剤の重合開始温度等に応じて適宜設定されるものであるが、例えば、５０℃以上２５０℃以下とすることができ、なかでも、１００℃以上２００℃以下であることが好ましく、特に、１００℃以上１５０℃以下であることが好ましい。なお、加熱温度は、本発明の組成物または硬化物の表面温度を示すものとする。また、加熱時間は、１０分以上２時間以下とすることができる。なお、加熱時間は、組成物または硬化物が所定の温度に到達した後、その温度を維持し続ける時間を示すものである。 1-3. Step of polymerizing cyclic ether groups This step is a step of polymerizing cyclic ether groups contained in the composition of the present invention by heat treatment. The heating temperature is appropriately set according to the thickness of the coating film or cured product of the composition to be treated, the polymerization initiation temperature of the thermal polymerization initiator, etc., and is, for example, 50 ° C. or more and 250 ° C. or less In particular, it is preferably 100 ° C. or more and 200 ° C. or less, and particularly preferably 100 ° C. or more and 150 ° C. or less. In addition, heating temperature shall show the surface temperature of the composition or hardened | cured material of this invention. The heating time can be 10 minutes or more and 2 hours or less. In addition, heating time shows the time which a composition or hardened | cured material keeps maintaining the temperature, after reaching predetermined | prescribed temperature.
１－４．その他の工程
　本発明の製造方法は、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、ラジカル重合性基同士を重合する工程および環状エーテル基同士を重合する工程の前に、本発明の組成物を塗布する工程、ラジカル重合性基同士を重合する工程または環状エーテル基同士を重合する工程の後に、被着体を硬化物に貼り合わせる工程等を挙げることができる。 1-4. Other Steps The production method of the present invention may have other steps as necessary. As such a step, prior to the step of polymerizing radically polymerizable groups and the step of polymerizing cyclic ether groups, a step of applying the composition of the present invention, a step of polymerizing radically polymerizable groups or cyclic After the process of polymerizing ether groups, the process etc. which bond a to-be-adhered body to hardened | cured material can be mentioned.
１－４－１．組成物を塗布する工程
　本発明の組成物を塗布する工程は、ラジカル重合性基同士を重合する工程および環状エーテル基同士を重合する工程の前に、組成物を塗布する工程である。塗布方法としては、ダイコーター、ロールコーター、カーテンコーター、各種の印刷、浸漬等の公知の方法を挙げることができる。本発明の組成物の塗布対象は、本発明の組成物により接着する被着体とすることができる。このような被着体を構成する材料としては、無機材料および有機材料等を挙げることができる。なお、無機材料および有機材料については、具体的には、本発明の組成物の説明で、詳細に説明したものと同様のものを用いることができる。 1-4-1. Step of Applying the Composition The step of applying the composition of the present invention is a step of applying the composition prior to the step of polymerizing radically polymerizable groups and the step of polymerizing cyclic ether groups. Examples of the coating method include known methods such as a die coater, a roll coater, a curtain coater, various types of printing, and immersion. The application target of the composition of the present invention can be an adherend adhered by the composition of the present invention. As a material which comprises such a to-be-adhered body, an inorganic material, an organic material, etc. can be mentioned. In addition, about an inorganic material and an organic material, the thing similar to what was demonstrated in detail by description of the composition of this invention can be used specifically.
１－４－２．貼り合わせる工程
　貼り合わせる工程は、ラジカル重合性基同士を重合する工程または環状エーテル基同士を重合する工程の後に、被着体を硬化物に貼り合わせる工程である。本工程を上記タイミングで行うことで、被着体を位置ずれ少なく貼り合わせ可能な硬化物を製造できる。本工程における被着体の貼り合わせ方法としては、被着体を硬化物に対して位置ずれ少なく貼り合わせ可能な方法であればよく、被着体を硬化物に接触させた後、加圧する方法等の公知の方法を用いることができる。 1-4-2. The step of bonding is a step of bonding an adherend to a cured product after the step of polymerizing radically polymerizable groups or the step of polymerizing cyclic ether groups. By performing this step at the above timing, it is possible to manufacture a cured product capable of bonding the adherend with less positional deviation. As a method of bonding the adherends in this step, any method may be used as long as the adherends can be bonded to the cured product with little positional deviation, and the adherend is pressed after being brought into contact with the cured product. Known methods such as can be used.
　第１実施形態により製造される硬化物は、半硬化状態の硬化物である。この硬化物の貯蔵弾性率等については、前述の接着容易性に優れたものとする、との観点で好ましいとされた範囲と同様とすることができる。 The cured product produced according to the first embodiment is a cured product in a semi-cured state. The storage elastic modulus and the like of the cured product can be the same as the preferred range from the viewpoint of excellent adhesion as described above.
２．第２実施形態
　本発明の硬化物の製造方法の第２実施形態は、ラジカル重合性基同士を光照射により重合する工程および環状エーテル基同士を加熱処理により重合する工程の両工程を含むものである。第２実施形態によれば、上記工程の両工程を含むことにより、まず、ラジカル重合性基同士を重合する工程および環状エーテル基同士を重合する工程のいずれか一方の工程を実施することにより、半硬化状態の硬化物を形成できる。また、一方の工程を実施した後に、他方の工程を実施することにより、本硬化状態の硬化物を形成できる。 2. Second Embodiment The second embodiment of the method for producing a cured product of the present invention includes both steps of polymerizing radically polymerizable groups with light and polymerizing cyclic ether groups with heat. According to the second embodiment, by including both steps of the above steps, first, one of the steps of polymerizing the radical polymerizable groups and polymerizing the cyclic ether groups is carried out, A cured product in a semi-cured state can be formed. In addition, after one process is performed, the other process can be performed to form a cured product in the main curing state.
　すなわち、第２実施形態は、半硬化および本硬化の２段階の硬化処理を経て、本硬化状態の硬化物を得ることができる。よって、第２実施形態は、例えば、ラジカル重合性基同士を重合する工程および環状エーテル基同士を重合する工程の間に、硬化物に対して被着体を貼り合わせる工程を有することで、被着体が位置ずれ少なく貼り合わせ、安定的に接着した硬化物を製造できる。以下、本形態の硬化物の製造方法に含まれる各工程について説明する。なお、ラジカル重合性基同士を光照射により重合する工程および環状エーテル基同士を加熱処理により重合する工程については、第１実施形態における説明と同様である。 That is, in the second embodiment, a cured product in the main curing state can be obtained through two-stage curing processing of semi-curing and main curing. Therefore, in the second embodiment, the adherend is attached to the cured product, for example, between the step of polymerizing the radically polymerizable groups and the step of polymerizing the cyclic ether groups. It is possible to produce a cured product in which the adherends are bonded together with little positional deviation and stably bonded. Hereinafter, each process included in the manufacturing method of the hardened | cured material of this form is demonstrated. The step of polymerizing radical polymerizable groups with light and the step of polymerizing cyclic ether groups with heat treatment are the same as those described in the first embodiment.
２－１．実施順位
　第２実施形態においては、ラジカル重合性基同士を光照射により重合する工程および環状エーテル基同士を加熱処理により重合する工程の実施順位は、両工程を同時に行うものであってもよいが、ラジカル重合性基同士を重合する工程および環状エーテル基同士を重合する工程を、順次行うものであることが好ましく、なかでも、ラジカル重合性基同士を重合する工程を実施した後、環状エーテル基同士を重合する工程を実施することが好ましい。本発明の組成物は、半硬化および本硬化の２段階の硬化処理を経て、本硬化状態の硬化物を得ることができるとの効果を効果的に発揮できるからである。ここで、上記重合する工程を順次行う場合、先に実施する一方の重合する工程の実施後の硬化物は、通常、ラジカル重合性化合物の重合体および環状エーテル化合物の重合体のいずれか一方を含み、他方の化合物の重合体を実質的に含まないものとすることができる。 2-1. In the second embodiment, the order of implementation of the step of polymerizing radically polymerizable groups with each other and the step of polymerizing cyclic ether groups with heat treatment may be to simultaneously perform both steps. It is preferable that the step of polymerizing radically polymerizable groups and the step of polymerizing cyclic ether groups are sequentially performed, and in particular, after carrying out the step of polymerizing radically polymerizable groups, a cyclic ether group It is preferable to carry out the step of polymerizing each other. This is because the composition of the present invention can effectively exhibit the effect of being able to obtain a cured product in the main curing state through the two-step curing process of semi-curing and main curing. Here, in the case where the above-mentioned polymerization step is sequentially performed, the cured product after the execution of one of the polymerization steps to be carried out first is usually either one of a polymer of a radically polymerizable compound and a polymer of a cyclic ether compound. It may be substantially free of the polymer of the other compound.
２－２．その他の工程
　第２実施形態は、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、ラジカル重合性基同士を重合する工程および環状エーテル基同士を重合する工程の前に、本発明の組成物を塗布する工程、ラジカル重合性基同士を重合する工程および環状エーテル基同士を重合する工程の間に、被着体を硬化物に貼り合わせる工程等を挙げることができる。なお、塗布する工程における塗布方法等および貼り合わせる工程における貼り合わせ方法等については、第１実施形態の説明の内容と同様とすることができる。 2-2. Other Steps The second embodiment may have other steps as necessary. As such steps, prior to the step of polymerizing radically polymerizable groups and the step of polymerizing cyclic ether groups, a step of applying the composition of the present invention, a step of polymerizing radically polymerizable groups and cyclic groups The process etc. which bond a to-be-adhered body to hardened | cured material between the process of superposing | polymerizing ether groups can be mentioned. The application method and the like in the applying step and the bonding method and the like in the bonding step can be the same as the contents of the description of the first embodiment.
　第２実施形態により製造される硬化物は、本硬化状態の硬化物である。第２実施形態における硬化物の貯蔵弾性率等については、前述の接着性に優れたものとする、との観点で好ましいとされた範囲と同様とすることができる。 The cured product produced according to the second embodiment is a cured product in the main curing state. About the storage elastic modulus etc. of the hardened | cured material in 2nd Embodiment, it can be made to be the same as the range made preferable in the viewpoint of making it excellent in the above-mentioned adhesiveness.
　ここまで、本発明の組成物、接着剤および硬化物について、好適な実施形態を用いて詳細に説明してきたが、上記の実施形態に限定されるものではない。また、本発明の製造方法についても、上記の第１実施形態および第２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。 So far, the composition, the adhesive and the cured product of the present invention have been described in detail using the preferred embodiments, but the present invention is not limited to the above embodiments. Further, the manufacturing method of the present invention is not limited to the first embodiment and the second embodiment described above. The above embodiment is an exemplification, and it has substantially the same configuration as the technical idea described in the claims of the present invention, and any one having the same function and effect can be used. It is included in the technical scope of the invention.
　以下、実施例等を挙げて、本発明を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 by way of examples and the like, but the present invention is not limited to these examples.
［実施例１～２９および比較例１～５］
　下記表１～５の配合に従って、環状エーテル化合物、ラジカル重合性化合物、光ラジカル開始剤、熱重合開始剤およびチオール化合物を配合して組成物を得た。各成分は以下のとおりである。得られた組成物を用いて、１．本硬化後の密着性、２．本硬化後の透明性、３．湿熱試験後の密着性、４．湿熱試験後の透明性、５．タック性、の評価をおこなった。なお、表１～５中の配合量は、各成分の質量部を表すものである。また、表中の「－」は、評価未実施または評価不可であったものを示すものである。 [Examples 1 to 29 and Comparative Examples 1 to 5]
A cyclic ether compound, a radically polymerizable compound, a photo radical initiator, a thermal polymerization initiator and a thiol compound were compounded according to the formulations in Tables 1 to 5 below to obtain a composition. Each component is as follows. Using the composition obtained, 1. Adhesion after main curing, Transparency after main curing, 3. Adhesion after wet heat test, 4. Transparency after wet heat test5. The tackiness was evaluated. The compounding amounts in Tables 1 to 5 represent parts by mass of each component. Also, "-" in the table indicates one that has not been evaluated or can not be evaluated.
（環状エーテル化合物）
Ａ－１：グリシジルエーテル型化合物およびエポキシクロアルキル型化合物以外のエポキシ化合物（（株）ダイセル社製ＥＨＰＥ－３１５０、高分子量化合物、固体化合物、軟化点７０℃～９０℃）
Ａ－２：グリシジルエーテル型化合物（日本化薬（株）社製ＥＰＰＮ－２０１、高分子量化合物、固体化合物、軟化点６５℃～７８℃）
Ａ－３：グリシジルエーテル型化合物（三菱化学（株）製ＪＥＲ１００７、高分子量化合物、重量平均分子量２，９００、固体化合物、軟化点１２８℃）
Ａ－４：グリシジルエーテル型化合物（三菱化学（株）製ＪＥＲ１００９、高分子量化合物、重量平均分子量３，８００、固体化合物、軟化点１４４℃）
Ａ－５：エポキシクロアルキル型化合物（（株）ダイセル社製セロキサイド２０２１Ｐ、分子量２５２、液体化合物）
Ａ－６：グリシジルエーテル型化合物（（株）ＡＤＥＫＡ社製ＥＤ－５２３Ｔ、低分子量化合物、液体化合物）
Ａ－７：グリシジルエーテル型化合物（（株）ＡＤＥＫＡ社製ＥＰ－４１００Ｅ、低分子量化合物、液体化合物）
Ａ－８：グリシジルエーテル型化合物（（株）ＡＤＥＫＡ社製ＥＰ－４０８０Ｅ、低分子量化合物、液体化合物）
Ａ－９：グリシジルエーテル型化合物（日本化薬（株）製ＮＣ－３０００、高分子量化合物、固体化合物、軟化点５３℃～６３℃）
Ａ－１０：グリシジルエーテル型化合物（日本化薬（株）製ＮＣ－２０００－Ｌ、高分子量化合物、固体化合物、軟化点４７℃～５７℃） (Cyclic ether compound)
A-1: Epoxy compounds other than glycidyl ether type compounds and epoxychloroalkyl type compounds (EHPE-3150 manufactured by Daicel Corporation, high molecular weight compounds, solid compounds, softening point 70 ° C to 90 ° C)
A-2: Glycidyl ether type compound (EPPN-201 manufactured by Nippon Kayaku Co., Ltd., high molecular weight compound, solid compound, softening point 65 ° C. to 78 ° C.)
A-3: Glycidyl ether type compound (Mitsubishi Chemical Corporation JER 1007, high molecular weight compound, weight average molecular weight 2,900, solid compound, softening point 128 ° C.)
A-4: Glycidyl ether type compound (Mitsubishi Chemical Corporation JER 1009, high molecular weight compound, weight average molecular weight 3,800, solid compound, softening point 144 ° C.)
A-5: Epoxy chloralkyl type compound (Celoxide 2021 P, manufactured by Daicel Corporation, molecular weight 252, liquid compound)
A-6: Glycidyl ether type compound (ED-523T manufactured by ADEKA Co., Ltd., low molecular weight compound, liquid compound)
A-7: Glycidyl ether type compound (EP-4100E manufactured by ADEKA Co., Ltd., low molecular weight compound, liquid compound)
A-8: Glycidyl ether type compound (EP-4080E manufactured by ADEKA Co., Ltd., low molecular weight compound, liquid compound)
A-9: Glycidyl ether type compound (NC-3000 manufactured by Nippon Kayaku Co., Ltd., high molecular weight compound, solid compound, softening point 53 ° C. to 63 ° C.)
A-10: Glycidyl ether type compound (NC-2000-L, manufactured by Nippon Kayaku Co., Ltd., high molecular weight compound, solid compound, softening point 47 ° C.-57 ° C.)
（ラジカル重合性化合物）
Ｂ－１：ウレタンアクリレート（根上工業（株）製ＵＮ－９０００ＰＥＰ、重量平均分子量（Ｍｗ）５，０００）
Ｂ－２：ウレタンアクリレート（根上工業（株）製ＵＮ－９２００Ａ、重量平均分子量１５，０００）
Ｂ－３：４－ヒドロキシブチルアクリレートグリシジルエーテル（単官能アクリレートモノマー、分子量２００）
Ｂ－４：４－ヒドロキシブチルアクリレート（単官能アクリレートモノマー、分子量１４４）
Ｂ－５：アクリロイルモルフォリン（単官能アクリレートモノマー、分子量１４１）
Ｂ－６：テトラヒドロフルフリルメタクリレート（単官能アクリレートモノマー、分子量１７０）
Ｂ－７：イソボルニルアクリレート（単官能アクリレートモノマー、分子量２０８） (Radical polymerizable compound)
B-1: Urethane acrylate (UN-9000 PEP, manufactured by Rygi Kogyo Co., Ltd., weight average molecular weight (Mw) 5,000)
B-2: Urethane Acrylate (UN-9200A, manufactured by KONAMI KOGYO CO., LTD., Weight average molecular weight 15,000)
B-3: 4-hydroxybutyl acrylate glycidyl ether (monofunctional acrylate monomer, molecular weight 200)
B-4: 4-hydroxybutyl acrylate (monofunctional acrylate monomer, molecular weight 144)
B-5: Acryloyl morpholine (monofunctional acrylate monomer, molecular weight 141)
B-6: Tetrahydrofurfuryl methacrylate (monofunctional acrylate monomer, molecular weight 170)
B-7: Isobornyl acrylate (monofunctional acrylate monomer, molecular weight 208)
（光ラジカル開始剤）
Ｃ－１：１－ヒドロキシ－シクロヘキシル－フェニルケトン (Photo radical initiator)
C-1: 1-hydroxy-cyclohexyl-phenyl ketone
（熱重合開始剤）
Ｄ－１：ジシアンジアミド（ＤＩＣＹ）（（株）ＡＤＥＫＡ社製ＥＨ－３６３６ＡＳ）
Ｄ－２：ジシアンジアミド（ＤＩＣＹ）（（株）ＡＤＥＫＡ社製ＥＨ－４３５１Ｓ）
Ｄ－３：２－エチル－４－メチルイミダゾール
Ｄ－４：２－ウンデシルイミダゾール
Ｄ－５：２－ヘプタデシルイミダゾール
Ｄ－６：ジシアンジアミド（ＤＩＣＹ）５０質量％イミダゾール類５０質量％の混合物（（株）ＡＤＥＫＡ社製アデカハードナーＥＨ－５９１０） (Thermal polymerization initiator)
D-1: Dicyandiamide (DICY) (EH-3636AS manufactured by ADEKA Corporation)
D-2: Dicyandiamide (DICY) (EH-4351S manufactured by ADEKA Corporation)
D-3: 2-ethyl-4-methylimidazole D-4: 2-undecylimidazole D-5: 2-heptadecylimidazole D-6: 50% by mass of dicyandiamide (DICY) 50% by mass of imidazoles (( Adeka Hardener EH-5910 manufactured by Adeka Co., Ltd.
（チオール化合物）
Ｅ－１：１，３，５－トリス（３－メルカプトブチリルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン (Thiol compound)
E-1: 1,3,5-Tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione
（評価用サンプル１の作成）
　各組成物を、三菱ガス化学（株）製ＦＥ－２０００（ポリカーボネートフィルム（以下、ＰＣ基材と称する場合がある。））上に塗布し膜厚５０μｍの塗膜を形成し、次いで、塗膜に対して、紫外線を１０００ｍＪ／ｃｍ２照射し（半硬化）、次いで、１２０℃３０分加熱処理（本硬化）を行うことで作成した。 (Creating sample 1 for evaluation)
Each composition is applied on Mitsubishi Gas Chemical Co., Ltd. FE-2000 (polycarbonate film (hereinafter sometimes referred to as PC base material)) to form a coating film having a thickness of 50 μm, and then a coating film On the other hand, it was created by irradiating an ultraviolet ray at 1000 mJ / cm 2 (semi-curing) and then performing heat treatment (main curing) at 120 ° C. for 30 minutes.
（評価用サンプル２の作成）
　各組成物を、ガラス基材（１０ｃｍ×１０ｃｍのガラス片）に塗布する以外は、上記評価用サンプル１の製造方法と同様の方法を用いて得た。 (Creating sample 2 for evaluation)
Except that each composition was apply | coated to a glass base material (10 cm x 10 cm piece of glass), it obtained using the method similar to the manufacturing method of the said sample 1 for evaluation.
１．本硬化後密着性
　評価用サンプル１を用いて９０°ピール試験を行い、以下の基準で評価した。なお、９０°ピール試験は、小型卓上荷重試験器ＭＯＤＥＬ－ＦＴＮ１－１３Ａ（アイコーエンジニアリング（株）製）を用いて、引張速度５０ｍｍ／ｍｉｎで９０°剥離して行った。 1. A 90 ° peel test was conducted using Sample 1 for evaluation of adhesion after main curing, and evaluation was made according to the following criteria. The 90 ° peel test was performed by peeling 90 ° at a tensile speed of 50 mm / min using a compact table-top load tester MODEL-FTN1-13A (manufactured by Aiko Engineering Co., Ltd.).
◎：材料破壊または１０Ｎ／１０ｍｍ以上
〇：５Ｎ／１０ｍｍ以上１０Ｎ／１０ｍｍ未満
△：１Ｎ／１０ｍｍ以上５Ｎ／１０ｍｍ未満
×：１Ｎ／１０ｍｍ未満
　評価基準が◎、〇または△である場合には、高い密着力を有し、接着剤として好ましく用いることができる。 :: material destruction or 10 N / 10 mm or more ○: 5 N / 10 mm or more but less than 10 N / 10 mm Δ: 1 N / 10 mm or more but less than 5 N / 10 mm ×: 1 N / 10 mm or less High when the evaluation standard is 〇, △ or Δ It has adhesion and can be preferably used as an adhesive.
２．本硬化後透明性
　評価用サンプル１および評価用サンプル２を目視にて観察し、以下の基準で評価した。 2. After the main curing, the transparency evaluation sample 1 and the evaluation sample 2 were visually observed and evaluated according to the following criteria.
〇：白濁が見られない。
△：白濁がわずかにみられる。
×：白濁が見られる。
　評価基準が〇または△である場合には、優れた透明性を有し、例えば、透明性が要求される部材の接着剤として好ましく用いることができる。 A: No cloudiness observed
Fair: slight turbidity is observed.
X: Cloudiness is observed.
When the evaluation standard is 〇 or 、, it has excellent transparency, and can be preferably used, for example, as an adhesive for members requiring transparency.
３．湿熱試験後密着性
　評価用サンプル１につき、湿熱試験を行い、その後、本硬化後の密着性と同様にして評価を行った。ここで、湿熱試験は、８５℃、８５ＲＨ％の環境下１２０時間保持することで行った。なお、評価基準は、１．本硬化後密着性と同じである。 3. After the heat and humidity test, the sample for evaluation 1 was subjected to the heat and humidity test, and thereafter evaluated in the same manner as the adhesion after the main curing. Here, the moist heat test was carried out by maintaining the environment at 85 ° C. and 85 RH% for 120 hours. Evaluation criteria are as follows. Same as adhesion after main curing.
４．湿熱試験後透明性
　評価用サンプル１および評価用サンプル２につき、湿熱試験を行い、その後、本硬化後の透明性と同様にして評価を行った。ここで、湿熱試験は、８５℃、８５ＲＨ％の環境下１２０時間保持することで行った。なお、評価基準は、２．本硬化後透明性と同じである。 4. After the heat-of-moisture test, the sample for evaluation 1 and the sample for evaluation 2 were subjected to a heat-of-moisture test, and then evaluated in the same manner as the transparency after main curing. Here, the moist heat test was carried out by maintaining the environment at 85 ° C. and 85 RH% for 120 hours. Evaluation criteria are as follows. Same as transparency after main curing.
５．タック性
　各組成物を用いて製造された半硬化評価用サンプルおよび本硬化評価用サンプルの貯蔵弾性率を測定して、以下の基準で判断した。 5. Tack property The storage elastic modulus of the sample for evaluation of semi-curing and the sample for full-curing evaluation manufactured using each composition was measured and judged based on the following criteria.
　貯蔵弾性率は、半硬化用評価用サンプルおよび本硬化用サンプルを、動的粘弾性測定装置を用いて測定した。各サンプルの膜厚は、５０μｍとした。貯蔵弾性率の測定条件は、より具体的には、８ｍｍパラレルプレートを用い、サンプル直径８ｍｍ、評価用サンプルの膜厚（ステージおよびパラレルプレートのギャップ）５０μｍ、周波数５Ｈｚ、振り角０．５％、温度２５℃とした。動的粘弾性測定装置としては、Ａｎｔｏｎ　Ｐａａｒ社製の動的粘弾性測定装置ＭＣＲ－３０２を用いた。 The storage elastic modulus was measured using a dynamic viscoelasticity measuring device for the evaluation sample for semi-curing and the sample for main curing. The film thickness of each sample was 50 μm. More specifically, the measurement conditions of storage modulus are 8 mm parallel plate, sample diameter 8 mm, film thickness of evaluation sample (gap between stage and parallel plate) 50 μm, frequency 5 Hz, swing angle 0.5%, The temperature was 25 ° C. As a dynamic viscoelasticity measuring device, a dynamic viscoelasticity measuring device MCR-302 manufactured by Anton Paar was used.
Ａ（タック性無）：貯蔵弾性率が１．０×１０５Ｐａ以上１．０×１０１０Ｐａ以下である。
Ｂ（タック性有）：貯蔵弾性率が１．０×１０３Ｐａ以上１．０×１０５Ｐａ未満である。
Ｃ（流動体）：貯蔵弾性率が１．０×１０３Ｐａ未満である。 A (tack-free): Storage elastic modulus is 1.0 × 10 5 Pa or more and 1.0 × 10 10 Pa or less.
B (with tackiness): Storage elastic modulus is 1.0 × 10 3 Pa or more and less than 1.0 × 10 5 Pa.
C (fluid): storage elastic modulus is less than 1.0 × 10 3 Pa.
　半硬化評価用サンプルは、Ｂ（タック性有）であることが好ましい。一方、半硬化評価用サンプルが、Ａ（タック性無）またはＣ（流動体）である場合、被着体と位置ずれ少なく貼り合わせることが困難となる場合がある。本硬化評価用サンプルは、光硬化Ａ（タック性無）であることが好ましい。一方、本硬化評価用サンプルが、Ｂ（タック性有）またはＣ（流動体）である場合、被着体との間で高い密着力を発揮できない場合がある。 The semi-cured evaluation sample is preferably B (having tackiness). On the other hand, when the semi-cured evaluation sample is A (tack free) or C (fluid), it may be difficult to bond the adherend with a small amount of positional deviation. It is preferable that the sample for the main curing evaluation is photo-curing A (no tackiness). On the other hand, when the sample for main curing evaluation is B (tackiness) or C (fluid), high adhesion to the adherend may not be exhibited.
　半硬化評価用サンプルの測定方法は、より具体的には、以下の方法を用いた。
（１）実施例および比較例で得られた組成物を、膜厚（ギャップ）が５０μｍとなるようにパラレルプレートで挟持した。
（２）次いで、パラレルプレートで挟持した状態で、組成物に対して紫外線を１０００ｍＪ／ｃｍ２照射し、半硬化の評価用サンプルを作製した。
（３）（２）で得られた半硬化評価用サンプルに対して、上記測定条件で貯蔵弾性率を測定した。 More specifically, the following method was used to measure the semi-cured evaluation sample.
(1) The compositions obtained in Examples and Comparative Examples were sandwiched by parallel plates such that the film thickness (gap) was 50 μm.
(2) Next, in a state of being sandwiched by parallel plates, the composition was irradiated with ultraviolet light at 1000 mJ / cm 2 to prepare a sample for evaluation of semi-curing.
(3) The storage elastic modulus was measured on the said measurement conditions with respect to the sample for semi-hardening evaluation obtained by (2).
　本硬化評価用サンプルの測定方法は、紫外線を１０００ｍＪ／ｃｍ２照射した後、昇温速度を５℃／分で、２５℃から１２０℃まで昇温し、１２０℃到達後３０分温度を保持し、次いで、降温速度５℃／分で、１２０℃から２５℃まで冷却し、２５℃に到達した本硬化評価用サンプルに対して貯蔵弾性率を測定した以外は、半硬化評価用サンプルと同様の方法を用いた。 The measurement method of the sample for this curing evaluation is that UV irradiation is performed at 1000 mJ / cm 2 , the temperature rising rate is raised from 25 ° C. to 120 ° C. at 5 ° C./min, and the temperature is maintained for 30 minutes after reaching 120 ° C. Then, it is cooled from 120 ° C. to 25 ° C. at a temperature decrease rate of 5 ° C./min, and the storage elastic modulus is measured with respect to the sample for main curing evaluation reaching 25 ° C. The method was used.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表１～５より、実施例の組成物は、硬化処理（本実施例では光照射処理）により、タック性を有する半硬化状態の硬化物を形成でき、例えば、被着体を位置ずれ少なく貼り合わせることができることが確認できた。 According to Tables 1 to 5, the compositions of the examples can form a cured product in a semi-cured state having tackiness by curing treatment (light irradiation treatment in this embodiment). It has been confirmed that it can be adjusted.
　また、実施例の組成物は、さらなる硬化処理（本実施例では加熱処理）により、タック性が低く、また、高温度および高湿度の環境下に置かれた場合でも高い密着力を示す本硬化状態の硬化物が得られることが確認できた。 In addition, the composition of the example has low tackiness due to the additional curing treatment (heat treatment in this example), and the main curing shows high adhesion even when placed under high temperature and high humidity environment. It was confirmed that a cured product of the state was obtained.
　以上より、本発明の組成物は、例えば、接着容易性および接着性に優れた接着剤として用いることができることが確認できた。また、光硬化および熱硬化の順で半硬化状態および本硬化状態の硬化物を形成できることから、本発明の組成物は、例えば、遮光部を有する被着体の接着にも有用であることが確認できた。 From the above, it has been confirmed that the composition of the present invention can be used, for example, as an adhesive excellent in ease of adhesion and adhesion. In addition, the composition of the present invention is also useful, for example, for adhesion of an adherend having a light shielding portion, since a cured product in a semi-cured state and a main cured state can be formed in the order of photocuring and thermal curing. It could be confirmed.
　一方、比較例では、半硬化状態を形成できなかった。比較例３および比較例４では、硬化状態を得ることができなかった。 On the other hand, in the comparative example, the semi-cured state could not be formed. In Comparative Example 3 and Comparative Example 4, the cured state could not be obtained.
　実施例４および実施例５の結果より、環状エーテル化合物として分子量の高いものを用いることで、接着性が向上することが確認できた。 From the results of Example 4 and Example 5, it was confirmed that the adhesiveness is improved by using a cyclic ether compound having a high molecular weight.

Claims (10)

  1. 　環状エーテル基を有する環状エーテル化合物と、ラジカル重合性基を有するラジカル重合性化合物と、前記ラジカル重合性基同士を重合可能な光ラジカル開始剤と、前記環状エーテル基同士を重合可能な熱重合開始剤と、を含有することを特徴とする組成物。 A cyclic ether compound having a cyclic ether group, a radical polymerizable compound having a radical polymerizable group, a photo radical initiator capable of polymerizing the radical polymerizable groups, and a thermal polymerization initiation capable of polymerizing the cyclic ether groups And an agent.
  2. 　前記熱重合開始剤が、アニオン重合開始剤を含む請求項１記載の組成物。 The composition according to claim 1, wherein the thermal polymerization initiator comprises an anionic polymerization initiator.
  3. 　前記アニオン重合開始剤が、硬化剤および硬化触媒からなる群から選択される少なくとも一種を含む請求項２記載の組成物。 The composition according to claim 2, wherein the anionic polymerization initiator comprises at least one selected from the group consisting of a curing agent and a curing catalyst.
  4. 　前記硬化剤が、ジシアンジアミドを含み、前記硬化触媒が、イミダゾール化合物を含む請求項３記載の組成物。 The composition of claim 3 wherein said curing agent comprises dicyandiamide and said curing catalyst comprises an imidazole compound.
  5. 　前記ラジカル重合性化合物の含有量が、前記環状エーテル化合物および前記ラジカル重合性化合物の合計１００質量部に対して１０質量部以上９０質量部以下である請求項１～４のうちいずれか一項記載の組成物。 The content of the radically polymerizable compound is 10 parts by mass or more and 90 parts by mass or less with respect to a total of 100 parts by mass of the cyclic ether compound and the radically polymerizable compound. Composition of
  6. 　請求項１～５のうちいずれか一項記載の組成物を含むことを特徴とする接着剤。 An adhesive comprising the composition according to any one of claims 1 to 5.
  7. 　請求項１～５のうちいずれか一項記載の組成物の硬化物であることを特徴とする硬化物。 A cured product characterized in that it is a cured product of the composition according to any one of claims 1 to 5.
  8. 　前記硬化物の、温度２５℃における貯蔵弾性率が、１．０×１０３Ｐａ以上１．０×１０５Ｐａ未満である請求項７記載の硬化物。 The cured product according to claim 7, wherein the storage elastic modulus at a temperature of 25 ° C. of the cured product is 1.0 × 10 3 Pa or more and less than 1.0 × 10 5 Pa.
  9. 　前記硬化物の、温度２５℃における貯蔵弾性率が、１．０×１０５Ｐａ以上１．０×１０１０Ｐａ以下である請求項７記載の硬化物。 The cured product according to claim 7, wherein the storage elastic modulus at a temperature of 25 ° C. of the cured product is 1.0 × 10 5 Pa or more and 1.0 × 10 10 Pa or less.
  10. 　組成物に含まれるラジカル重合性基同士を光照射により重合する工程、および組成物に含まれる環状エーテル基同士を加熱処理により重合する工程のうち少なくとも一方の工程を有する硬化物の製造方法であって、
    　前記組成物が、請求項１～５のうちいずれかの一項記載の組成物であることを特徴とする硬化物の製造方法。     A method for producing a cured product comprising at least one of a step of polymerizing radical polymerizable groups contained in a composition by light irradiation, and a step of polymerizing cyclic ether groups contained in a composition by heat treatment ,
    The method for producing a cured product, wherein the composition is the composition according to any one of claims 1 to 5.
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