WO2024062865A1 - 2-cyanoacrylate adhesive composition - Google Patents

2-cyanoacrylate adhesive composition Download PDF

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Publication number
WO2024062865A1
WO2024062865A1 PCT/JP2023/031389 JP2023031389W WO2024062865A1 WO 2024062865 A1 WO2024062865 A1 WO 2024062865A1 JP 2023031389 W JP2023031389 W JP 2023031389W WO 2024062865 A1 WO2024062865 A1 WO 2024062865A1
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Prior art keywords
group
anhydride
carbon atoms
general formula
adhesive composition
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PCT/JP2023/031389
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French (fr)
Japanese (ja)
Inventor
文哉 尾崎
美幸 石黒
稜平 宮下
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田岡化学工業株式会社
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Publication of WO2024062865A1 publication Critical patent/WO2024062865A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

  • the present invention relates to a 2-cyanoacrylate adhesive composition known as an instant adhesive.
  • 2-cyanoacrylate adhesive compositions initiate polymerization with a small amount of moisture adhering to the surface of the adherend, and cure, resulting in various adhesive properties. This allows materials to be firmly bonded in a short time. Therefore, it is widely used as a so-called instant adhesive in industrial, medical, household, and other fields.
  • the inventors focused on an adhesive composition containing an alkoxyalkyl 2-cyanoacrylate as a main component in order to improve the odor, irritation, and whitening phenomenon that occurs when using a 2-cyanoacrylate adhesive composition.
  • an adhesive composition containing an alkoxyalkyl 2-cyanoacrylate as a main component in order to improve the odor, irritation, and whitening phenomenon that occurs when using a 2-cyanoacrylate adhesive composition.
  • they exposed adherends bonded with the adhesive composition to high temperature and humidity conditions. They found that the adhesive strength was significantly reduced compared to that of an adhesive composition containing ethyl 2-cyanoacrylate as a main component, which is commonly used as a 2-cyanoacrylate adhesive composition, and in some cases the adhesive composition completely peeled off.
  • An object of the present invention is to provide an adhesive composition containing alkoxyalkyl 2-cyanoacrylate as a main component and having improved heat and humidity resistance.
  • the present inventors have developed an adhesive composition containing a compound having a plurality of specific acid anhydride groups in a specific ratio to alkoxyalkyl 2-cyanoacrylate. It has been found that the above problem can be solved by doing so.
  • the present invention includes the following inventions.
  • [1] Contains the following (A), (B) and (C), the content of (B) is 0.05 to 5 parts by weight per 100 parts by weight of (A), and the content of (C) is (A). ) Adhesive composition in an amount of 0.05 to 5 parts by weight per 100 parts by weight.
  • R 1 represents an optionally branched alkyl group having 4 to 20 carbon atoms, or an optionally branched alkenyl group having 4 to 20 carbon atoms.
  • a compound represented by (C) The following general formula (2):
  • R 2 is a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and an optionally branched alkenyl group having 2 to 20 carbon atoms. group, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms.
  • R 3 is a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and an optionally branched alkenyl group having 2 to 20 carbon atoms. group, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms.
  • R 4a and R 4b are Each independently a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, an alkenyl group having 2 to 20 carbon atoms which may have a branch, (Indicates an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 18 carbon atoms.)
  • R 5a and R 5b each independently represent a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and a cycloalkyl group having 3 to 9 carbon atoms, which may have a branch)
  • N1 represents an integer of 0 to 9.
  • X2 represents an alkylidene group having 1 to 6 carbon atoms which may be branched, a cycloalkylidene group having 5 to 14 carbon atoms which may be branched, a 1-phenylethane-1,1-diyl group, a 1,1-diphenylmethane-1,1-diyl group, a hexafluoroisopropylidene group, or a fluorenylidene group.
  • R 6a and R 6b are each independently an optionally branched alkyl group having 1 to 6 carbon atoms. group, phenyl group, or benzyl group. n 2a and n 2b each independently represent an integer of 0 to 4.)
  • an adhesive composition containing alkoxyalkyl 2-cyanoacrylate as a main component and having improved heat and humidity resistance has excellent moisture and heat resistance when bonding adherends, including steel plates, which are particularly susceptible to a decrease in adhesive strength. - Since it has superior whitening properties compared to adhesive compositions containing cyanoacrylate as a main component, it can be suitably used for adhesion of electronic parts for home appliances and automobiles, and for products with high design. Further, since the adhesive composition of the present invention provides a cured product with no clouding and excellent transparency, it can also be suitably used in fields where transparency is particularly required.
  • Component (A) is an alkoxyalkyl 2-cyanoacrylate.
  • alkoxyalkyl 2-cyanoacrylate in the present invention include methoxyethyl, methoxypropyl, methoxyisopropyl, methoxybutyl, ethoxyethyl, ethoxypropyl, ethoxyisobutyl, propoxymethyl, propoxyethyl, propoxypropyl of 2-cyanoacrylate, Examples include esters such as butoxymethyl, butoxyethyl, butoxypropyl, butoxyisopropyl, and butoxybutyl.
  • alkoxyalkyl 2-cyanoacrylates ethoxyethyl 2-cyanoacrylate and methoxyethyl 2-cyanoacrylate are preferred because they have a large effect of reducing odor and irritation of the adhesive composition and are easy to improve adhesive properties.
  • alkoxyalkyl 2-cyanoacrylates may be used alone or in combination of two or more.
  • alkoxyalkyl 2-cyanoacrylates can be produced by conventional methods (for example, Knoevenagel condensation of alkoxyalkyl 2-cyanoacetate and formaldehyde, followed by thermal depolymerization), and commercially available products are also available. It is.
  • the weight percentage of the alkoxyalkyl 2-cyanoacrylate in the total amount of the adhesive composition of the present invention is, for example, 50% by weight or more, preferably 70% by weight or more, and more preferably 80% by weight or more.
  • Component (B) is a compound having an acid anhydride group represented by the above general formula (1).
  • R 1 represents an optionally branched alkyl group having 4 to 20 carbon atoms or an optionally branched alkenyl group having 4 to 20 carbon atoms, preferably 6 carbon atoms. -18 alkenyl groups, more preferably C8-15 alkenyl groups.
  • Specific examples of the optionally branched alkyl group having 4 to 20 carbon atoms include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group.
  • tridecyl group tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.
  • the optionally branched alkenyl group having 4 to 20 carbon atoms include butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, Examples include tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, and icosenyl group.
  • Specific examples of the compound represented by the above general formula (1) include 2-methylpropylsuccinic anhydride, (2-methylpropen-2-yl)succinic anhydride, butylsuccinic anhydride, (2-methylpropen-2-yl)succinic anhydride, -buten-1-yl)succinic anhydride, hexylsuccinic anhydride, (2-hexen-1-yl)succinic anhydride, octylsuccinic anhydride, 2-octenylsuccinic anhydride, nonylsuccinic anhydride, Nonenyl succinic anhydride, isononyl succinic anhydride, isononenyl succinic anhydride, tetrapropenyl succinic anhydride, decyl succinic anhydride, decenyl succinic anhydride, dodecyl succinic anhydride, dodecenyl succin
  • butylsuccinic anhydride (2-buten-1-yl)succinic anhydride, 2-octenylsuccinic anhydride, nonenylsuccinic anhydride, tetrapropenylsuccinic anhydride, Anhydride, dodecenylsuccinic anhydride, (2-dodecen-1-yl)succinic anhydride and isooctadecenylsuccinic anhydride are preferred.
  • component (B) is preferably liquid at 25°C, and among the specific compounds mentioned above, (2-buten-1-yl)succinic anhydride, 2-octenylsuccinic anhydride, nonenylsuccinic anhydride, Acid anhydrides, tetrapropenylsuccinic anhydride, dodecenylsuccinic anhydride and isooctadecenylsuccinic anhydride are more preferred, and nonenylsuccinic anhydride, tetrapropenylsuccinic anhydride, dodecenylsuccinic anhydride and isooctadecenylsuccinic anhydride are more preferred. Nylsuccinic anhydride is particularly preferred. These compounds represented by the above general formula (1) may be used alone or in combination of two or more.
  • the content of component (B) is usually 0.05 to 5 parts by weight, preferably 0.08 to 4 parts by weight, based on 100 parts by weight of component (A) alkoxyalkyl 2-cyanoacrylate. Parts by weight.
  • Component (C) is a compound having at least one acid anhydride group selected from the group consisting of compounds represented by the above general formulas (2) to (7).
  • examples of the optionally branched alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 2,-methylbutyl group, 1-ethylpropyl group, n-hexyl group , isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2,-methylpentyl group, 3-methylpentyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group , 2-ethylbutyl group,
  • examples of the cycloalkyl group having 3 to 9 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, etc. Can be mentioned.
  • examples of the optionally branched alkenyl group having 2 to 20 carbon atoms include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, and a 1-butenyl group.
  • examples of the aryl group having 6 to 14 carbon atoms include phenyl group, tolyl group, t-butylphenyl group, naphthyl group, and anthracenyl group.
  • examples of the aralkyl group having 7 to 18 carbon atoms include benzyl group, phenethyl group, cumyl group, hydrocinnamyl group, benzhydryl group, methylbenzyl group, t-butylbenzyl group, etc. Can be mentioned.
  • compounds represented by the above general formula (2) are preferred, and 5-norbornene-2 ,3-dicarboxylic anhydride and methyl-5-norbornene-2,3-dicarboxylic anhydride are more preferred, and 5-norbornene-2,3-dicarboxylic anhydride is even more preferred.
  • an alkyl group having 1 to 20 carbon atoms which may have a branch an alkyl group having 1 to 20 carbon atoms which may have a branch, a cycloalkyl group having 3 to 9 carbon atoms which may have a branch, and a cycloalkyl group having 2 to 20 carbon atoms which may have a branch.
  • Examples of the alkenyl group, the aryl group having 6 to 14 carbon atoms, and the aralkyl group having 7 to 18 carbon atoms include the same ones as the substituent R 2 in the above general formula (2), and the preferred embodiments are also the same. It is.
  • examples of the optionally branched alkylidene group having 1 to 6 carbon atoms include an isopropylidene group, a methylene group, an ethylidene group, a butane-2,2-diyl group, etc. can be mentioned.
  • examples of the cycloalkylidene group having 5 to 14 carbon atoms which may have a branch include a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, and a cyclododecylidene group.
  • Examples of the oxocycloalkylene group having 5 to 14 carbon atoms which may have a branch include an oxocyclopentylene group, an oxocyclohexylene group, an oxocyclododecylene group, and the like.
  • R 4a and R 4b of the above general formula (4) an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and a cycloalkyl group having 2 carbon atoms optionally having a branch.
  • -20 alkenyl groups, aryl groups having 6 to 14 carbon atoms, and aralkyl groups having 7 to 18 carbon atoms include, for example, the same groups as R 2 in the above general formula (2), and preferred embodiments are also mentioned. It's the same.
  • R 5a and R 5b of the above general formula (5) an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and a cycloalkyl group having 2 carbon atoms optionally having a branch.
  • -20 alkenyl groups, aryl groups having 6 to 14 carbon atoms, and aralkyl groups having 7 to 18 carbon atoms include, for example, the same groups as R 2 in the above general formula (2), and preferred embodiments are also mentioned. It's the same.
  • n 1 represents an integer of 0 to 9, preferably 0 to 1.
  • norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'',6,6''-tetra Carboxylic dianhydrides are preferred.
  • ENEHYDE BzDA manufactured by ENEOS
  • ENEHYDE BzDAxx manufactured by ENEOS
  • ENEHYDE CpODA manufactured by ENEOS
  • the optionally branched alkylidene group having 1 to 6 carbon atoms and the optionally branched cycloalkylidene group having 5 to 14 carbon atoms include, for example, the above-mentioned
  • the same compounds as X 1 in the above general formula (4) can be mentioned.
  • Examples of the compound represented by the above general formula (6) include 4,4'-(isopropylidene) diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 4,4' -(methylene)diphthalic anhydride, 4,4'-(ethylidene)diphthalic anhydride, 4,4'-(butane-2,2-diyl)diphthalic anhydride, 4,4'-(cyclohexylidene) ) diphthalic anhydride, 4,4'-(3,5,5-trimethylcyclohexylidene) diphthalic anhydride, 4,4'-(cyclododecylidene) diphthalic anhydride, 4,4'-( 1-phenylethane-1,1-diyl) diphthalic anhydride, 4,4'-(1,1-diphenylmethane-1,1-diyl) diphthalic anhydride, 9,9-bis
  • 4,4'-(isopropylidene) diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 4,4'- (Cyclododecylidene) diphthalic anhydride and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride are preferred, and 4,4'-(hexafluoroisopropylidene) diphthalic anhydride and 9, 9-bis(3,4-dicarboxyphenyl)fluorene dianhydride is more preferred, and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride is even more preferred.
  • the optionally branched alkylidene group having 1 to 6 carbon atoms and the optionally branched cycloalkylidene group having 5 to 14 carbon atoms include, for example, the above-mentioned
  • the same compounds as X 1 in the above general formula (4) can be mentioned.
  • examples of the optionally branched alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n- Examples include butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, and the like.
  • n2a and n2b each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0.
  • n2a is 2 or more
  • multiple R6a may be the same or different from each other
  • n2b is 2 or more
  • multiple R6b may be the same or different from each other.
  • Specific examples of the compound represented by the above general formula (7) include 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride, 4,4'-(4,4' -methylenediphenoxy)diphthalic anhydride, 4,4'-(4,4'-methylenediphenoxy)diphthalic anhydride, 4,4'-(4,4'-ethylidene diphenoxy)diphthalic anhydride, 4,4'-[4,4'-(butane-2,2-diyl)diphenoxy]diphthalic anhydride, 4,4'-(4,4'-cyclohexylidene diphenoxy)diphthalic anhydride, 4, 4'-[4,4'-(3,5,5-trimethylcyclohexylidene)diphenoxy]diphthalic anhydride, 4,4'-(4,4'-cyclododecylidene diphenoxy)diphthalic anhydride , 4,4'-[4,4'
  • 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride 4,4'-(4,4'-methylenediphenoxy ) diphthalic anhydride and 4,4'-(4,4'-fluorenylidene diphenoxy) diphthalic anhydride are preferred, and 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride is more preferable.
  • 5-norbornene-2,3-dicarboxylic anhydride methyl-5-norbornene-2,3-dicarboxylic anhydride
  • 5-norbornane-2,3-dicarboxylic anhydride methyl-5-norbornane-2,3-dicarboxylic anhydride
  • 5-norbornane-2,3-dicarboxylic anhydride methyl-5-norbornane-2,3-dicarboxylic anhydride
  • norbornane-2 -Spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride 9,9-bis(3,4-di carboxyphenyl) fluorene dianhydride, 4,4'-(4,4'-
  • the content of component (C) is usually 0.05 to 5 parts by weight, preferably 0.08 to 4 parts by weight, based on 100 parts by weight of component (A) alkoxyalkyl 2-cyanoacrylate. Parts by weight.
  • the adhesive composition of the present invention may optionally contain various additives commonly used in 2-cyanoacrylate adhesive compositions. May be included. Examples of additives that may be included are shown below.
  • the thickener is not particularly limited as long as it dissolves in the alkoxyalkyl 2-cyanoacrylate and exhibits a thickening effect; for example, a polymer of methacrylic acid ester and/or acrylic acid ester may be used. Examples include certain acrylic resins, acrylic rubbers, polyvinyl chloride, polystyrene, cellulose esters, polyalkyl-2-cyanoacrylates, and ethylene-vinyl acetate copolymers.
  • methacrylate ester examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, and 2-methacrylate.
  • acrylic ester examples include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, and 2-acrylate.
  • Ethylhexyl, nonyl acrylate, methoxyethyl acrylate, methoxypropyl acrylate, ethoxyethyl acrylate, ethoxypropyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, allyl acrylate, tetrahydrofurfuryl acrylate, etc. can be mentioned.
  • acrylic resins include homopolymers of the above monomers such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, and polybutyl methacrylate, copolymers of two or more types, terpolymers, tetramers, etc. Examples include copolymers.
  • acrylic resins are preferred, methacrylic acid ester polymers are more preferred, and methyl methacrylate polymers are even more preferred. These thickeners may be used alone or in combination of two or more.
  • a thickener When a thickener is included, its content is, for example, 0.5 to 25 parts by weight, preferably 1.0 to 15 parts by weight, based on 100 parts by weight of alkoxyalkyl 2-cyanoacrylate. If the amount is in the range of 0.5 to 25 parts by weight, a sufficient thickening effect can improve handling during application and suppress deterioration of storage stability.
  • the adhesive composition of the present invention contains stabilizers (e.g., radical polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, catechol, pyrogallol, sulfur dioxide, methanesulfonic acid, etc.). , alkyl sulfonic acids such as trifluoromethanesulfonic acid, aromatic sulfonic acids such as p-toluenesulfonic acid, boron trifluoride complexes such as boron trifluoride diethyl ether complex, anions such as borohydrofluoric acid, trialkylborates, etc.
  • stabilizers e.g., radical polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, catechol, pyrogallol, sulfur dioxide, methanesulfonic acid, etc.
  • alkyl sulfonic acids such as trifluoromethane
  • polymerization inhibitors e.g., adhesion improvers (e.g., aromatic carboxylic acids and their esters, aromatic polyhydric hydroxy compounds, etc.), curing accelerators (e.g., polyalkylene oxide derivatives, calixarene compounds, etc.), plasticizers (e.g. , dimethyl phthalate, diethyl phthalate, diisodecyl phthalate, acetyl triethyl citrate, acetyl tributyl citrate, etc.), colorants (dyes, pigments, fluorescent agents), fragrances, solvents, etc.
  • Various additives commonly used in products may be included. The above additives may be used alone or in combination of two or more.
  • the present invention can also be expressed as follows. [1] Contains the following (A), (B) and (C), the content of (B) is 0.05 to 5 parts by weight per 100 parts by weight of (A), and the content of (C) is (A). ) 0.05 to 5 parts by weight per 100 parts by weight of an adhesive composition. (A) Alkoxyalkyl 2-cyanoacrylate. (B) The following general formula (1):
  • R 1 represents an optionally branched alkyl group having 4 to 20 carbon atoms, or an optionally branched alkenyl group having 4 to 20 carbon atoms.
  • a compound represented by (C) The following general formula (2):
  • R 2 is a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and an optionally branched alkenyl group having 2 to 20 carbon atoms. group, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms.
  • R 3 is a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and an optionally branched alkenyl group having 2 to 20 carbon atoms. group, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms.
  • R 4a and R 4b are Each independently a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, an alkenyl group having 2 to 20 carbon atoms which may have a branch, (Indicates an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 18 carbon atoms.)
  • R5a and R5b each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be branched, a cycloalkyl group having 3 to 9 carbon atoms, an alkenyl group having 2 to 20 carbon atoms which may be branched, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms; and n1 represents an integer of 0 to 9.
  • R 6a and R 6b are each independently an optionally branched alkyl group having 1 to 6 carbon atoms. group, phenyl group, or benzyl group.
  • n 2a and n 2b each independently represent an integer from 0 to 4.
  • a compound having at least one acid anhydride group selected from the group consisting of compounds represented by:
  • (B) is (2-buten-1-yl)succinic anhydride, 2-octenylsuccinic anhydride, nonenylsuccinic anhydride, tetrapropenylsuccinic anhydride, dodecenylsuccinic anhydride, and isooctadecenylsuccinic anhydride.
  • the adhesive composition according to [1] which is at least one compound selected from the group consisting of:
  • (C) is 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 5-norbornane-2,3-dicarboxylic anhydride, methyl-5-norbornane -2,3-dicarboxylic anhydride, 5,5'-(1,4-phenylene)bis(hexahydro-4,7-methanoisobenzofuran-1,3-dione), norbornane-2-spiro- ⁇ -cyclo Pentanone- ⁇ '-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthal At least one acid selected from the group consisting of acid anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, and 9,9-bis
  • (B) is (2-buten-1-yl)succinic anhydride, 2-octenylsuccinic anhydride, nonenylsuccinic anhydride, tetrapropenylsuccinic anhydride, dodecenylsuccinic anhydride, and isooctadecenylsuccinic anhydride.
  • At least one compound selected from the group consisting of anhydrides is 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 5 -norbornane-2,3-dicarboxylic anhydride, methyl-5-norbornane-2,3-dicarboxylic anhydride, 5,5'-(1,4-phenylene)bis(hexahydro-4,7-methanoisobenzofuran) -1,3-dione), norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, and
  • the prepared test pieces were subjected to a moist heat accelerated test at 70°C and 95% RH for 168 hours, and then the test pieces were returned to room temperature and the steel-to-steel tensile shear bond strength (N/mm 2 ) was measured in accordance with JIS K6861-6 at 25°C. From the obtained steel-to-steel tensile shear bond strength measurement results, moist heat resistance was evaluated according to the following evaluation criteria.
  • B After accelerated heat and humidity testing, adhesion peeled off or adhesion strength was less than 5.0 N/ mm2 .
  • Example 1 To 100 parts by weight of ethoxyethyl 2-cyanoacrylate, 2.0 parts by weight of tetrapropenylsuccinic anhydride (Rikacid DDSA manufactured by Shin Nihon Rika), 2.0 parts by weight of 5-norbornene-2,3-dicarboxylic anhydride, 0.4 parts by weight of methoxypolyethylene glycol methacrylate as a curing accelerator, 4.5 parts by weight of PMMA (polymethyl methacrylate, molecular weight 450,000 g/mol) as a thickener, 0 parts by weight of garlic acid monohydrate as an adhesion improver.
  • tetrapropenylsuccinic anhydride Rosinic anhydride
  • 5-norbornene-2,3-dicarboxylic anhydride 0.4 parts by weight of methoxypolyethylene glycol methacrylate as a curing accelerator
  • PMMA polymethyl methacrylate, molecular weight 450,000 g/mol
  • Example 2 Comparative Examples 1 to 9
  • tetrapropenylsuccinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, the amounts added thereof, and the amount added of the thickener (PMMA) were changed as shown in Tables 1 and 2.
  • An adhesive composition was prepared in the same manner as in Example 1 except that the above-mentioned tests were conducted. The results are shown in Tables 1 and 2.
  • Example 1 ethyl 2-cyanoacrylate was used instead of ethoxyethyl 2-cyanoacrylate, and tetrapropenylsuccinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, their addition amounts, and the increase
  • An adhesive composition was prepared in the same manner as in Example 1, except that the amount of adhesive (PMMA) added was changed as shown in Table 2, and the above-mentioned tests were conducted. The results are shown in Table 2.

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Abstract

The present invention addresses the problem of providing a 2-cyanoacrylate adhesive composition that has improved moist heat resistance and includes alkoxyalkyl 2-cyanoacrylate as a main component. By using an adhesive composition comprising a compound, which includes a plurality of specific acid anhydride groups, at a specific ratio with respect to alkoxyalkyl 2-cyanoacrylate, it is possible to provide an adhesive compound that has improved moist heat resistance and includes alkoxyalkyl 2-cyanoacrylate as a main component, thereby solving the abovementioned problem.

Description

２－シアノアクリレート系接着剤組成物2-Cyanoacrylate adhesive composition
　本発明は瞬間接着剤として知られている２－シアノアクリレート系接着剤組成物に関する。 The present invention relates to a 2-cyanoacrylate adhesive composition known as an instant adhesive.
　２－シアノアクリレート系接着剤組成物は、主成分である２－シアノアクリレートのもつ特異なアニオン重合性により、被着材料表面に付着するわずかな水分等によって重合を開始し、硬化することで各種材料を短時間で強固に接着することができるものである。そのため、いわゆる瞬間接着剤として工業用、医療用、家庭用等の分野において広く用いられている。 Due to the unique anionic polymerizability of 2-cyanoacrylate, which is the main component, 2-cyanoacrylate adhesive compositions initiate polymerization with a small amount of moisture adhering to the surface of the adherend, and cure, resulting in various adhesive properties. This allows materials to be firmly bonded in a short time. Therefore, it is widely used as a so-called instant adhesive in industrial, medical, household, and other fields.
　しかしながら、一般的な２－シアノアクリレート系接着剤組成物は優れた接着速度（硬化速度）を有する反面、特有の臭気や刺激性を示す場合や、被着体周辺への汚染が生じる（白化現象）場合があり、これらの改善が求められている。前記した課題（臭気、刺激性及び白化現象）は、２－シアノアクリレート系接着剤組成物で通常使用されるエチル２－シアノアクリレートが有する高い反応性と高い蒸気圧が一因とされ、該課題を解決し得る方法の一つとして、アルコキシアルキル２－シアノアクリレート等の分子量が大きく、蒸気圧の低い２－シアノアクリレートモノマーを２－シアノアクリレート系接着剤組成物の主成分として用いる方法が知られている（例えば特許文献１）。 However, although common 2-cyanoacrylate adhesive compositions have excellent adhesion speeds (curing speeds), they sometimes exhibit a unique odor or irritation, or cause contamination around the adherend (whitening phenomenon). ), and these improvements are required. The above-mentioned problems (odor, irritation, and whitening phenomenon) are said to be caused in part by the high reactivity and high vapor pressure of ethyl 2-cyanoacrylate, which is commonly used in 2-cyanoacrylate adhesive compositions. One known method for solving this problem is to use a 2-cyanoacrylate monomer such as alkoxyalkyl 2-cyanoacrylate, which has a large molecular weight and low vapor pressure, as the main component of a 2-cyanoacrylate adhesive composition. (For example, Patent Document 1).
日本国特開平１０－１７６１４２号公報Japanese Patent Application Publication No. 10-176142
　本発明者らは、２－シアノアクリレート系接着剤組成物使用時の臭気や刺激性、白化現象の改善を目的としてアルコキシアルキル２－シアノアクリレートを主成分として含む接着剤組成物に着眼すると共に、該接着剤組成物の耐湿熱性を評価すべく、該接着剤組成物を用いて接着した被着体を高温高湿条件下に暴露したところ、２－シアノアクリレート系接着剤組成物として汎用されているエチル２－シアノアクリレートを主成分として含む接着剤組成物を使用したものに比べて接着強度が著しく低下し、場合によっては完全に剥離してしまうことが判明した。 The inventors focused on an adhesive composition containing an alkoxyalkyl 2-cyanoacrylate as a main component in order to improve the odor, irritation, and whitening phenomenon that occurs when using a 2-cyanoacrylate adhesive composition. In addition, to evaluate the moist heat resistance of the adhesive composition, they exposed adherends bonded with the adhesive composition to high temperature and humidity conditions. They found that the adhesive strength was significantly reduced compared to that of an adhesive composition containing ethyl 2-cyanoacrylate as a main component, which is commonly used as a 2-cyanoacrylate adhesive composition, and in some cases the adhesive composition completely peeled off.
　本発明は、耐湿熱性が改善された、アルコキシアルキル２－シアノアクリレートを主成分として含む接着剤組成物を提供することを目的とする。 An object of the present invention is to provide an adhesive composition containing alkoxyalkyl 2-cyanoacrylate as a main component and having improved heat and humidity resistance.
　本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、アルコキシアルキル２－シアノアクリレートに対し、複数の特定の酸無水物基を有する化合物を、特定の割合で含む接着剤組成物とすることにより、上記課題が解決可能であることを見出した。具体的には、本発明は以下の発明を含む。 As a result of extensive research to solve the above problems, the present inventors have developed an adhesive composition containing a compound having a plurality of specific acid anhydride groups in a specific ratio to alkoxyalkyl 2-cyanoacrylate. It has been found that the above problem can be solved by doing so. Specifically, the present invention includes the following inventions.
　〔１〕
　下記（Ａ）、（Ｂ）及び（Ｃ）を含有し、（Ｂ）の含有量が（Ａ）１００重量部に対し０．０５～５重量部であり、（Ｃ）の含有量が（Ａ）１００重量部に対し０．０５～５重量部である接着剤組成物。
　（Ａ）アルコキシアルキル２－シアノアクリレート。
　（Ｂ）下記一般式（１）： [1]
Contains the following (A), (B) and (C), the content of (B) is 0.05 to 5 parts by weight per 100 parts by weight of (A), and the content of (C) is (A). ) Adhesive composition in an amount of 0.05 to 5 parts by weight per 100 parts by weight.
(A) Alkoxyalkyl 2-cyanoacrylate.
(B) The following general formula (1):
Figure JPOXMLDOC01-appb-C000008
 （式中、Ｒ１は分岐を有してもよい炭素数４～２０のアルキル基、又は分岐を有してもよい炭素数４～２０のアルケニル基を示す。）
で表される化合物。
　（Ｃ）下記一般式（２）：
Figure JPOXMLDOC01-appb-C000008
 (In the formula, R 1 represents an optionally branched alkyl group having 4 to 20 carbon atoms, or an optionally branched alkenyl group having 4 to 20 carbon atoms.)
A compound represented by
(C) The following general formula (2):
Figure JPOXMLDOC01-appb-C000009
 （式中、Ｒ２は水素原子、分岐を有してもよい炭素数１～２０のアルキル基、炭素数３～９のシクロアルキル基、分岐を有してもよい炭素数２～２０のアルケニル基、炭素数６～１４のアリール基又は炭素数７～１８のアラルキル基を示す。）
で表される化合物、下記一般式（３）：
Figure JPOXMLDOC01-appb-C000009
 (In the formula, R 2 is a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and an optionally branched alkenyl group having 2 to 20 carbon atoms. group, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms.)
A compound represented by the following general formula (3):
Figure JPOXMLDOC01-appb-C000010
 （式中、Ｒ３は水素原子、分岐を有してもよい炭素数１～２０のアルキル基、炭素数３～９のシクロアルキル基、分岐を有してもよい炭素数２～２０のアルケニル基、炭素数６～１４のアリール基又は炭素数７～１８のアラルキル基を示す。）
で表される化合物、下記一般式（４）：
Figure JPOXMLDOC01-appb-C000010
 (In the formula, R 3 is a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and an optionally branched alkenyl group having 2 to 20 carbon atoms. group, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms.)
A compound represented by the following general formula (4):
Figure JPOXMLDOC01-appb-C000011
 （式中、Ｘ１は単結合、分岐を有してもよい炭素数１～６のアルキリデン基、分岐を有してもよい炭素数５～１４のシクロアルキリデン基、分岐を有してもよい炭素数５～１４のオキソシクロアルキレン基、フェニレン基、１－フェニルエタン－１，１－ジイル基、１，１－ジフェニルメタン－１，１－ジイル基またはフルオレニリデン基を示す。Ｒ４ａ及びＲ４ｂはそれぞれ独立して、水素原子、分岐を有してもよい炭素数１～２０のアルキル基、炭素数３～９のシクロアルキル基、分岐を有してもよい炭素数２～２０のアルケニル基、炭素数６～１４のアリール基又は炭素数７～１８のアラルキル基を示す。）
で表される化合物、下記一般式（５）：
Figure JPOXMLDOC01-appb-C000011
 (In the formula , Represents an oxocycloalkylene group, phenylene group, 1-phenylethane-1,1-diyl group, 1,1-diphenylmethane-1,1-diyl group or fluorenylidene group having 5 to 14 carbon atoms.R 4a and R 4b are Each independently a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, an alkenyl group having 2 to 20 carbon atoms which may have a branch, (Indicates an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 18 carbon atoms.)
A compound represented by the following general formula (5):
Figure JPOXMLDOC01-appb-C000012
 （式中、Ｒ５ａ及びＲ５ｂはそれぞれ独立して、水素原子、分岐を有してもよい炭素数１～２０のアルキル基、炭素数３～９のシクロアルキル基、分岐を有してもよい炭素数２～２０のアルケニル基、炭素数６～１４のアリール基又は炭素数７～１８のアラルキル基を示す。ｎ１は０～９の整数を示す。）
で表される化合物、下記一般式（６）：
Figure JPOXMLDOC01-appb-C000012
 (In the formula, R 5a and R 5b each independently represent a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and a cycloalkyl group having 3 to 9 carbon atoms, which may have a branch) ( N1 represents an integer of 0 to 9.)
A compound represented by the following general formula (6):
Figure JPOXMLDOC01-appb-C000013
 （式中、Ｘ２は分岐を有してもよい炭素数１～６のアルキリデン基、分岐を有してもよい炭素数５～１４のシクロアルキリデン基、１－フェニルエタン－１，１－ジイル基、１，１－ジフェニルメタン－１，１－ジイル基、ヘキサフルオロイソプロピリデン基またはフルオレニリデン基を示す。）
で表される化合物、及び下記一般式（７）：
Figure JPOXMLDOC01-appb-C000013
 (In the formula, X2 represents an alkylidene group having 1 to 6 carbon atoms which may be branched, a cycloalkylidene group having 5 to 14 carbon atoms which may be branched, a 1-phenylethane-1,1-diyl group, a 1,1-diphenylmethane-1,1-diyl group, a hexafluoroisopropylidene group, or a fluorenylidene group.)
and a compound represented by the following general formula (7):
Figure JPOXMLDOC01-appb-C000014
 （式中、Ｘ３は分岐を有してもよい炭素数１～６のアルキリデン基、分岐を有してもよい炭素数５～１４のシクロアルキリデン基、１－フェニルエタン－１，１－ジイル基、１，１－ジフェニルメタン－１，１－ジイル基、ヘキサフルオロイソプロピリデン基またはフルオレニリデン基を示す。Ｒ６ａ及びＲ６ｂはそれぞれ独立して分岐を有してもよい炭素数１～６のアルキル基、フェニル基またはベンジル基を示す。ｎ２ａ及びｎ２ｂはそれぞれ独立して０～４の整数を示す。）
で表される化合物からなる群から選ばれる少なくとも１種の酸無水物基を有する化合物。
Figure JPOXMLDOC01-appb-C000014
 (In the formula , group, 1,1-diphenylmethane-1,1-diyl group, hexafluoroisopropylidene group, or fluorenylidene group.R 6a and R 6b are each independently an optionally branched alkyl group having 1 to 6 carbon atoms. group, phenyl group, or benzyl group. n 2a and n 2b each independently represent an integer of 0 to 4.)
A compound having at least one acid anhydride group selected from the group consisting of compounds represented by:
　本発明によれば、耐湿熱性が改善されたアルコキシアルキル２－シアノアクリレートを主成分として含む接着剤組成物が提供可能となる。本発明の接着剤組成物は、特に接着強度の低下を起こしやすい鋼板を含む被着体の接着時の耐湿熱性に優れ、また、２－シアノアクリレート系接着剤組成物として汎用されているエチル２－シアノアクリレートを主成分として含む接着剤組成物に比べて低白化性にも優れることから、家電や自動車向け電材部品の接着、及び意匠性の高い製品に好適に用いることができる。また、本発明の接着剤組成物は、白濁がなく透明性に優れた硬化物を与えることから、特に透明性が求められる分野においても好適に用いることができる。 According to the present invention, it is possible to provide an adhesive composition containing alkoxyalkyl 2-cyanoacrylate as a main component and having improved heat and humidity resistance. The adhesive composition of the present invention has excellent moisture and heat resistance when bonding adherends, including steel plates, which are particularly susceptible to a decrease in adhesive strength. - Since it has superior whitening properties compared to adhesive compositions containing cyanoacrylate as a main component, it can be suitably used for adhesion of electronic parts for home appliances and automobiles, and for products with high design. Further, since the adhesive composition of the present invention provides a cured product with no clouding and excellent transparency, it can also be suitably used in fields where transparency is particularly required.
＜成分（Ａ）＞
　成分（Ａ）は、アルコキシアルキル２－シアノアクリレートである。本発明におけるアルコキシアルキル２－シアノアクリレートとしては、例えば、２－シアノアクリル酸のメトキシエチル、メトキシプロピル、メトキシイソプロピル、メトキシブチル、エトキシエチル、エトキシプロピル、エトキシイソブチル、プロポキシメチル、プロポキシエチル、プロポキシプロピル、ブトキシメチル、ブトキシエチル、ブトキシプロピル、ブトキシイソプロピル、ブトキシブチル等のエステル類が挙げられる。これらアルコキシアルキル２－シアノアクリレートの中でも、接着剤組成物の臭気や刺激性の低減効果が大きく、接着特性を向上させやすいことからエトキシエチル２－シアノアクリレート及びメトキシエチル２－シアノアクリレートが好ましい。これらアルコキシアルキル２－シアノアクリレートは単独で用いてもよく、２種以上を併用してもよい。 <Component (A)>
Component (A) is an alkoxyalkyl 2-cyanoacrylate. Examples of the alkoxyalkyl 2-cyanoacrylate in the present invention include methoxyethyl, methoxypropyl, methoxyisopropyl, methoxybutyl, ethoxyethyl, ethoxypropyl, ethoxyisobutyl, propoxymethyl, propoxyethyl, propoxypropyl of 2-cyanoacrylate, Examples include esters such as butoxymethyl, butoxyethyl, butoxypropyl, butoxyisopropyl, and butoxybutyl. Among these alkoxyalkyl 2-cyanoacrylates, ethoxyethyl 2-cyanoacrylate and methoxyethyl 2-cyanoacrylate are preferred because they have a large effect of reducing odor and irritation of the adhesive composition and are easy to improve adhesive properties. These alkoxyalkyl 2-cyanoacrylates may be used alone or in combination of two or more.
　これらアルコキシアルキル２－シアノアクリレートは、常法（例えば、アルコキシアルキル２－シアノアセテートとホルムアルデヒドのクネーフェナーゲル縮合と、続く熱解重合により製造する方法）によって製造される他、市販品も入手可能である。 These alkoxyalkyl 2-cyanoacrylates can be produced by conventional methods (for example, Knoevenagel condensation of alkoxyalkyl 2-cyanoacetate and formaldehyde, followed by thermal depolymerization), and commercially available products are also available. It is.
　本発明の接着剤組成物全量に占めるアルコキシアルキル２－シアノアクリレートの重量割合は、例えば、５０重量％以上、好ましくは７０重量％以上、より好ましくは８０％以上である。 The weight percentage of the alkoxyalkyl 2-cyanoacrylate in the total amount of the adhesive composition of the present invention is, for example, 50% by weight or more, preferably 70% by weight or more, and more preferably 80% by weight or more.
＜成分（Ｂ）＞
　成分（Ｂ）は、上記一般式（１）で表される酸無水物基を有する化合物である。 <Component (B)>
Component (B) is a compound having an acid anhydride group represented by the above general formula (1).
　上記一般式（１）において、Ｒ１は分岐を有してもよい炭素数４～２０のアルキル基または分岐を有してもよい炭素数４～２０のアルケニル基を示し、好ましくは炭素数６～１８のアルケニル基、より好ましくは炭素数８～１５のアルケニル基である。分岐を有してもよい炭素数４～２０のアルキル基として具体的には、例えば、ブチル基、ペンチル基、ヘキシル基、へプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基等が挙げられる。分岐を有してもよい炭素数４～２０のアルケニル基として具体的には、例えば、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、トリデセニル基、テトラデセニル基、ペンタデセニル基、ヘキサデセニル基、ヘプタデセニル基、オクタデセニル基、ノナデセニル基、イコセニル基等が挙げられる。 In the above general formula (1), R 1 represents an optionally branched alkyl group having 4 to 20 carbon atoms or an optionally branched alkenyl group having 4 to 20 carbon atoms, preferably 6 carbon atoms. -18 alkenyl groups, more preferably C8-15 alkenyl groups. Specific examples of the optionally branched alkyl group having 4 to 20 carbon atoms include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. , tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like. Specific examples of the optionally branched alkenyl group having 4 to 20 carbon atoms include butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, Examples include tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, and icosenyl group.
　上記一般式（１）で表される化合物として具体的には、例えば、２－メチルプロピルコハク酸無水物、（２－メチルプロペン－２－イル）コハク酸無水物、ブチルコハク酸無水物、（２－ブテン－１－イル）コハク酸無水物、ヘキシルコハク酸無水物、（２－ヘキセン－１－イル）コハク酸無水物、オクチルコハク酸無水物、２－オクテニルコハク酸無水物、ノニルコハク酸無水物、ノネニルコハク酸無水物、イソノニルコハク酸無水物、イソノネニルコハク酸無水物、テトラプロペニルコハク酸無水物、デシルコハク酸無水物、デセニルコハク酸無水物、ドデシルコハク酸無水物、ドデセニルコハク酸無水物、イソドデセニルコハク酸無水物、（２－ドデセン－１－イル）コハク酸無水物、テトラドデシルコハク酸無水物、テトラデセニルコハク酸無水物、ヘキサデシルコハク酸無水物、ヘキサデセニルコハク酸無水物、オクタデシルコハク酸無水物、オクタデセニルコハク酸無水物、イソオクタデシルコハク酸無水物、イソオクタデセニルコハク酸無水物等が挙げられる。 Specific examples of the compound represented by the above general formula (1) include 2-methylpropylsuccinic anhydride, (2-methylpropen-2-yl)succinic anhydride, butylsuccinic anhydride, (2-methylpropen-2-yl)succinic anhydride, -buten-1-yl)succinic anhydride, hexylsuccinic anhydride, (2-hexen-1-yl)succinic anhydride, octylsuccinic anhydride, 2-octenylsuccinic anhydride, nonylsuccinic anhydride, Nonenyl succinic anhydride, isononyl succinic anhydride, isononenyl succinic anhydride, tetrapropenyl succinic anhydride, decyl succinic anhydride, decenyl succinic anhydride, dodecyl succinic anhydride, dodecenyl succinic anhydride, isodode Cenylsuccinic anhydride, (2-dodecen-1-yl)succinic anhydride, tetradodecylsuccinic anhydride, tetradecenylsuccinic anhydride, hexadecylsuccinic anhydride, hexadecenylsuccinic acid Examples include anhydride, octadecylsuccinic anhydride, octadecenylsuccinic anhydride, isooctadecylsuccinic anhydride, isooctadecenylsuccinic anhydride, and the like.
　これら上記一般式（１）で表される化合物の中でも、ブチルコハク酸無水物、（２－ブテン－１－イル）コハク酸無水物、２－オクテニルコハク酸無水物、ノネニルコハク酸無水物、テトラプロペニルコハク酸無水物、ドデセニルコハク酸無水物、（２－ドデセン－１－イル）コハク酸無水物及びイソオクタデセニルコハク酸無水物が好ましい。また、本発明において成分（Ｂ）は２５℃で液体であることが好ましく、前記した具体的化合物の中でも、（２－ブテン－１－イル）コハク酸無水物、２－オクテニルコハク酸無水物、ノネニルコハク酸無水物、テトラプロペニルコハク酸無水物、ドデセニルコハク酸無水物及びイソオクタデセニルコハク酸無水物がより好ましく、ノネニルコハク酸無水物、テトラプロペニルコハク酸無水物、ドデセニルコハク酸無水物及びイソオクタデセニルコハク酸無水物が特に好ましい。これら上記一般式（１）で表される化合物は、単独で用いてもよく、２種以上を併用してもよい。 Among these compounds represented by the above general formula (1), butylsuccinic anhydride, (2-buten-1-yl)succinic anhydride, 2-octenylsuccinic anhydride, nonenylsuccinic anhydride, tetrapropenylsuccinic anhydride, Anhydride, dodecenylsuccinic anhydride, (2-dodecen-1-yl)succinic anhydride and isooctadecenylsuccinic anhydride are preferred. In the present invention, component (B) is preferably liquid at 25°C, and among the specific compounds mentioned above, (2-buten-1-yl)succinic anhydride, 2-octenylsuccinic anhydride, nonenylsuccinic anhydride, Acid anhydrides, tetrapropenylsuccinic anhydride, dodecenylsuccinic anhydride and isooctadecenylsuccinic anhydride are more preferred, and nonenylsuccinic anhydride, tetrapropenylsuccinic anhydride, dodecenylsuccinic anhydride and isooctadecenylsuccinic anhydride are more preferred. Nylsuccinic anhydride is particularly preferred. These compounds represented by the above general formula (1) may be used alone or in combination of two or more.
　本発明の接着剤組成物において、成分（Ｂ）の含有量は、成分（Ａ）アルコキシアルキル２－シアノアクリレート１００重量部に対し、通常０．０５～５重量部、好ましくは０．０８～４重量部である。含有量を０．０５～５重量部の範囲とすることにより、接着層への湿気の侵入が抑えられ、耐湿熱性を向上させることができ、また、保存安定性に優れる接着剤組成物とすることができる。 In the adhesive composition of the present invention, the content of component (B) is usually 0.05 to 5 parts by weight, preferably 0.08 to 4 parts by weight, based on 100 parts by weight of component (A) alkoxyalkyl 2-cyanoacrylate. Parts by weight. By setting the content in the range of 0.05 to 5 parts by weight, the intrusion of moisture into the adhesive layer can be suppressed, the moisture and heat resistance can be improved, and the adhesive composition can have excellent storage stability. be able to.
＜成分（Ｃ）＞
　成分（Ｃ）は、上記一般式（２）～（７）で表される化合物からなる群から選ばれる少なくとも１種の酸無水物基を有する化合物である。 <Component (C)>
Component (C) is a compound having at least one acid anhydride group selected from the group consisting of compounds represented by the above general formulas (2) to (7).
　上記一般式（２）のＲ２において、分岐を有してもよい炭素数１～２０のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ｓｅｃ－ペンチル基、ｔｅｒｔ－ペンチル基、ネオペンチル基、２，－メチルブチル基、１－エチルプロピル基、ｎ－ヘキシル基、イソヘキシル基、ｓｅｃ－ヘキシル基、ｔｅｒｔ－ヘキシル基、ネオヘキシル基、２，－メチルペンチル基、３－メチルペンチル基、１，２－ジメチルブチル基、２，２－ジメチルブチル基、１－エチルブチル基、２－エチルブチル基、ｎ－ヘプチル基、イソヘプチル基、ｓｅｃ－ヘプチル基、ｔｅｒｔ－ヘプチル基、ネオヘプチル基、２－メチルヘキシル基、３－メチルヘキシル基、２，２－ジメチルペンチル基、３－エチルペンチル基、２，４－ジメチルペンチル基、１－エチル－１－メチルブチル基、１，２，３－トリメチルブチル基、ｎ－オクチル基、イソオクチル基、ｓｅｃ－オクチル基、ｔｅｒｔ－オクチル基、ネオオクチル基、ｎ－ノニル基、イソノニル基、ｓｅｃ－ノニル基、ｔｅｒｔ－ノニル基、ネオノニル基等が挙げられる。これら分岐を有してもよい炭素数１～２０のアルキル基の中でも、炭素数１～９アルキル基が好ましい。 In R 2 of the above general formula (2), examples of the optionally branched alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 2,-methylbutyl group, 1-ethylpropyl group, n-hexyl group , isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2,-methylpentyl group, 3-methylpentyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group , 2-ethylbutyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, neoheptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 3-ethyl group Pentyl group, 2,4-dimethylpentyl group, 1-ethyl-1-methylbutyl group, 1,2,3-trimethylbutyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, neooctyl group , n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, neononyl group, etc. Among these alkyl groups having 1 to 20 carbon atoms which may have branches, alkyl groups having 1 to 9 carbon atoms are preferred.
　上記一般式（２）のＲ２において、炭素数３～９のシクロアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基等が挙げられる。 In R 2 of the above general formula (2), examples of the cycloalkyl group having 3 to 9 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, etc. Can be mentioned.
　上記一般式（２）のＲ２において、分岐を有してもよい炭素数２～２０のアルケニル基としては、例えば、ビニル基、アリル基、１－プロペニル基、イソプロペニル基、１－ブテニル基、２－ブテニル基、３－ブテニル基、２－メチル－２－プロペニル基、１－ペンテニル基、２－ペンテニル基、３－ペンテニル基、４－ペンテニル基、２－メチル－２－ブテニル基、１，２－ジメチル－２－プロペニル基、１－ヘキセニル基、２－ヘキセニル基、３－ヘキセニル基、４－ヘキセニル基、５－ヘキセニル基、２－メチル－２－ペンテニル基、１－ヘプテニル基、２－ヘプテニル基、３－ヘプテニル基、４－ヘプテニル基、５－ヘプテニル基、６－ヘプテニル基、１－オクテニル基、２－オクテニル基、１－ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、トリデセニル基、テトラデセニル基、ペンタデセニル基、ヘキサデセニル基、ヘプタデセニル基、オクタデセニル基、ノナデセニル基等が挙げられる。これら分岐を有してもよい炭素数２～２０のアルケニル基の中でも、炭素数２～１２のアルケニル基が好ましい。 In R 2 of the above general formula (2), examples of the optionally branched alkenyl group having 2 to 20 carbon atoms include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, and a 1-butenyl group. , 2-butenyl group, 3-butenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 2-methyl-2-butenyl group, 1 , 2-dimethyl-2-propenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 2-methyl-2-pentenyl group, 1-heptenyl group, 2 -heptenyl group, 3-heptenyl group, 4-heptenyl group, 5-heptenyl group, 6-heptenyl group, 1-octenyl group, 2-octenyl group, 1-nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group , a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadecenyl group, and the like. Among these alkenyl groups having 2 to 20 carbon atoms which may have branches, alkenyl groups having 2 to 12 carbon atoms are preferred.
　上記一般式（２）のＲ２において、炭素数６～１４のアリール基としては、例えば、フェニル基、トリル基、ｔ－ブチルフェニル基、ナフチル基、アントラセニル基等が挙げられる。 In R 2 of the above general formula (2), examples of the aryl group having 6 to 14 carbon atoms include phenyl group, tolyl group, t-butylphenyl group, naphthyl group, and anthracenyl group.
　上記一般式（２）のＲ２において、炭素数７～１８のアラルキル基としては、例えば、ベンジル基、フェネチル基、クミル基、ヒドロシンナミル基、ベンスヒドリル基、メチルベンジル基、ｔ－ブチルベンジル基等が挙げられる。 In R 2 of the above general formula (2), examples of the aralkyl group having 7 to 18 carbon atoms include benzyl group, phenethyl group, cumyl group, hydrocinnamyl group, benzhydryl group, methylbenzyl group, t-butylbenzyl group, etc. Can be mentioned.
　上記一般式（２）で表される化合物の中でも、Ｒ２が水素原子、または炭素数１～９のアルキル基である上記一般式（２）で表される化合物が好ましく、５－ノルボルネン－２，３－ジカルボン酸無水物及びメチル－５－ノルボルネン－２，３－ジカルボン酸無水物がより好ましく、５－ノルボルネン－２，３－ジカルボン酸無水物が更に好ましい。 Among the compounds represented by the above general formula (2), compounds represented by the above general formula (2) in which R 2 is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms are preferred, and 5-norbornene-2 ,3-dicarboxylic anhydride and methyl-5-norbornene-2,3-dicarboxylic anhydride are more preferred, and 5-norbornene-2,3-dicarboxylic anhydride is even more preferred.
　上記一般式（３）のＲ３において、分岐を有してもよい炭素数１～２０のアルキル基、炭素数３～９のシクロアルキル基、分岐を有してもよい炭素数２～２０のアルケニル基、炭素数６～１４のアリール基及び炭素数７～１８のアラルキル基としては、例えば、上述した上記一般式（２）の置換基Ｒ２と同じものが挙げられ、好ましい態様についても同じである。 In R 3 of the above general formula (3), an alkyl group having 1 to 20 carbon atoms which may have a branch, a cycloalkyl group having 3 to 9 carbon atoms which may have a branch, and a cycloalkyl group having 2 to 20 carbon atoms which may have a branch. Examples of the alkenyl group, the aryl group having 6 to 14 carbon atoms, and the aralkyl group having 7 to 18 carbon atoms include the same ones as the substituent R 2 in the above general formula (2), and the preferred embodiments are also the same. It is.
　上記一般式（３）で表される化合物の中でも、Ｒ３が水素原子、または炭素数１～９のアルキル基である上記一般式（３）で表される化合物が好ましく、５－ノルボルナン－２，３－ジカルボン酸無水物及びメチル－５－ノルボルナン－２，３－ジカルボン酸無水物がより好ましい。 Among the compounds represented by the above general formula (3), compounds represented by the above general formula (3) in which R 3 is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms are preferred, and 5-norbornane-2 , 3-dicarboxylic anhydride and methyl-5-norbornane-2,3-dicarboxylic anhydride are more preferred.
　上記一般式（２）で表される化合物および上記一般式（３）で表される化合物の市販品としては、例えば、５－ノルボルネン－２，３－ジカルボン酸無水物（東京化成工業社製）、カヤハードＣＤ、カヤハードＭＣＤ（日本化薬社製）、ＭＨＡＣ－Ｐ（昭和電工マテリアルズ社製）、無水ハイミック酸／無水ナジック酸（Ｐｕｙａｎｇ　Ｈｕｉｇｈｅｎｇ　Ｅｌｅｃｔｒｏｎｉｃ　Ｍａｔｅｒｉａｌ　Ｃｏ．，Ｌｔｄ．製）、ヘキサヒドロ－４，７－メタノイソベンゾフラン－１，３－ジオン（５－ノルボルナン－２，３－ジカルボン酸無水物／富士フイルム和光純薬（株））等が挙げられる。 Commercially available products of the compound represented by the above general formula (2) and the compound represented by the above general formula (3) include, for example, 5-norbornene-2,3-dicarboxylic anhydride (Tokyo Chemical Industry Co., Ltd.), Kayahard CD, Kayahard MCD (Nippon Kayaku Co., Ltd.), MHAC-P (Showa Denko Materials Co., Ltd.), Himic anhydride/Nadic anhydride (Puyang Huigheng Electronic Material Co., Ltd.), and hexahydro-4,7-methanoisobenzofuran-1,3-dione (5-norbornane-2,3-dicarboxylic anhydride/FUJIFILM Wako Pure Chemical Industries, Ltd.).
　上記一般式（４）のＸ１において、分岐を有してもよい炭素数１～６のアルキリデン基としては、例えば、イソプロピリデン基、メチレン基、エチリデン基、ブタン－２，２－ジイル基等が挙げられる。分岐を有してもよい炭素数５～１４のシクロアルキリデン基としては、例えば、シクロヘキシリデン基、３，５，５－トリメチルシクロヘキシリデン基、シクロドデシリデン基等が挙げられる。分岐を有してもよい炭素数５～１４のオキソシクロアルキレン基としては、例えば、オキソシクロペンチレン基、オキソシクロヘキシレン基、オキソシクロドデシレン基等が挙げられる。 In X 1 of the above general formula (4), examples of the optionally branched alkylidene group having 1 to 6 carbon atoms include an isopropylidene group, a methylene group, an ethylidene group, a butane-2,2-diyl group, etc. can be mentioned. Examples of the cycloalkylidene group having 5 to 14 carbon atoms which may have a branch include a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, and a cyclododecylidene group. Examples of the oxocycloalkylene group having 5 to 14 carbon atoms which may have a branch include an oxocyclopentylene group, an oxocyclohexylene group, an oxocyclododecylene group, and the like.
　上記一般式（４）のＲ４ａ及びＲ４ｂにおいて、分岐を有してもよい炭素数１～２０のアルキル基、炭素数３～９のシクロアルキル基、分岐を有してもよい炭素数２～２０のアルケニル基、炭素数６～１４のアリール基及び炭素数７～１８のアラルキル基としては、例えば、上述した上記一般式（２）のＲ２と同じものが挙げられ、好ましい態様についても同じである。 In R 4a and R 4b of the above general formula (4), an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and a cycloalkyl group having 2 carbon atoms optionally having a branch. -20 alkenyl groups, aryl groups having 6 to 14 carbon atoms, and aralkyl groups having 7 to 18 carbon atoms include, for example, the same groups as R 2 in the above general formula (2), and preferred embodiments are also mentioned. It's the same.
　上記一般式（４）で表される化合物の中でも、立体異性体を含めて、５，５’－（１，４－フェニレン）ビス（ヘキサヒドロ－４，７－メタノイソベンゾフラン－１，３－ジオン）及びドデカヒドロ（５，５’－ビ－４，７－メタノイソベンゾフラン）－１，１’，３，３’－テトラオンが好ましく、５，５’－（１，４－フェニレン）ビス（ヘキサヒドロ－４，７－メタノイソベンゾフラン－１，３－ジオン）がより好ましい。 Among the compounds represented by the above general formula (4), including stereoisomers, 5,5'-(1,4-phenylene)bis(hexahydro-4,7-methanoisobenzofuran-1,3-dione) ) and dodecahydro(5,5'-bi-4,7-methanoisobenzofuran)-1,1',3,3'-tetraone are preferred, and 5,5'-(1,4-phenylene)bis(hexahydro- 4,7-methanoisobenzofuran-1,3-dione) is more preferred.
　上記一般式（５）のＲ５ａ及びＲ５ｂにおいて、分岐を有してもよい炭素数１～２０のアルキル基、炭素数３～９のシクロアルキル基、分岐を有してもよい炭素数２～２０のアルケニル基、炭素数６～１４のアリール基及び炭素数７～１８のアラルキル基としては、例えば、上述した上記一般式（２）のＲ２と同じものが挙げられ、好ましい態様についても同じである。また、ｎ１は０～９の整数を示し、好ましくは０～１である。 In R 5a and R 5b of the above general formula (5), an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and a cycloalkyl group having 2 carbon atoms optionally having a branch. -20 alkenyl groups, aryl groups having 6 to 14 carbon atoms, and aralkyl groups having 7 to 18 carbon atoms include, for example, the same groups as R 2 in the above general formula (2), and preferred embodiments are also mentioned. It's the same. Further, n 1 represents an integer of 0 to 9, preferably 0 to 1.
　上記一般式（５）で表される化合物の中でも、ノルボルナン－２－スピロ－α－シクロペンタノン－α’－スピロ－２’’－ノルボルナン－５，５’’，６，６’’－テトラカルボン酸二無水物が好ましい。 Among the compounds represented by the general formula (5), norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetra Carboxylic dianhydrides are preferred.
　上記一般式（４）で表される化合物および上記一般式（５）で表される化合物の市販品としては、例えば、ＥＮＥＨＹＤＥ　ＢｚＤＡ（ＥＮＥＯＳ社製）、ＥＮＥＨＹＤＥ　ＢｚＤＡｘｘ（ＥＮＥＯＳ社製）、ＥＮＥＨＹＤＥ　ＣｐＯＤＡ（ＥＮＥＯＳ社製）等が挙げられる。 Commercial products of the compound represented by the above general formula (4) and the compound represented by the above general formula (5) include, for example, ENEHYDE BzDA (manufactured by ENEOS), ENEHYDE BzDAxx (manufactured by ENEOS), and ENEHYDE CpODA (manufactured by ENEOS). (manufactured by ENEOS), etc.
　上記一般式（６）のＸ２において、分岐を有してもよい炭素数１～６のアルキリデン基および分岐を有してもよい炭素数５～１４のシクロアルキリデン基としては、例えば、上述した上記一般式（４）のＸ１と同じものが挙げられる。 In X 2 of the above general formula (6), the optionally branched alkylidene group having 1 to 6 carbon atoms and the optionally branched cycloalkylidene group having 5 to 14 carbon atoms include, for example, the above-mentioned The same compounds as X 1 in the above general formula (4) can be mentioned.
　上記一般式（６）で表される化合物としては、例えば、４，４’－（イソプロピリデン）ジフタル酸無水物、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物、４，４’－（メチレン）ジフタル酸無水物、４，４’－（エチリデン）ジフタル酸無水物、４，４’－（ブタン－２，２－ジイル）ジフタル酸無水物、４，４’－（シクロヘキシリデン）ジフタル酸無水物、４，４’－（３，５，５－トリメチルシクロヘキシリデン）ジフタル酸無水物、４，４’－（シクロドデシリデン）ジフタル酸無水物、４，４’－（１－フェニルエタン－１，１－ジイル）ジフタル酸無水物、４，４’－（１，１－ジフェニルメタン－１，１－ジイル）ジフタル酸無水物、９，９－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物等が挙げられる。これら上記一般式（１）で表される化合物の中でも、４，４’－（イソプロピリデン）ジフタル酸無水物、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物、４，４’－（シクロドデシリデン）ジフタル酸無水物及び９，９－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物が好ましく、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物及び９，９－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物がより好ましく、９，９－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物が更に好ましい。 Examples of the compound represented by the above general formula (6) include 4,4'-(isopropylidene) diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 4,4' -(methylene)diphthalic anhydride, 4,4'-(ethylidene)diphthalic anhydride, 4,4'-(butane-2,2-diyl)diphthalic anhydride, 4,4'-(cyclohexylidene) ) diphthalic anhydride, 4,4'-(3,5,5-trimethylcyclohexylidene) diphthalic anhydride, 4,4'-(cyclododecylidene) diphthalic anhydride, 4,4'-( 1-phenylethane-1,1-diyl) diphthalic anhydride, 4,4'-(1,1-diphenylmethane-1,1-diyl) diphthalic anhydride, 9,9-bis(3,4-diyl) (carboxyphenyl)fluorene dianhydride and the like. Among these compounds represented by the above general formula (1), 4,4'-(isopropylidene) diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 4,4'- (Cyclododecylidene) diphthalic anhydride and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride are preferred, and 4,4'-(hexafluoroisopropylidene) diphthalic anhydride and 9, 9-bis(3,4-dicarboxyphenyl)fluorene dianhydride is more preferred, and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride is even more preferred.
　上記一般式（７）のＸ３において、分岐を有してもよい炭素数１～６のアルキリデン基および分岐を有してもよい炭素数５～１４のシクロアルキリデン基としては、例えば、上述した上記一般式（４）のＸ１と同じものが挙げられる。 In X 3 of the above general formula (7), the optionally branched alkylidene group having 1 to 6 carbon atoms and the optionally branched cycloalkylidene group having 5 to 14 carbon atoms include, for example, the above-mentioned The same compounds as X 1 in the above general formula (4) can be mentioned.
　上記一般式（７）のＲ６ａ及びＲ６ｂにおいて、分岐を有してもよい炭素数１～６のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基等が挙げられる。 In R 6a and R 6b of the above general formula (7), examples of the optionally branched alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n- Examples include butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, and the like.
　上記一般式（７）においてｎ２ａ及びｎ２ｂはそれぞれ独立して０～４の整数を示し、好ましくは０～２の整数、より好ましくは０である。なお、ｎ２ａが２以上である場合、複数あるＲ６ａは互いに同一であっても異なってもよく、ｎ２ｂが２以上である場合、複数あるＲ６ｂは互いに同一であっても異なってもよい。 In the above general formula (7), n2a and n2b each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0. When n2a is 2 or more, multiple R6a may be the same or different from each other, and when n2b is 2 or more, multiple R6b may be the same or different from each other.
　上記一般式（７）で表される化合物として具体的には、例えば、４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸無水物、４，４’－（４，４’－メチレンジフェノキシ）ジフタル酸無水物、４，４’－（４，４’－メチレンジフェノキシ）ジフタル酸無水物、４，４’－（４，４’－エチリデンジフェノキシ）ジフタル酸無水物、４，４’－［４，４’－（ブタン－２，２－ジイル）ジフェノキシ］ジフタル酸無水物、４，４’－（４，４’－シクロヘキシリデンジフェノキシ）ジフタル酸無水物、４，４’－［４，４’－（３，５，５－トリメチルシクロヘキシリデン）ジフェノキシ］ジフタル酸無水物、４，４’－（４，４’－シクロドデシリデンジフェノキシ）ジフタル酸無水物、４，４’－［４，４’－（１－フェニルエタン－１，１－ジイル）ジフェノキシ］ジフタル酸無水物、４，４’－［４，４’－（１，１－ジフェニルメタン－１，１－ジイル）ジフェノキシ］ジフタル酸無水物、４，４’－（４，４’－フルオレニリデンジフェノキシ）ジフタル酸無水物等が挙げられる。これら上記一般式（７）で表される化合物の中でも、４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸無水物、４，４’－（４，４’－メチレンジフェノキシ）ジフタル酸無水物及び４，４’－（４，４’－フルオレニリデンジフェノキシ）ジフタル酸無水物が好ましく、４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸無水物がより好ましい。 Specific examples of the compound represented by the above general formula (7) include 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride, 4,4'-(4,4' -methylenediphenoxy)diphthalic anhydride, 4,4'-(4,4'-methylenediphenoxy)diphthalic anhydride, 4,4'-(4,4'-ethylidene diphenoxy)diphthalic anhydride, 4,4'-[4,4'-(butane-2,2-diyl)diphenoxy]diphthalic anhydride, 4,4'-(4,4'-cyclohexylidene diphenoxy)diphthalic anhydride, 4, 4'-[4,4'-(3,5,5-trimethylcyclohexylidene)diphenoxy]diphthalic anhydride, 4,4'-(4,4'-cyclododecylidene diphenoxy)diphthalic anhydride , 4,4'-[4,4'-(1-phenylethane-1,1-diyl)diphenoxy]diphthalic anhydride, 4,4'-[4,4'-(1,1-diphenylmethane-1 , 1-diyl)diphenoxy]diphthalic anhydride, 4,4'-(4,4'-fluorenylidene diphenoxy)diphthalic anhydride, and the like. Among these compounds represented by the above general formula (7), 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride, 4,4'-(4,4'-methylenediphenoxy ) diphthalic anhydride and 4,4'-(4,4'-fluorenylidene diphenoxy) diphthalic anhydride are preferred, and 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride is more preferable.
　また、これら成分（Ｃ）の中でも、５－ノルボルネン－２，３－ジカルボン酸無水物、メチル－５－ノルボルネン－２，３－ジカルボン酸無水物、５－ノルボルナン－２，３－ジカルボン酸無水物、メチル－５－ノルボルナン－２，３－ジカルボン酸無水物、５，５’－（１，４－フェニレン）ビス（ヘキサヒドロ－４，７－メタノイソベンゾフラン－１，３－ジオン）、ノルボルナン－２－スピロ－α－シクロペンタノン－α’－スピロ－２’’－ノルボルナン－５，５’’，６，６’’－テトラカルボン酸二無水物、９，９－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物、４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸二無水物、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物および上記一般式（３）で表される化合物が好ましく、５－ノルボルネン－２，３－ジカルボン酸無水物、５，５’－（１，４－フェニレン）ビス（ヘキサヒドロ－４，７－メタノイソベンゾフラン－１，３－ジオン）、９，９－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物、及び４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸二無水物がより好ましい。また、成分（Ｃ）として挙げたこれらの化合物は、単独で用いてもよく、２種以上を併用してもよい。 Also, among these components (C), 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 5-norbornane-2,3-dicarboxylic anhydride , methyl-5-norbornane-2,3-dicarboxylic anhydride, 5,5'-(1,4-phenylene)bis(hexahydro-4,7-methanoisobenzofuran-1,3-dione), norbornane-2 -Spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, 9,9-bis(3,4-di carboxyphenyl) fluorene dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride and the above general formula ( Compounds represented by 3) are preferred, including 5-norbornene-2,3-dicarboxylic anhydride, 5,5'-(1,4-phenylene)bis(hexahydro-4,7-methanoisobenzofuran-1,3 -dione), 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic dianhydride are more preferred. Further, these compounds listed as component (C) may be used alone or in combination of two or more.
　本発明の接着剤組成物において、成分（Ｃ）の含有量は、成分（Ａ）アルコキシアルキル２－シアノアクリレート１００重量部に対し、通常０．０５～５重量部、好ましくは０．０８～４重量部である。含有量を０．０５～５重量部の範囲とすることにより、接着層への湿気の侵入が抑えられ、耐湿熱性を向上させることができ、また、保存安定性に優れる接着剤組成物とすることができる。 In the adhesive composition of the present invention, the content of component (C) is usually 0.05 to 5 parts by weight, preferably 0.08 to 4 parts by weight, based on 100 parts by weight of component (A) alkoxyalkyl 2-cyanoacrylate. Parts by weight. By setting the content in the range of 0.05 to 5 parts by weight, the intrusion of moisture into the adhesive layer can be suppressed, the moisture and heat resistance can be improved, and the adhesive composition can have excellent storage stability. be able to.
　本発明の接着剤組成物には、上記成分（Ａ）、（Ｂ）及び（Ｃ）の他、必要に応じ、２－シアノアクリレート系接着剤組成物において一般的に用いられる各種添加剤等が含まれていてもよい。以下、含まれていてもよい添加剤について例示する。 In addition to the above-mentioned components (A), (B), and (C), the adhesive composition of the present invention may optionally contain various additives commonly used in 2-cyanoacrylate adhesive compositions. May be included. Examples of additives that may be included are shown below.
＜増粘剤＞
　増粘剤としては、アルコキシアルキル２－シアノアクリレートに溶解し、増粘効果を発現するものであれば、特に限定されるものではなく、例えば、メタクリル酸エステルおよび／またはアクリル酸エステルの重合体であるアクリル樹脂、アクリルゴム、ポリ塩化ビニル、ポリスチレン、セルロースエステル、ポリアルキル－２－シアノアクリレート、エチレン－酢酸ビニル共重合体等が挙げられる。前記メタクリル酸エステルとしては、例えば、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸イソプロピル、メタクリル酸ブチル、メタクリル酸イソブチル、メタクリル酸ヘキシル、メタクリル酸ヘプチル、メタクリル酸オクチル、メタクリル酸－２－エチルヘキシル、メタクリル酸ノニル、メタクリル酸メトキシエチル、メタクリル酸メトキシプロピル、メタクリル酸エトキシエチル、メタクリル酸エトキシプロピル、メタクリル酸ヒドロキシエチル、メタクリル酸ヒドロキシプロピル、メタクリル酸ヒドロキシブチル、メタクリル酸アリル、メタクリル酸テトラヒドロフリフリル等が挙げられる。前記アクリル酸エステルとしては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸イソプロピル、アクリル酸ブチル、アクリル酸イソブチル、アクリル酸ヘキシル、アクリル酸ヘプチル、アクリル酸オクチル、アクリル酸－２－エチルヘキシル、アクリル酸ノニル、アクリル酸メトキシエチル、アクリル酸メトキシプロピル、アクリル酸エトキシエチル、アクリル酸エトキシプロピル、アクリル酸ヒドロキシエチル、アクリル酸ヒドロキシプロピル、アクリル酸ヒドロキシブチルアクリル酸アリル、アクリル酸テトラヒドロフリフリル等が挙げられる。アクリル樹脂の具体例としては、ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリメタクリル酸プロピル、ポリメタクリル酸ブチル等の前記モノマーの単独重合体や、２種以上からなるコポリマー、ターポリマー、テトラマー等の共重合体が挙げられる。これら増粘剤の中でも、アクリル樹脂が好ましく、メタクリル酸エステルの重合体がより好ましく、メタクリル酸メチルの重合体がさらに好ましい。これら増粘剤は、単独で用いてもよく、２種以上を併用してもよい。 <Thickener>
The thickener is not particularly limited as long as it dissolves in the alkoxyalkyl 2-cyanoacrylate and exhibits a thickening effect; for example, a polymer of methacrylic acid ester and/or acrylic acid ester may be used. Examples include certain acrylic resins, acrylic rubbers, polyvinyl chloride, polystyrene, cellulose esters, polyalkyl-2-cyanoacrylates, and ethylene-vinyl acetate copolymers. Examples of the methacrylate ester include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, and 2-methacrylate. Ethylhexyl, nonyl methacrylate, methoxyethyl methacrylate, methoxypropyl methacrylate, ethoxyethyl methacrylate, ethoxypropyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, allyl methacrylate, tetrahydrofurifuryl methacrylate etc. Examples of the acrylic ester include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, and 2-acrylate. Ethylhexyl, nonyl acrylate, methoxyethyl acrylate, methoxypropyl acrylate, ethoxyethyl acrylate, ethoxypropyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, allyl acrylate, tetrahydrofurfuryl acrylate, etc. can be mentioned. Specific examples of acrylic resins include homopolymers of the above monomers such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, and polybutyl methacrylate, copolymers of two or more types, terpolymers, tetramers, etc. Examples include copolymers. Among these thickeners, acrylic resins are preferred, methacrylic acid ester polymers are more preferred, and methyl methacrylate polymers are even more preferred. These thickeners may be used alone or in combination of two or more.
　増粘剤を含む場合、その含有量は、例えば、アルコキシアルキル２－シアノアクリレート１００重量部に対し０．５～２５重量部、好ましくは１．０～１５重量部である。０．５～２５重量部の範囲であれば、充分な増粘効果により、塗布時のハンドリング性の向上や、貯蔵安定性の悪化の抑制が可能となる。 When a thickener is included, its content is, for example, 0.5 to 25 parts by weight, preferably 1.0 to 15 parts by weight, based on 100 parts by weight of alkoxyalkyl 2-cyanoacrylate. If the amount is in the range of 0.5 to 25 parts by weight, a sufficient thickening effect can improve handling during application and suppress deterioration of storage stability.
＜その他の添加剤＞
　本発明の接着剤組成物には、上述した増粘剤の他、安定剤（例えば、ハイドロキノン、ハイドロキノンモノメチルエーテル、ｔ－ブチルカテコール、カテコール、ピロガロール等のラジカル重合禁止剤、二酸化硫黄、メタンスルホン酸、トリフルオロメタンスルホン酸等のアルキルスルホン酸、ｐ－トルエンスルホン酸等の芳香族スルホン酸、三弗化ホウ素ジエチルエーテル錯体等の三弗化ホウ素錯体、ホウ弗化水素酸、トリアルキルボレート等のアニオン重合禁止剤）、密着性向上剤（例えば、芳香族カルボン酸およびそのエステル、芳香族多価ヒドロキシ化合物等）、硬化促進剤（例えば、ポリアルキレンオキサイド誘導体、カリックスアレン化合物等）、可塑剤（例えば、フタル酸ジメチル、フタル酸ジエチル、フタル酸ジイソデシル、アセチルクエン酸トリエチル、アセチルクエン酸トリブチル等）、着色剤（染料、顔料、蛍光剤）、香料、溶剤、等の２－シアノアクリレート系接着剤組成物にて一般的に用いられる各種添加剤が含まれていてもよい。上記した添加剤は単独で用いてもよく、２種以上を併用してもよい。 <Other additives>
In addition to the above-mentioned thickeners, the adhesive composition of the present invention contains stabilizers (e.g., radical polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, catechol, pyrogallol, sulfur dioxide, methanesulfonic acid, etc.). , alkyl sulfonic acids such as trifluoromethanesulfonic acid, aromatic sulfonic acids such as p-toluenesulfonic acid, boron trifluoride complexes such as boron trifluoride diethyl ether complex, anions such as borohydrofluoric acid, trialkylborates, etc. polymerization inhibitors), adhesion improvers (e.g., aromatic carboxylic acids and their esters, aromatic polyhydric hydroxy compounds, etc.), curing accelerators (e.g., polyalkylene oxide derivatives, calixarene compounds, etc.), plasticizers (e.g. , dimethyl phthalate, diethyl phthalate, diisodecyl phthalate, acetyl triethyl citrate, acetyl tributyl citrate, etc.), colorants (dyes, pigments, fluorescent agents), fragrances, solvents, etc. Various additives commonly used in products may be included. The above additives may be used alone or in combination of two or more.
　本発明は、以下のように表現することもできる。
　〔１〕
　下記（Ａ）、（Ｂ）及び（Ｃ）を含有し、（Ｂ）の含有量が（Ａ）１００重量部に対し０．０５～５重量部であり、（Ｃ）の含有量が（Ａ）１００重量部に対し０．０５～５重量部である接着剤組成物。
　（Ａ）アルコキシアルキル２－シアノアクリレート。
　（Ｂ）下記一般式（１）： The present invention can also be expressed as follows.
[1]
Contains the following (A), (B) and (C), the content of (B) is 0.05 to 5 parts by weight per 100 parts by weight of (A), and the content of (C) is (A). ) 0.05 to 5 parts by weight per 100 parts by weight of an adhesive composition.
(A) Alkoxyalkyl 2-cyanoacrylate.
(B) The following general formula (1):
Figure JPOXMLDOC01-appb-C000015
 （式中、Ｒ１は分岐を有してもよい炭素数４～２０のアルキル基、又は分岐を有してもよい炭素数４～２０のアルケニル基を示す。）
で表される化合物。
　（Ｃ）下記一般式（２）：
Figure JPOXMLDOC01-appb-C000015
 (In the formula, R 1 represents an optionally branched alkyl group having 4 to 20 carbon atoms, or an optionally branched alkenyl group having 4 to 20 carbon atoms.)
A compound represented by
(C) The following general formula (2):
Figure JPOXMLDOC01-appb-C000016
 （式中、Ｒ２は水素原子、分岐を有してもよい炭素数１～２０のアルキル基、炭素数３～９のシクロアルキル基、分岐を有してもよい炭素数２～２０のアルケニル基、炭素数６～１４のアリール基又は炭素数７～１８のアラルキル基を示す。）
で表される化合物、下記一般式（３）：
Figure JPOXMLDOC01-appb-C000016
 (In the formula, R 2 is a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and an optionally branched alkenyl group having 2 to 20 carbon atoms. group, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms.)
A compound represented by the following general formula (3):
Figure JPOXMLDOC01-appb-C000017
 （式中、Ｒ３は水素原子、分岐を有してもよい炭素数１～２０のアルキル基、炭素数３～９のシクロアルキル基、分岐を有してもよい炭素数２～２０のアルケニル基、炭素数６～１４のアリール基又は炭素数７～１８のアラルキル基を示す。）
で表される化合物、下記一般式（４）：
Figure JPOXMLDOC01-appb-C000017
 (In the formula, R 3 is a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and an optionally branched alkenyl group having 2 to 20 carbon atoms. group, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms.)
A compound represented by the following general formula (4):
Figure JPOXMLDOC01-appb-C000018
 （式中、Ｘ１は単結合、分岐を有してもよい炭素数１～６のアルキリデン基、分岐を有してもよい炭素数５～１４のシクロアルキリデン基、分岐を有してもよい炭素数５～１４のオキソシクロアルキレン基、フェニレン基、１－フェニルエタン－１，１－ジイル基、１，１－ジフェニルメタン－１，１－ジイル基またはフルオレニリデン基を示す。Ｒ４ａ及びＲ４ｂはそれぞれ独立して、水素原子、分岐を有してもよい炭素数１～２０のアルキル基、炭素数３～９のシクロアルキル基、分岐を有してもよい炭素数２～２０のアルケニル基、炭素数６～１４のアリール基又は炭素数７～１８のアラルキル基を示す。）
で表される化合物、下記一般式（５）：
Figure JPOXMLDOC01-appb-C000018
 (In the formula , Represents an oxocycloalkylene group, phenylene group, 1-phenylethane-1,1-diyl group, 1,1-diphenylmethane-1,1-diyl group or fluorenylidene group having 5 to 14 carbon atoms.R 4a and R 4b are Each independently a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, an alkenyl group having 2 to 20 carbon atoms which may have a branch, (Indicates an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 18 carbon atoms.)
A compound represented by the following general formula (5):
Figure JPOXMLDOC01-appb-C000019
 （式中、Ｒ５ａ及びＲ５ｂはそれぞれ独立して、水素原子、分岐を有してもよい炭素数１～２０のアルキル基、炭素数３～９のシクロアルキル基、分岐を有してもよい炭素数２～２０のアルケニル基、炭素数６～１４のアリール基又は炭素数７～１８のアラルキル基を示す。ｎ１は０～９の整数を示す。）
で表される化合物、下記一般式（６）：
Figure JPOXMLDOC01-appb-C000019
 (In the formula, R5a and R5b each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be branched, a cycloalkyl group having 3 to 9 carbon atoms, an alkenyl group having 2 to 20 carbon atoms which may be branched, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms; and n1 represents an integer of 0 to 9.)
A compound represented by the following general formula (6):
Figure JPOXMLDOC01-appb-C000020
 （式中、Ｘ２は分岐を有してもよい炭素数１～６のアルキリデン基、分岐を有してもよい炭素数５～１４のシクロアルキリデン基、１－フェニルエタン－１，１－ジイル基、１，１－ジフェニルメタン－１，１－ジイル基、ヘキサフルオロイソプロピリデン基またはフルオレニリデン基を示す。）
で表される化合物、及び下記一般式（７）：
Figure JPOXMLDOC01-appb-C000020
 (In the formula , group, 1,1-diphenylmethane-1,1-diyl group, hexafluoroisopropylidene group, or fluorenylidene group.)
A compound represented by and the following general formula (7):
Figure JPOXMLDOC01-appb-C000021
 （式中、Ｘ３は分岐を有してもよい炭素数１～６のアルキリデン基、分岐を有してもよい炭素数５～１４のシクロアルキリデン基、１－フェニルエタン－１，１－ジイル基、１，１－ジフェニルメタン－１，１－ジイル基、ヘキサフルオロイソプロピリデン基またはフルオレニリデン基を示す。Ｒ６ａ及びＲ６ｂはそれぞれ独立して分岐を有してもよい炭素数１～６のアルキル基、フェニル基またはベンジル基を示す。ｎ２ａ及びｎ２ｂはそれぞれ独立して０～４の整数を示す。）
で表される化合物からなる群から選ばれる少なくとも１種の酸無水物基を有する化合物。
Figure JPOXMLDOC01-appb-C000021
 (In the formula , group, 1,1-diphenylmethane-1,1-diyl group, hexafluoroisopropylidene group, or fluorenylidene group.R 6a and R 6b are each independently an optionally branched alkyl group having 1 to 6 carbon atoms. group, phenyl group, or benzyl group. n 2a and n 2b each independently represent an integer from 0 to 4.)
A compound having at least one acid anhydride group selected from the group consisting of compounds represented by:
　〔２〕
　（Ｂ）が（２－ブテン－１－イル）コハク酸無水物、２－オクテニルコハク酸無水物、ノネニルコハク酸無水物、テトラプロペニルコハク酸無水物、ドデセニルコハク酸無水物及びイソオクタデセニルコハク酸無水物からなる群から選ばれる少なくとも１種の化合物である、〔１〕に記載の接着剤組成物。 [2]
(B) is (2-buten-1-yl)succinic anhydride, 2-octenylsuccinic anhydride, nonenylsuccinic anhydride, tetrapropenylsuccinic anhydride, dodecenylsuccinic anhydride, and isooctadecenylsuccinic anhydride. The adhesive composition according to [1], which is at least one compound selected from the group consisting of:
　〔３〕
　（Ｃ）が５－ノルボルネン－２，３－ジカルボン酸無水物、メチル－５－ノルボルネン－２，３－ジカルボン酸無水物、５－ノルボルナン－２，３－ジカルボン酸無水物、メチル－５－ノルボルナン－２，３－ジカルボン酸無水物、５，５’－（１，４－フェニレン）ビス（ヘキサヒドロ－４，７－メタノイソベンゾフラン－１，３－ジオン）、ノルボルナン－２－スピロ－α－シクロペンタノン－α’－スピロ－２’’－ノルボルナン－５，５’’，６，６’’－テトラカルボン酸二無水物、４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸無水物、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物、及び９，９－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物からなる群から選ばれる少なくとも１種の酸無水物基を有する化合物である、〔１〕又は〔２〕に記載の接着剤組成物。 [3]
(C) is 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 5-norbornane-2,3-dicarboxylic anhydride, methyl-5-norbornane -2,3-dicarboxylic anhydride, 5,5'-(1,4-phenylene)bis(hexahydro-4,7-methanoisobenzofuran-1,3-dione), norbornane-2-spiro-α-cyclo Pentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthal At least one acid selected from the group consisting of acid anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride The adhesive composition according to [1] or [2], which is a compound having an anhydride group.
　〔４〕
　（Ｂ）が（２－ブテン－１－イル）コハク酸無水物、２－オクテニルコハク酸無水物、ノネニルコハク酸無水物、テトラプロペニルコハク酸無水物、ドデセニルコハク酸無水物、及びイソオクタデセニルコハク酸無水物からなる群から選ばれる少なくとも１種の化合物であり、且つ（Ｃ）が５－ノルボルネン－２，３－ジカルボン酸無水物、メチル－５－ノルボルネン－２，３－ジカルボン酸無水物、５－ノルボルナン－２，３－ジカルボン酸無水物、メチル－５－ノルボルナン－２，３－ジカルボン酸無水物、５，５’－（１，４－フェニレン）ビス（ヘキサヒドロ－４，７－メタノイソベンゾフラン－１，３－ジオン）、ノルボルナン－２－スピロ－α－シクロペンタノン－α’－スピロ－２’’－ノルボルナン－５，５’’，６，６’’－テトラカルボン酸二無水物、４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸無水物、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物、及び９，９－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物からなる群から選ばれる少なくとも１種の酸無水物基を有する化合物である、〔１〕～〔３〕のいずれかに記載の接着剤組成物。 [4]
(B) is (2-buten-1-yl)succinic anhydride, 2-octenylsuccinic anhydride, nonenylsuccinic anhydride, tetrapropenylsuccinic anhydride, dodecenylsuccinic anhydride, and isooctadecenylsuccinic anhydride. at least one compound selected from the group consisting of anhydrides, and (C) is 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 5 -norbornane-2,3-dicarboxylic anhydride, methyl-5-norbornane-2,3-dicarboxylic anhydride, 5,5'-(1,4-phenylene)bis(hexahydro-4,7-methanoisobenzofuran) -1,3-dione), norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, and 9,9-bis(3,4-dicarboxy) The adhesive composition according to any one of [1] to [3], which is a compound having at least one acid anhydride group selected from the group consisting of phenyl)fluorene dianhydride.
　〔５〕
　更に増粘剤を（Ａ）１００重量部に対し０．５～２５重量部含む、〔１〕～〔４〕のいずれかに記載の接着剤組成物。 [5]
The adhesive composition according to any one of [1] to [4], further comprising 0.5 to 25 parts by weight of a thickener per 100 parts by weight of (A).
　本発明は上述した各実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。さらに、各実施形態にそれぞれ開示された技術的手段を組み合わせることにより、新しい技術的特徴を形成することができる。 The present invention is not limited to the embodiments described above, and various modifications can be made within the scope of the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. are also included within the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment.
　以下、実施例等を挙げて本発明をより詳細に説明するが、本発明はこれらに何ら限定されるものではない。 Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these in any way.
＜試験方法＞
　（１）均一性
　ＪＩＳ　Ｋ６８６１－４に準拠した方法によりサンプルを調製し、目視により硬化前の接着剤組成物中の各種添加剤の溶け残りによる濁りを確認した。
Ａ：溶け残りなし、透明。
Ｂ：溶け残りあり、不透明、固体分散。 <Test method>
(1) Uniformity A sample was prepared according to a method in accordance with JIS K6861-4, and turbidity due to undissolved various additives in the adhesive composition before curing was visually confirmed.
A: No undissolved material, transparent.
B: Undissolved, opaque, solid dispersion.
　（２）硬化物の透明性
　接着剤組成物を６０℃９５％ＲＨの温湿度に制御されたオーブン内に１日静置して硬化させ、厚み約７ｍｍの硬化物を作製した。作製した硬化物を通して紙面に印刷した文字を視認することで、硬化物の透明性を目視により評価した。
Ａ：硬化物が透明であり、紙面に印刷した文字が視認できる。
Ｂ：硬化物が白濁、濁りがあり、紙面に印刷した文字が視認できない、あるいは困難である。 (2) Transparency of cured product The adhesive composition was cured by leaving it in an oven controlled at a temperature and humidity of 60° C. and 95% RH for one day to produce a cured product with a thickness of about 7 mm. The transparency of the cured product was visually evaluated by visually recognizing the characters printed on the paper surface through the prepared cured product.
A: The cured product is transparent and the characters printed on the paper are visible.
B: The cured product is cloudy or cloudy, and the characters printed on the paper are not visible or difficult to see.
　（３）低汚染性
　接着剤組成物１滴を黒色ＥＰＤＭ試験片上に載せ、４０℃８０％ＲＨの温湿度に制御されたオーブン内に１時間静置して硬化させた後、硬化物周辺の黒色ＥＰＤＭ試験片の白化具合を目視により評価した。
Ａ：白化なし。
Ｂ：白化あり。 (3) Low staining property One drop of the adhesive composition was placed on a black EPDM test piece and left to harden for one hour in an oven controlled at a temperature and humidity of 40°C and 80% RH. The degree of whitening of the black EPDM test piece was visually evaluated.
A: No whitening.
B: Whitening.
　（４）耐湿熱性
　表面を研磨した軟鋼板（ＪＩＳＧ３１４１　ＳＰＣＣ－ＳＢ：１．６×２５×１００ｍｍ）を、接着剤組成物を用いて２２℃、６０％ＲＨ環境下で貼り合わせ、圧着したまま２２℃、６０％ＲＨ環境下で２４時間静置して養生することで試験片を作製した。 (4) Moisture and heat resistance Mild steel plates (JISG3141 SPCC-SB: 1.6 x 25 x 100 mm) with polished surfaces were bonded together using an adhesive composition in an environment of 22°C and 60% RH. A test piece was prepared by leaving it for 24 hours and curing it in an environment of 60% RH at ℃.
　作製した試験片に対し、７０℃９５％ＲＨで１６８時間湿熱促進試験を行った後、試験片を室温に戻し、２５℃にてＪＩＳ　Ｋ６８６１－６に準じて鋼－鋼引張せん断接着強さ（Ｎ／ｍｍ２）を測定した。得られた鋼－鋼引張せん断接着強さの測定結果から、以下の評価基準に従って耐湿熱性を評価した。
Ａ：湿熱促進後の接着強度が５．０Ｎ／ｍｍ２以上。
Ｂ：湿熱促進後に接着剥離、または接着強度が５．０Ｎ／ｍｍ２未満。 The prepared test pieces were subjected to a moist heat accelerated test at 70°C and 95% RH for 168 hours, and then the test pieces were returned to room temperature and the steel-to-steel tensile shear bond strength (N/mm 2 ) was measured in accordance with JIS K6861-6 at 25°C. From the obtained steel-to-steel tensile shear bond strength measurement results, moist heat resistance was evaluated according to the following evaluation criteria.
A: The adhesive strength after accelerated heat and humidity treatment is 5.0 N/mm2 or more.
B: After accelerated heat and humidity testing, adhesion peeled off or adhesion strength was less than 5.0 N/ mm2 .
　（実施例１）
　エトキシエチル２－シアノアクリレート１００重量部に対し、テトラプロペニルコハク酸無水物（新日本理化製リカシッドＤＤＳＡ）２．０重量部、５－ノルボルネン－２，３－ジカルボン酸無水物２．０重量部、硬化促進剤としてメトキシポリエチレングリコールメタクリレート０．４重量部、増粘剤としてＰＭＭＡ（ポリメタクリル酸メチル、分子量４５万ｇ／ｍｏｌ）４．５重量部、密着性向上剤としてガーリック酸一水和物０．０１重量部、アニオン重合禁止剤としてＨＢＦ４１０ｐｐｍ、ラジカル重合禁止剤としてハイドロキノン１０００ｐｐｍを添加し、窒素雰囲気下４０～６０℃の温度で２４時間撹拌して接着剤組成物を調製した。調製後、得られた２－シアノアクリレート系接着剤組成物について、上述した各試験を実施した。結果を表１に示す。 (Example 1)
To 100 parts by weight of ethoxyethyl 2-cyanoacrylate, 2.0 parts by weight of tetrapropenylsuccinic anhydride (Rikacid DDSA manufactured by Shin Nihon Rika), 2.0 parts by weight of 5-norbornene-2,3-dicarboxylic anhydride, 0.4 parts by weight of methoxypolyethylene glycol methacrylate as a curing accelerator, 4.5 parts by weight of PMMA (polymethyl methacrylate, molecular weight 450,000 g/mol) as a thickener, 0 parts by weight of garlic acid monohydrate as an adhesion improver. 01 parts by weight, 410 ppm of HBF as an anionic polymerization inhibitor, and 1000 ppm of hydroquinone as a radical polymerization inhibitor were added and stirred for 24 hours at a temperature of 40 to 60° C. under a nitrogen atmosphere to prepare an adhesive composition. After preparation, the above-mentioned tests were conducted on the obtained 2-cyanoacrylate adhesive composition. The results are shown in Table 1.
　（実施例２～８、比較例１～９）
　実施例１において、テトラプロペニルコハク酸無水物、５－ノルボルネン－２，３－ジカルボン酸無水物及びこれらの添加量、並びに増粘剤（ＰＭＭＡ）の添加量を表１及び表２に示す通り変更した以外は実施例１と同様にして接着剤組成物を調製し、上述した各試験を実施した。結果を表１及び表２に示す。 (Examples 2 to 8, Comparative Examples 1 to 9)
In Example 1, tetrapropenylsuccinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, the amounts added thereof, and the amount added of the thickener (PMMA) were changed as shown in Tables 1 and 2. An adhesive composition was prepared in the same manner as in Example 1 except that the above-mentioned tests were conducted. The results are shown in Tables 1 and 2.
　（参考例１）
　実施例１において、エトキシエチル２－シアノアクリレートの代わりにエチル２－シアノアクリレートを使用し、テトラプロペニルコハク酸無水物、５－ノルボルネン－２，３－ジカルボン酸無水物及びこれらの添加量、並びに増粘剤（ＰＭＭＡ）の添加量を表２に示す通り変更した以外は実施例１と同様にして接着剤組成物を調製し、上述した各試験を実施した。結果を表２に示す。 (Reference example 1)
In Example 1, ethyl 2-cyanoacrylate was used instead of ethoxyethyl 2-cyanoacrylate, and tetrapropenylsuccinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, their addition amounts, and the increase An adhesive composition was prepared in the same manner as in Example 1, except that the amount of adhesive (PMMA) added was changed as shown in Table 2, and the above-mentioned tests were conducted. The results are shown in Table 2.
　なお、表１及び表２における各略号は、下記の化合物を意味する。 The abbreviations in Tables 1 and 2 refer to the following compounds.
＜酸無水物（１）＞
Ｂ－１：テトラプロペニルコハク酸無水物（新日本理化製リカシッドＤＤＳＡ）
Ｂ－２：ドデセニルコハク酸無水物（三洋化成工業製ＤＳＡ）
Ｂ－３：ノネニルコハク酸無水物
Ｂ－４：イソオクタデセニルコハク酸無水物
＜酸無水物（２）＞
Ｃ－１：５－ノルボルネン－２，３－ジカルボン酸無水物
Ｃ－２：４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸無水物
Ｃ－３：５，５’－（１，４－フェニレン）ビス（ヘキサヒドロ－４，７－メタノイソベンゾフラン－１，３－ジオン）
Ｃ－４：９，９－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物 <Acid anhydride (1)>
B-1: Tetrapropenylsuccinic anhydride (Ricasid DDSA manufactured by Shin Nippon Chemical)
B-2: Dodecenyl succinic anhydride (DSA manufactured by Sanyo Chemical Industries)
B-3: Nonenyl succinic anhydride B-4: Isooctadecenyl succinic anhydride <Acid anhydride (2)>
C-1: 5-norbornene-2,3-dicarboxylic anhydride C-2: 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride C-3: 5,5'-( 1,4-phenylene)bis(hexahydro-4,7-methanoisobenzofuran-1,3-dione)
C-4: 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023

Claims (5)

  1. 　下記（Ａ）、（Ｂ）及び（Ｃ）を含有し、（Ｂ）の含有量が（Ａ）１００重量部に対し０．０５～５重量部であり、（Ｃ）の含有量が（Ａ）１００重量部に対し０．０５～５重量部である接着剤組成物。
    　（Ａ）アルコキシアルキル２－シアノアクリレート。
    　（Ｂ）下記一般式（１）：
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１は分岐を有してもよい炭素数４～２０のアルキル基、又は分岐を有してもよい炭素数４～２０のアルケニル基を示す。）
    で表される化合物。
    　（Ｃ）下記一般式（２）：
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ２は水素原子、分岐を有してもよい炭素数１～２０のアルキル基、炭素数３～９のシクロアルキル基、分岐を有してもよい炭素数２～２０のアルケニル基、炭素数６～１４のアリール基又は炭素数７～１８のアラルキル基を示す。）
    で表される化合物、下記一般式（３）：
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ３は水素原子、分岐を有してもよい炭素数１～２０のアルキル基、炭素数３～９のシクロアルキル基、分岐を有してもよい炭素数２～２０のアルケニル基、炭素数６～１４のアリール基又は炭素数７～１８のアラルキル基を示す。）
    で表される化合物、下記一般式（４）：
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｘ１は単結合、分岐を有してもよい炭素数１～６のアルキリデン基、分岐を有してもよい炭素数５～１４のシクロアルキリデン基、分岐を有してもよい炭素数５～１４のオキソシクロアルキレン基、フェニレン基、１－フェニルエタン－１，１－ジイル基、１，１－ジフェニルメタン－１，１－ジイル基またはフルオレニリデン基を示す。Ｒ４ａ及びＲ４ｂはそれぞれ独立して、水素原子、分岐を有してもよい炭素数１～２０のアルキル基、炭素数３～９のシクロアルキル基、分岐を有してもよい炭素数２～２０のアルケニル基、炭素数６～１４のアリール基又は炭素数７～１８のアラルキル基を示す。）
    で表される化合物、下記一般式（５）：
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ｒ５ａ及びＲ５ｂはそれぞれ独立して、水素原子、分岐を有してもよい炭素数１～２０のアルキル基、炭素数３～９のシクロアルキル基、分岐を有してもよい炭素数２～２０のアルケニル基、炭素数６～１４のアリール基又は炭素数７～１８のアラルキル基を示す。ｎ１は０～９の整数を示す。）
    で表される化合物、下記一般式（６）：
    Figure JPOXMLDOC01-appb-C000006
     （式中、Ｘ２は分岐を有してもよい炭素数１～６のアルキリデン基、分岐を有してもよい炭素数５～１４のシクロアルキリデン基、１－フェニルエタン－１，１－ジイル基、１，１－ジフェニルメタン－１，１－ジイル基、ヘキサフルオロイソプロピリデン基またはフルオレニリデン基を示す。）
    で表される化合物、及び下記一般式（７）：
    Figure JPOXMLDOC01-appb-C000007
     （式中、Ｘ３は分岐を有してもよい炭素数１～６のアルキリデン基、分岐を有してもよい炭素数５～１４のシクロアルキリデン基、１－フェニルエタン－１，１－ジイル基、１，１－ジフェニルメタン－１，１－ジイル基、ヘキサフルオロイソプロピリデン基またはフルオレニリデン基を示す。Ｒ６ａ及びＲ６ｂはそれぞれ独立して分岐を有してもよい炭素数１～６のアルキル基、フェニル基またはベンジル基を示す。ｎ２ａ及びｎ２ｂはそれぞれ独立して０～４の整数を示す。）
    で表される化合物からなる群から選ばれる少なくとも１種の酸無水物基を有する化合物。     Contains the following (A), (B) and (C), the content of (B) is 0.05 to 5 parts by weight per 100 parts by weight of (A), and the content of (C) is (A). ) 0.05 to 5 parts by weight per 100 parts by weight of an adhesive composition.
    (A) Alkoxyalkyl 2-cyanoacrylate.
    (B) The following general formula (1):
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, R 1 represents an optionally branched alkyl group having 4 to 20 carbon atoms, or an optionally branched alkenyl group having 4 to 20 carbon atoms.)
    A compound represented by
    (C) The following general formula (2):
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, R 2 is a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and an optionally branched alkenyl group having 2 to 20 carbon atoms. group, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms.)
    A compound represented by the following general formula (3):
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, R 3 is a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and an optionally branched alkenyl group having 2 to 20 carbon atoms. group, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms.)
    A compound represented by the following general formula (4):
    Figure JPOXMLDOC01-appb-C000004
     (In the formula , Represents an oxocycloalkylene group, phenylene group, 1-phenylethane-1,1-diyl group, 1,1-diphenylmethane-1,1-diyl group or fluorenylidene group having 5 to 14 carbon atoms.R 4a and R 4b are Each independently a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, an alkenyl group having 2 to 20 carbon atoms which may have a branch, (Indicates an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 18 carbon atoms.)
    A compound represented by the following general formula (5):
    Figure JPOXMLDOC01-appb-C000005
     (In the formula, R 5a and R 5b each independently represent a hydrogen atom, an optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 9 carbon atoms, and a cycloalkyl group having 3 to 9 carbon atoms, which may have a branch) ( N1 represents an integer of 0 to 9.)
    A compound represented by the following general formula (6):
    Figure JPOXMLDOC01-appb-C000006
     (In the formula , group, 1,1-diphenylmethane-1,1-diyl group, hexafluoroisopropylidene group, or fluorenylidene group.)
    A compound represented by and the following general formula (7):
    Figure JPOXMLDOC01-appb-C000007
     (In the formula , group, 1,1-diphenylmethane-1,1-diyl group, hexafluoroisopropylidene group, or fluorenylidene group.R 6a and R 6b are each independently an optionally branched alkyl group having 1 to 6 carbon atoms. group, phenyl group, or benzyl group. n 2a and n 2b each independently represent an integer of 0 to 4.)
    A compound having at least one acid anhydride group selected from the group consisting of compounds represented by:
  2. 　（Ｂ）が（２－ブテン－１－イル）コハク酸無水物、２－オクテニルコハク酸無水物、ノネニルコハク酸無水物、テトラプロペニルコハク酸無水物、ドデセニルコハク酸無水物及びイソオクタデセニルコハク酸無水物からなる群から選ばれる少なくとも１種の化合物である、請求項１に記載の接着剤組成物。 (B) is (2-buten-1-yl)succinic anhydride, 2-octenylsuccinic anhydride, nonenylsuccinic anhydride, tetrapropenylsuccinic anhydride, dodecenylsuccinic anhydride, and isooctadecenylsuccinic anhydride. The adhesive composition according to claim 1, wherein the adhesive composition is at least one compound selected from the group consisting of:
  3. 　（Ｃ）が５－ノルボルネン－２，３－ジカルボン酸無水物、メチル－５－ノルボルネン－２，３－ジカルボン酸無水物、５－ノルボルナン－２，３－ジカルボン酸無水物、メチル－５－ノルボルナン－２，３－ジカルボン酸無水物、５，５’－（１，４－フェニレン）ビス（ヘキサヒドロ－４，７－メタノイソベンゾフラン－１，３－ジオン）、ノルボルナン－２－スピロ－α－シクロペンタノン－α’－スピロ－２’’－ノルボルナン－５，５’’，６，６’’－テトラカルボン酸二無水物、４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸無水物、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物、及び９，９－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物からなる群から選ばれる少なくとも１種の酸無水物基を有する化合物である、請求項１に記載の接着剤組成物。 (C) is 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 5-norbornane-2,3-dicarboxylic anhydride, methyl-5-norbornane -2,3-dicarboxylic anhydride, 5,5'-(1,4-phenylene)bis(hexahydro-4,7-methanoisobenzofuran-1,3-dione), norbornane-2-spiro-α-cyclo Pentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthal At least one acid selected from the group consisting of acid anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride The adhesive composition according to claim 1, which is a compound having an anhydride group.
  4. 　（Ｂ）が（２－ブテン－１－イル）コハク酸無水物、２－オクテニルコハク酸無水物、ノネニルコハク酸無水物、テトラプロペニルコハク酸無水物、ドデセニルコハク酸無水物、及びイソオクタデセニルコハク酸無水物からなる群から選ばれる少なくとも１種の化合物であり、且つ（Ｃ）が５－ノルボルネン－２，３－ジカルボン酸無水物、メチル－５－ノルボルネン－２，３－ジカルボン酸無水物、５－ノルボルナン－２，３－ジカルボン酸無水物、メチル－５－ノルボルナン－２，３－ジカルボン酸無水物、５，５’－（１，４－フェニレン）ビス（ヘキサヒドロ－４，７－メタノイソベンゾフラン－１，３－ジオン）、ノルボルナン－２－スピロ－α－シクロペンタノン－α’－スピロ－２’’－ノルボルナン－５，５’’，６，６’’－テトラカルボン酸二無水物、４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸無水物、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物、及び９，９－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物からなる群から選ばれる少なくとも１種の酸無水物基を有する化合物である、請求項１に記載の接着剤組成物。 (B) is (2-buten-1-yl)succinic anhydride, 2-octenylsuccinic anhydride, nonenylsuccinic anhydride, tetrapropenylsuccinic anhydride, dodecenylsuccinic anhydride, and isooctadecenylsuccinic anhydride. at least one compound selected from the group consisting of anhydrides, and (C) is 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 5 -norbornane-2,3-dicarboxylic anhydride, methyl-5-norbornane-2,3-dicarboxylic anhydride, 5,5'-(1,4-phenylene)bis(hexahydro-4,7-methanoisobenzofuran) -1,3-dione), norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, and 9,9-bis(3,4-dicarboxy) The adhesive composition according to claim 1, which is a compound having at least one acid anhydride group selected from the group consisting of phenyl)fluorene dianhydride.
  5. 　更に増粘剤を（Ａ）１００重量部に対し０．５～２５重量部含む、請求項１～４のいずれか一項に記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 4, further comprising a thickener in an amount of 0.5 to 25 parts by weight per 100 parts by weight of (A).
PCT/JP2023/031389 2022-09-20 2023-08-30 2-cyanoacrylate adhesive composition WO2024062865A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
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JP2014522899A (en) * 2011-07-15 2014-09-08 ヘンケル アイルランド リミテッド Cyanoacrylate composition
JP2015510003A (en) * 2012-01-25 2015-04-02 ヘンケル ユーエス アイピー エルエルシー Cyanoacrylate composition
JP2016511317A (en) * 2013-03-15 2016-04-14 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング Cyanoacrylate composition
JP2021500453A (en) * 2017-10-27 2021-01-07 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング Cyanoacrylate composition
CN112322219A (en) * 2020-10-30 2021-02-05 河北诚信集团有限公司 Composition for reducing adhesive whitening phenomenon and alpha-cyanoacrylate adhesive

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014522899A (en) * 2011-07-15 2014-09-08 ヘンケル アイルランド リミテッド Cyanoacrylate composition
JP2015510003A (en) * 2012-01-25 2015-04-02 ヘンケル ユーエス アイピー エルエルシー Cyanoacrylate composition
JP2016511317A (en) * 2013-03-15 2016-04-14 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング Cyanoacrylate composition
JP2021500453A (en) * 2017-10-27 2021-01-07 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング Cyanoacrylate composition
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