Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
  • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/106—Esters of polycondensation macromers
  • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
• • 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
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
  • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups

Definitions

• the present invention relates to an anaerobic curing adhesive composition, an adhesive laminate, and a motor.
• Patent Document 1 discloses an anaerobic curing adhesive containing a phosphate ester compound.
• Patent Document 1 relates to an anaerobic curing adhesive containing a phosphate ester compound, and proposes a method in which an organic solvent and an anaerobic curing accelerator are dissolved in punching oil, the resulting solution is applied to a steel plate, the punching oil is substantially evaporated in a drying step at room temperature, and the anaerobic curing adhesive is then cured at room temperature.
• high temperatures are applied during the manufacture and operation of motor cores, and therefore adhesives are also required to have adhesive strength at high temperatures, i.e., adhesive strength at high temperatures is important.
• An anaerobic curing adhesive composition comprising a difunctional ethylenically unsaturated compound, a tri- or higher functional polyfunctional ethylenically unsaturated compound, a radical polymerization initiator, and an anaerobic curing catalyst, in which the content of the difunctional ethylenically unsaturated compound is 2% by mass to 30% by mass, the content of the tri- or higher functional polyfunctional ethylenically unsaturated compound is 2% by mass or more, and the content of the radical polymerization initiator is 2.0% by mass or less.
• ⁇ 2> The anaerobically curable adhesive composition according to ⁇ 1>, wherein a ratio (M M /M R ) of a total content M M (unit: mole) of the difunctional ethylenically unsaturated compound and the tri- or higher functional polyfunctional ethylenically unsaturated compound to a content M R ( unit : mole ) of the radical polymerization initiator is 0.8 to 30.
• ⁇ 3> The anaerobically curable adhesive composition according to ⁇ 1> or ⁇ 2>, wherein the ratio (M M3 /M R ) of the content M M3 (unit: mole) of the tri- or higher functional polyfunctional ethylenically unsaturated compound to the content M R (unit: mole) of the radical polymerization initiator is 0.6 to 27.
• ⁇ 4> The anaerobic curing adhesive composition according to any one of ⁇ 1> to ⁇ 3>, wherein the bifunctional ethylenically unsaturated compound is a polymer or oligomer having two or more (meth)acryloyl groups in one molecule.
• ⁇ 5> The anaerobic curing adhesive composition according to any one of ⁇ 1> to ⁇ 4>, wherein the polymer or oligomer having two or more (meth)acryloyl groups in one molecule contains a urethane (meth)acrylate.
• ⁇ 6> The anaerobically curable adhesive composition according to any one of ⁇ 1> to ⁇ 5>, wherein the polyfunctional ethylenically unsaturated compound includes a pentafunctional ethylenically unsaturated compound or a hexafunctional ethylenically unsaturated compound.
• ⁇ 7> The anaerobically curable adhesive composition according to any one of ⁇ 1> to ⁇ 6>, wherein the content of the radical polymerization initiator is 0.1% by mass to 2.0% by mass.
• ⁇ 8> The anaerobic curing adhesive composition according to any one of ⁇ 1> to ⁇ 7>, which is an anaerobic curing adhesive composition for steel plates.
• ⁇ 9> The anaerobic curing adhesive composition according to any one of ⁇ 1> to ⁇ 8>, which is an anaerobic curing adhesive composition for preventing loosening of screws.
• ⁇ 10> The anaerobic curing adhesive composition according to any one of ⁇ 1> to ⁇ 9>, which is an anaerobic curing adhesive composition for fittings.
• ⁇ 11> An adhesive laminate obtained by bonding and laminating two or more steel plates with the anaerobic curing adhesive composition according to any one of ⁇ 1> to ⁇ 8>.
• ⁇ 12> A motor comprising the adhesive laminate according to ⁇ 12>.
• an anaerobic curing adhesive composition that has excellent adhesive strength at high temperatures (150° C.). Furthermore, according to the present invention, it is possible to provide an adhesive laminate and a motor using the above-mentioned anaerobic curing adhesive composition.
• the word "to” is used to mean that the numerical values before and after it are included as the lower limit and upper limit.
• the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range.
• the upper or lower limit of the numerical range may be replaced with a value shown in the examples.
• “mass %” and “weight %” are synonymous, and “parts by mass” and “parts by weight” are synonymous.
• a combination of two or more preferred embodiments is a more preferred embodiment. The present invention will be described in detail below.
• the anaerobic curing adhesive composition of the present invention comprises a bifunctional ethylenically unsaturated compound, a tri- or higher functional polyfunctional ethylenically unsaturated compound, a radical polymerization initiator, and an anaerobic curing catalyst, in which the content of the bifunctional ethylenically unsaturated compound is 2% by mass to 30% by mass, the content of the tri- or higher functional polyfunctional ethylenically unsaturated compound is 2% by mass or more, and the content of the radical polymerization initiator is 2.0% by mass or less.
• the anaerobically curable adhesive composition of the present invention can also be suitably used as an anaerobically curable adhesive composition for steel plates.
• anaerobic curing adhesive composition of the present invention is not particularly limited, but since it has excellent adhesive strength at high temperatures, it can be suitably used in the production of adhesive laminates in which steel plates are bonded and laminated, motor cores, motors, etc.
• the anaerobic curing adhesive composition of the present invention can also be suitably used as an anaerobic curing adhesive composition for preventing loosening of screws or for fittings.
• the anaerobic curing adhesive composition of the present invention contains a difunctional ethylenically unsaturated compound.
• the difunctional ethylenically unsaturated compound may be a monomer, but is preferably a polymer and/or oligomer.
• Preferred difunctional ethylenically unsaturated compounds include polymers and/or oligomers having two or more (meth)acryloyl groups in one molecule.
• an oligomer is a polymer having a weight average molecular weight of 500 or more and less than 5,000
• a polymer is a polymer having a weight average molecular weight of 5,000 or more.
• the molecular weight means a value obtained by converting the weight average molecular weight measured by GPC (gel permeation chromatography) using polystyrene as a standard substance.
• the weight average molecular weight can be determined, for example, by the following procedure. Separation is performed by gel permeation chromatography (HLC-8320GPC, manufactured by Tosoh Corporation) in tetrahydrofuran solvent at 40° C. using a GPC column "TSK gel SuperMultiporeHZ-M" (manufactured by Tosoh Corporation), and the weight average molecular weight converted into standard polystyrene is calculated from the retention time.
• the (meth)acryloyl group contained in the polymer or oligomer having two or more (meth)acryloyl groups in one molecule is preferably located at a terminal position, but may be contained in a monomer unit constituting the main chain of the polymer or oligomer.
• the polymer and/or oligomer having two or more (meth)acryloyl groups in one molecule is not particularly limited, but from the viewpoint of adhesive strength at high temperatures, it is preferably at least one compound selected from the group consisting of urethane (meth)acrylate, epoxy (meth)acrylate, ester (meth)acrylate, isoprene-based (meth)acrylate, hydrogenated isoprene-based (meth)acrylate, and (meth)acrylic group-containing acrylic polymer, more preferably urethane (meth)acrylate or epoxy (meth)acrylate, even more preferably urethane (meth)acrylate, and particularly preferably urethane methacrylate.
• the polymer and/or oligomer having two or more (meth)acryloyl groups in one molecule is preferably a polymer or oligomer having a methacryloyl group at its terminal.
• the urethane (meth)acrylate may be a reaction product of a polyhydric alcohol, a polyisocyanate, and a hydroxy(meth)acrylate compound, or a reaction product of a polyisocyanate and a hydroxy(meth)acrylate compound without using a polyhydric alcohol.
• polyhydric alcohols include polyether polyols such as polypropylene glycol and polytetramethylene glycol, polyester polyols obtained by reacting a polyhydric alcohol with a polybasic acid, caprolactone polyols obtained by reacting a polyhydric alcohol with a polybasic acid and ⁇ -caprolactone, and polycarbonate polyols (e.g., polycarbonate polyols obtained by reacting 1,6-hexanediol with diphenyl carbonate).
• polyether polyols such as polypropylene glycol and polytetramethylene glycol
• polyester polyols obtained by reacting a polyhydric alcohol with a polybasic acid
• caprolactone polyols obtained by reacting a polyhydric alcohol with a polybasic acid and ⁇ -caprolactone
• polycarbonate polyols e.g., polycarbonate polyols obtained by reacting 1,6-hexanediol with di
• organic polyisocyanates include alicyclic polyisocyanates (isophorone diisocyanate, dicyclopentanyl diisocyanate, etc.), aliphatic polyisocyanates (hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.), and aromatic polyisocyanates (tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, etc.).
• alicyclic polyisocyanates isophorone diisocyanate, dicyclopentanyl diisocyanate, etc.
• aliphatic polyisocyanates hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.
• aromatic polyisocyanates tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, etc.
• the urethane (meth)acrylate is preferably produced from a polyether polyol, a polyester polyol, or a polycarbonate polyol as a raw material polyol, in view of excellent adhesive strength, and the urethane (meth)acrylate is preferably produced from an isophorone diisocyanate, a hexamethylene diisocyanate, or a xylene diisocyanate as a raw material organic polyisocyanate, in view of excellent adhesive strength.
• examples of the urethane (meth)acrylate include urethane (meth)acrylate having a polybutadiene skeleton, urethane (meth)acrylate having a hydrogenated polybutadiene skeleton, urethane (meth)acrylate having a polycarbonate skeleton, urethane (meth)acrylate having a hydrogenated bisphenol A skeleton, urethane (meth)acrylate having a polyether skeleton, urethane (meth)acrylate having a polyester skeleton, and urethane (meth)acrylate having a castor oil skeleton.
• epoxy (meth)acrylates include those obtained by reacting conventionally known epoxy resins, such as aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins, with (meth)acrylic acid.
• the polymer or oligomer having two or more (meth)acryloyl groups in one molecule preferably contains a compound in which the maximum value of tan ⁇ observed in dynamic viscoelasticity measurement (1 Hz, 2°C/min.) is observed at 25°C or less.
• tan ⁇ is calculated from the ratio of the storage modulus and loss modulus detected during measurement, and the maximum value of tan ⁇ is confirmed under the following conditions: for example, a cured adhesive sample cut to 50 mm x 20 mm and 1 mm thick is attached to the measuring device, cooled to -60°C, and held isothermal for 5 minutes, and then heated to 250°C at 2°C/min while being periodically stretched at a frequency of 1 Hz.
• the polymer or oligomer having a (meth)acryloyl group at the end contains a compound having a viscosity of 500 mPa ⁇ s or more at 25°C as measured with an E-type viscometer.
• the polymer or oligomer having two or more (meth)acryloyl groups in one molecule preferably includes a compound whose maximum value of tan ⁇ observed in dynamic viscoelasticity measurement (1 Hz, 2°C/min.) is observed at 25°C or lower, and a compound whose maximum value of tan ⁇ observed in dynamic viscoelasticity measurement (1 Hz, 2°C/min.) is observed above 25°C.
• the polymer or oligomer having two or more (meth)acryloyl groups in one molecule preferably contains a compound whose maximum tan ⁇ value observed in dynamic viscoelasticity measurement (1 Hz, 2°C/min.) is observed at 25°C or lower, and a compound whose maximum tan ⁇ value is 30°C or higher than the maximum tan ⁇ value of the compound.
• the polymer or oligomer having two or more (meth)acryloyl groups in one molecule preferably contains two or more compounds having a viscosity of 1,000 mPa ⁇ s or more at 25°C as measured with an E-type viscometer.
• Bifunctional ethylenically unsaturated compound monomers include, but are not limited to, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethylene oxide modified neopentyl glycol di(meth)acrylate, propylene oxide, Examples of such compounds include modified neopentyl glycol di(meth)acrylate, hydroxypivalic acid ester neopentyl glycol diacrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol diacrylate, neopentyl glycol-modified trimethylol
• the anaerobically curable adhesive composition of the present invention may contain one type of the bifunctional ethylenically unsaturated compound alone, or may contain two or more types of the bifunctional ethylenically unsaturated compound.
• the content of the bifunctional ethylenically unsaturated compound is 2% by mass to 30% by mass, and from the viewpoint of adhesive strength at high temperatures, the content is preferably 4% by mass to 27% by mass, more preferably 10% by mass to 25% by mass, and particularly preferably 15% by mass to 25% by mass, relative to the total mass of the adhesive composition.
• the anaerobically curable adhesive composition of the present invention contains a tri- or higher functional polyfunctional ethylenically unsaturated compound.
• the "polyfunctional ethylenically unsaturated compound” in the present invention refers to a polyfunctional ethylenically unsaturated compound having three or more functional groups.
• the polyfunctional ethylenically unsaturated compound may be a compound having three or more ethylenically unsaturated groups.
• the compound contains a polyfunctional (meth)acrylate compound having three or more functional groups.
• the number of functions in the polyfunctional ethylenic compound is not particularly limited, but from the viewpoint of adhesive strength at high temperatures, it is preferable for the polyfunctional compound to contain a trifunctional to decafunctional ethylenic unsaturated compound, more preferably a trifunctional to decafunctional ethylenic unsaturated compound, even more preferably a tetrafunctional to octafunctional ethylenic unsaturated compound, and particularly preferably a pentafunctional or hexafunctional ethylenic unsaturated compound.
• polyfunctional ethylenically unsaturated compounds include, but are not limited to, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, epichlorohydrin modified trimethylolpropane tri(meth)acrylate, epichlorohydrin modified glycerol tri(meth)acrylate, tris(acryloyloxyethyl)isocyanurate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, alkyl modified dipentaerythritol pentaacrylate, dipentaerythritol hexa(meth)acrylate, and caprol
• the anaerobically curable adhesive composition of the present invention may contain one type of polyfunctional ethylenically unsaturated compound alone, or may contain two or more types of polyfunctional ethylenically unsaturated compounds.
• the content of the polyfunctional ethylenically unsaturated compound is 2% by mass or more, and from the viewpoint of adhesive strength at high temperatures, it is preferably 2% by mass to 80% by mass, more preferably 3% by mass to 60% by mass, even more preferably 3% by mass to 20% by mass, and particularly preferably 5% by mass to 10% by mass, relative to the total mass of the adhesive composition.
• the anaerobically curable adhesive composition of the present invention preferably contains a monofunctional ethylenically unsaturated compound.
• the monofunctional ethylenically unsaturated compound may be a compound having only one ethylenically unsaturated group.
• the monofunctional ethylenically unsaturated compounds include lauryl (meth)acrylate, stearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol ( (meth)acrylate, nonylphenoxyethyl (meth)acrylate, nonylphenoxytetraethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, butoxyethy
• the monofunctional ethylenically unsaturated compound preferably contains a monofunctional ethylenically unsaturated compound having a hydroxy group, and more preferably contains a monofunctional (meth)acrylate compound having a hydroxy group.
• Preferred examples of the monofunctional ethylenically unsaturated compound having a hydroxy group include those having a hydroxy group among the above-mentioned monofunctional ethylenically unsaturated compounds.
• the anaerobically curable adhesive composition of the present invention may contain one type of monofunctional ethylenically unsaturated compound having a hydroxy group, or may contain two or more types of such monofunctional ethylenically unsaturated compounds.
• the content of the monofunctional ethylenically unsaturated compound having a hydroxy group is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 85% by mass, even more preferably 20% by mass to 80% by mass, and particularly preferably 30% by mass to 75% by mass, relative to the total mass of the adhesive composition.
• the content of the monofunctional ethylenically unsaturated compound having a hydroxy group is preferably 40 mass% or more, based on the total mass of the adhesive composition, from the viewpoints of the viscosity of the composition, the adhesion of the cured product, and the adhesive strength at high temperatures.
• the monofunctional ethylenically unsaturated compound preferably includes a monofunctional ethylenically unsaturated compound having a carboxy group or an acid anhydride structure.
• Suitable examples of the monofunctional ethylenically unsaturated compound having a carboxy group include unsaturated carboxylic acids.
• unsaturated carboxylic acids include (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, cinnamic acid, and monoalkyl esters of unsaturated dicarboxylic acids (monoalkyl esters of maleic acid, fumaric acid, itaconic acid, citraconic acid, etc.).
• Suitable examples of the monofunctional ethylenically unsaturated compound having an acid anhydride group include unsaturated carboxylic acid anhydrides.
• unsaturated carboxylic acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, and 4-methylphthalic anhydride.
• (meth)acrylic acid is preferred from the viewpoints of heat resistance and adhesion to metal materials.
• the anaerobically curable adhesive composition of the present invention may contain one type of monofunctional ethylenically unsaturated compound having a carboxy group or an acid anhydride structure, or may contain two or more types of such monofunctional ethylenically unsaturated compounds.
• the content of the monofunctional ethylenically unsaturated compound having a carboxy group or an acid anhydride structure is preferably 0.01 mass % to 10 mass %, more preferably 0.05 mass % to 5 mass %, and particularly preferably 0.1 mass % to 3 mass %, relative to the total mass of the adhesive composition.
• the anaerobic curing adhesive composition of the present invention may contain one type of monofunctional ethylenically unsaturated compound alone, or may contain two or more types of monofunctional ethylenically unsaturated compounds. From the viewpoint of adhesive strength at high temperatures, however, it is preferable to contain two or more types, and more preferable to contain three or more types. From the viewpoint of adhesive strength at high temperatures, the content of the monofunctional ethylenically unsaturated compound is preferably 10% by mass to 90% by mass, more preferably 50% by mass to 80% by mass, and particularly preferably 60% by mass to 80% by mass, relative to the total mass of the adhesive composition.
• the anaerobic curing adhesive composition of the present invention contains a radical polymerization initiator.
• the radical polymerization initiator include a thermal radical polymerization initiator and a photoradical polymerization initiator. From the viewpoint of anaerobic curability, the thermal radical polymerization initiator is preferred.
• the thermal radical polymerization initiator is not particularly limited, but examples include organic peroxides and azo compounds, with organic peroxides being particularly preferred.
• organic peroxide examples include hydroperoxides such as cumene hydroperoxide, t-butyl hydroperoxide, p-methane hydroperoxide, methyl ethyl ketone peroxide, cyclohexane peroxide, dicumyl peroxide, and diisopropylbenzene hydroperoxide, as well as other organic peroxides such as ketone peroxides, diallyl peroxides, and peroxy esters.
• examples of the azo compound include azobisisobutyronitrile, azobisisovaleronitrile, and azobisisocapronitrile. Among these, hydroperoxides are preferably used from the viewpoint of storage stability.
• the organic peroxide is preferably an organic peroxide with a one-hour half-life temperature in the range of 80°C to 300°C, and more preferably an organic peroxide with a one-hour half-life temperature in the range of 100°C to 200°C.
• the one-hour half-life temperature is a value measured by pyrolysis in benzene at a peroxide concentration of 0.1 mol/L.
• the organic peroxides whose one-hour half-life temperature is in the range of 80°C to 300°C include hydroperoxides.
• hydroperoxides include p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide.
• the photoradical generator is not particularly limited, but examples thereof include acetophenone-based photoradical polymerization initiators, benzoin-based photoradical polymerization initiators, benzophenone-based photoradical polymerization initiators, thioxanthone-based photoradical polymerization initiators, acylphosphine oxide-based photoradical polymerization initiators, and titanocene-based photoradical polymerization initiators.
• acetophenone-based photoradical polymerization initiator examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer.
• acetophenone-based photoradical polymerization initiators include IRGACURE184, IRGACUR1173, IRGACURE2959, IRGACURE127 (manufactured by BASF), and ESACUREKIP-150 (manufactured by Lamberti spa).
• acylphosphine oxide-based photoradical polymerization initiator include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
• acylphosphine oxide-based photoradical polymerization initiator Commercially available products of the acylphosphine oxide-based photoradical polymerization initiator include Omnirad TPO, Omnirad 819 (manufactured by IGM Resins B.V.), and IRGACURE 819DW (manufactured by BASF).
• the anaerobically curable adhesive composition of the present invention may contain one type of radical polymerization initiator alone, or may contain two or more types of radical polymerization initiators.
• the content of the radical polymerization initiator is 2.0 mass % or less, and from the viewpoints of anaerobic curability and adhesive strength at high temperatures, the content is preferably 0.01 mass % to 2.0 mass %, more preferably 0.05 mass % to 1.5 mass %, and particularly preferably 0.1 mass % to 1.0 mass %, relative to the total mass of the adhesive composition.
• the ratio (M M /M R ) of the total content M M (unit: mole) of the difunctional ethylenically unsaturated compound and the tri- or higher functional polyfunctional ethylenically unsaturated compound to the content M R (unit: mole ) of the radical polymerization initiator is preferably 0.8 to 30, more preferably 1 to 10, and particularly preferably 1.5 to 4, from the viewpoint of adhesive strength at high temperatures.
• the ratio (M M3 /M R ) of the content M M3 (unit: mole) of the trifunctional or higher polyfunctional ethylenically unsaturated compound to the content M R (unit: mole) of the radical polymerization initiator is preferably 0.6 to 27, and more preferably 0.7 to 6, from the viewpoint of adhesive strength at high temperatures.
• the ratio (M M3 /M M2 ) of the content M M3 (unit: mole) of a trifunctional or higher polyfunctional ethylenically unsaturated compound to the content M M2 (unit: mole) of a bifunctional ethylenically unsaturated compound is preferably 1 to 40, more preferably 2 to 15, and particularly preferably 3 to 12.
• the anaerobic curing adhesive composition of the present invention contains an anaerobic curing catalyst.
• the anaerobic curing catalyst include saccharin, amine compounds, azole compounds, mercaptan compounds, hydrazine compounds, and salts thereof.
• a combination of saccharin and a hydrazine compound or a salt thereof is preferred from the viewpoint of anaerobic curing properties.
• amine compounds examples include secondary heterocyclic amines such as 1,2,3,4-tetrahydroquinoline and 1,2,3,4-tetrahydroquinaldine, tertiary heterocyclic amines such as quinoline, methylquinoline, quinaldine and quinoxalinephenazine, and tertiary aromatic amines such as N,N-dimethyl-anisidine, N,N-dimethylaniline and N,N'-dimethyl-p-toluidine.
• secondary heterocyclic amines such as 1,2,3,4-tetrahydroquinoline and 1,2,3,4-tetrahydroquinaldine
• tertiary heterocyclic amines such as quinoline, methylquinoline, quinaldine and quinoxalinephenazine
• tertiary aromatic amines such as N,N-dimethyl-anisidine, N,N-dimethylaniline and N,N'-dimethyl-p-toluidine.
• azole compounds examples include 1,2,4-triazole, oxazole, oxadiazole, thiadiazole, benzotriazole, hydroxybenzotriazole, benzoxazole, 1,2,3-benzothiadiazole, and 3-mercaptobenzotriazole.
• mercaptan compounds examples include linear mercaptans such as n-dodecyl mercaptan, ethyl mercaptan, and butyl mercaptan.
• Examples of the hydrazine compound include 1-acetyl-2-phenylhydrazine, 1-acetyl-2(p-tolyl)hydrazine, 1-benzoyl-2-phenylhydrazine, 1-(1',1',1'-trifluoro)acetyl-2-phenylhydrazine, 1,5-diphenyl-carbohydrazine, 1-formyl-2-phenylhydrazine, 1-acetyl-2-(p-bromophenyl)hydrazine, 1-acetyl-2-(p-nitrophenyl)hydrazine, 1-acetyl-2-(2'-phenylethylhydrazine), p-nitrophenylhydrazine, and p-trisulfonylhydrazide.
• Examples of the salts of the hydrazine compounds include 4-methylsulfonylphenylhydrazine hydrochloride, hydrazine monohydrochlor
• the anaerobic curing adhesive composition of the present invention may contain one type of anaerobic curing catalyst alone, or may contain two or more types of anaerobic curing catalysts.
• the content of the anaerobic curing catalyst is preferably 0.05% by mass to 30% by mass, more preferably 0.1% by mass to 20% by mass, and particularly preferably 0.2% by mass to 10% by mass, relative to the total mass of the adhesive composition.
• the anaerobically curable adhesive composition of the present invention may contain an acid and/or an acid anhydride that does not have an ethylenically unsaturated group.
• the acid or acid anhydride is not particularly limited, and any known acid or acid anhydride can be used, but an organic acid or organic acid anhydride is preferred, and a carboxylic acid or carboxylic acid anhydride is more preferred.
• preferred examples include pyromellitic acid, trimellitic anhydride, and the like.
• the anaerobically curable adhesive composition of the present invention may contain one kind of acid or acid anhydride alone, or may contain two or more kinds of acids or acid anhydrides, or may use an acid and an acid anhydride in combination.
• the content of the acid and acid anhydride is preferably 0.01% by mass to 10% by mass, and more preferably 0.05% by mass to 5% by mass, relative to the total mass of the adhesive composition.
• the anaerobic curing adhesive composition of the present invention may contain, as components other than those described above, additives such as fillers, various elastomers, storage stabilizers, antioxidants, light stabilizers, heavy metal deactivators, silane coupling agents, tackifiers, plasticizers, defoamers, pigments, rust inhibitors, leveling agents, dispersants, rheology adjusters and flame retardants, provided such additives do not impair the object of the present invention.
• additives such as fillers, various elastomers, storage stabilizers, antioxidants, light stabilizers, heavy metal deactivators, silane coupling agents, tackifiers, plasticizers, defoamers, pigments, rust inhibitors, leveling agents, dispersants, rheology adjusters and flame retardants, provided such additives do not impair the object of the present invention.
• the anaerobic curing adhesive composition of the present invention may be added with a filler to an extent that does not impair storage stability.
• a filler include organic powders, inorganic powders, etc.
• inorganic powder fillers include, but are not limited to, glass, fumed silica, alumina, mica, ceramics, silicone rubber powder, calcium carbonate, aluminum nitride, carbon powder, kaolin clay, dried clay minerals, and dried diatomaceous earth.
• the content of the inorganic powder is preferably 0.1 parts by mass to 100 parts by mass relative to 100 parts by mass of the polymerization components (the total content of the polymer and/or oligomer having a (meth)acryloyl group at the end, the polyfunctional ethylenically unsaturated compound, the compound having an aromatic ring and an ethylenically unsaturated group, and other ethylenically unsaturated compounds, the same below).
• Fumed silica is blended for the purpose of adjusting the viscosity of the anaerobic curing adhesive composition or improving the mechanical strength of the cured product.
• fumed silica surface-treated with dimethylsilane, trimethylsilane, alkylsilane, methacryloxysilane, organochlorosilane, polydimethylsiloxane, hexamethyldisilazane, or the like is used.
• fumed silica products include, for example, Aerosil (registered trademark) R972, R972V, R972CF, R974, R976, R976S, R9200, RX50, NAX50, NX90, RX200, RX300, R812, R812S, R8200, RY50, NY50, RY200S, RY200, RY300, R104, R106, R202, R805, R816, T805, R711, RM50, and R7200 (all manufactured by Nippon Aerosil Co., Ltd.).
• the organic powder filler is not particularly limited, but examples thereof include polyethylene, polypropylene, nylon (registered trademark), cross-linked acrylic, cross-linked polystyrene, polyester, polyvinyl alcohol, polyvinyl butyral, polycarbonate, and the like.
• the content of the organic powder is preferably 0.1 to 100 parts by mass based on 100 parts by mass of the polymerizable components.
• the anaerobically curable adhesive composition of the present invention may contain a storage stabilizer.
• a storage stabilizer radical polymerization inhibitors such as benzoquinone, hydroquinone, and hydroquinone monomethyl ether, metal chelating agents such as ethylenediaminetetraacetic acid or its disodium salt, oxalic acid, acetylacetone, and o-aminophenol, and the like can also be added.
• the anaerobic curing adhesive composition of the present invention preferably contains a radical polymerization inhibitor and a metal chelating agent, and more preferably contains at least one selected from the group consisting of hydroquinone and hydroquinone monomethyl ether, and at least one selected from the group consisting of ethylenediaminetetraacetic acid and ethylenediaminetetraacetic acid disodium salt.
• the content of the storage stabilizer is preferably 0.0001 to 1 part by mass based on 100 parts by mass of the polymerization components.
• the anaerobically curable adhesive composition of the present invention may contain an antioxidant.
• the antioxidant include quinone compounds such as ⁇ -naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, and 2,5-di-tert-butyl-p-benzoquinone; phenothiazine, 2,2-methylene-bis(4-methyl-6-tert-butylphenol), catechol, tert-butylcatechol, 2 -butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy
• the anaerobically curable adhesive composition of the present invention may contain a silane coupling agent.
• silane coupling agent include, but are not limited to, ⁇ -chloropropyltrimethoxysilane, octenyltrimethoxysilane, glycidoxyoctyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -ureidopropyltriethoxysilane, p-styryltrimethoxysilane, and 3-(meth)acryloxypropyltrimethoxysilane.
• the content of the silane coupling agent is preferably 0.05 parts by mass to 30 parts by mass, and more preferably 0.2 parts by mass to 10 parts by mass, per 100 parts by mass of the polymerization components, from the viewpoint of adhesion to metal materials.
• the method for producing the anaerobic curing adhesive composition of the present invention is not particularly limited, and the composition can be produced by a known method.
• the composition can be produced by blending predetermined amounts of each component and mixing the components using a mixing means such as a mixer at a temperature of preferably 10°C to 100°C for preferably 0.1 to 5 hours.
• the viscosity of the anaerobic curing adhesive composition of the present invention at 25°C is preferably 10,000 mPa ⁇ s or less, more preferably 10 mPa ⁇ s to 8,000 mPa ⁇ s, even more preferably 25 mPa ⁇ s to 5,000 mPa ⁇ s, and particularly preferably 50 mPa ⁇ s to 3,000 mPa ⁇ s, from the viewpoints of the ease with which the adhesive composition applied to a metal material spreads and that the adhesive composition does not excessively protrude from the bonding surfaces when bonded.
• the viscosity of the anaerobically curable adhesive composition of the present invention is measured by the following method. A specified amount of the adhesive composition is sampled and dispensed into a measuring cup. The viscosity is measured using an EHD viscometer (manufactured by Toki Sangyo Co., Ltd.) at 25° C. and a shear rate of 76.6 (1/s).
• the adhesive laminate of the present invention may be any adhesive laminate formed by bonding with the anaerobic curing adhesive composition of the present invention, but it is preferably an adhesive laminate formed by bonding and laminating two or more metal materials with the anaerobic curing adhesive composition of the present invention. Also suitable is an adhesive laminate obtained by bonding two or more threaded members (e.g., a screw and a threaded hole, etc.) or two or more fitting members (e.g., a convex member and a concave member, or a rod member and a hole member, etc.) with the anaerobic curing adhesive composition of the present invention.
• threaded members e.g., a screw and a threaded hole, etc.
• fitting members e.g., a convex member and a concave member, or a rod member and a hole member, etc.
• the anaerobic curing adhesive of the present invention is suitable for bonding steel sheets, which are not particularly limited and suitable examples include electrical steel sheets and cold-rolled steel sheets.
• the electrical steel sheet may be either an oriented electrical steel sheet or a non-oriented electrical steel sheet, but when used for motor cores, rotors, stators, etc., which will be described later, the non-oriented electrical steel sheet is preferred.
• the applications of the adhesive laminate of the present invention are not particularly limited, and it can be used for a variety of applications.
• the adhesive laminate of the present invention is preferably used for motor cores of motors and the like because it is insulated by the cured product of the anaerobic curing adhesive composition of the present invention, has low current loss, has high performance and high reliability, and distributes stress over a surface without causing stress concentration or strain concentration.
• the method for producing the adhesive laminate of the present invention is not particularly limited, but preferably includes the steps of applying a primer composition containing a solvent and an organometallic complex to at least one of the metal materials to be adhered, applying an anaerobic curing adhesive composition to at least one of the metal materials to be adhered, and laminating another metal material to the metal material to which the adhesive composition has been applied.
• the primer composition used in the present invention is not particularly limited, but examples thereof include compositions obtained by diluting organometallic complexes such as copper ethylhexanoate, iron pentadione, cobalt pentadione, copper pentadione, propylenediamine copper, ethylenediamine copper, iron naphthate, nickel naphthate, cobalt naphthate, copper naphthate, copper octate, iron hexoate, iron propionate, and vanadium acetylacetonate with a solvent such as ethanol, toluene, acetone, or heptone.
• the oil may be, for example, punching oil.
• the punching oil is an oil used for the purpose of preventing galling and seizure.
• the components of the punching oil are not particularly limited, but examples thereof include those mainly composed of mineral oils or synthetic oils, and may further contain rust inhibitors, preservatives, etc. as optional components.
• heating can be carried out in order to cure the adhesive composition in a shorter time.
• the heating method is not particularly limited, but examples thereof include a thermostatic bath and a far-infrared heater.
• the temperature and time during heating may be any conditions that allow sufficient curing, but it is preferable to heat at a temperature of preferably 40° C. to 300° C., more preferably 60° C. to 150° C., for preferably 10 seconds to 3 hours, more preferably 20 seconds to 60 minutes.
• it is preferable to fix it in advance with a fixing tool or the like to prevent positional deviation.
• the method for applying the primer composition and the adhesive composition is not particularly limited, but any known method can be used. Examples of application methods include roller, dispensing, spray, inkjet, dipping, etc.
• the manufacturing method described below may be carried out by appropriately changing the order of steps and conditions according to the adhesive laminate to be manufactured, and further steps may be added.
• the primer composition may be applied by dipping, and the anaerobic curing adhesive composition may be applied by a roller, and so on.
• the number of layers of the adhesive laminate obtained in the manufacturing method described below is not particularly limited.
• the adhesive laminate can be manufactured by sequentially stacking and adhering the metal adherends.
• An unfinished adhesive laminate that has not yet reached the desired number of layers has layers that include the adherend metal that has already been adhered and laminated, and an adhesive laminate can be manufactured by stacking and adhering an unlaminated adherend metal to the topmost layer or the bottommost layer.
• adherend metals are stacked and adhered sequentially, the topmost layer or the bottommost layer of the unfinished adhesive laminate may be considered to be the adherend metal.
• the method for producing an adhesive laminate includes the steps of (1) preparing a first metal substrate having at least one surface coated with a primer composition, (2) preparing a second metal substrate having at least one surface coated with an anaerobic curing adhesive composition, and (3) overlapping the surface of the first metal substrate coated with the primer composition and the surface of the second metal substrate coated with the anaerobic curing adhesive composition.
• the method for producing an adhesive laminate includes a step (1) of preparing a plurality of metal substrates each having a primer composition applied to one side and an anaerobic curing adhesive composition applied to the other side, and a step (2) of stacking the plurality of metal substrates prepared in step (1) so that the surface coated with the primer composition and the surface coated with the anaerobic curing adhesive composition are in contact with each other.
• the method for producing an adhesive laminate includes the steps of (1) preparing a plurality of first metal adherends each having a primer composition applied to both sides thereof, (2) preparing a plurality of second metal adherends each having an anaerobic curing adhesive composition applied to both sides thereof, and (3) stacking the first metal adherends and the second metal adherends alternately so that the surface of the first metal adherend coated with the primer composition and the surface of the second metal adherend coated with the anaerobic curing adhesive composition are in contact with each other.
• a laminate of adherend metals may be formed before applying at least one of the primer composition and the anaerobic curing adhesive composition to the adherend metals, and then the primer composition and the anaerobic curing adhesive composition that have not been applied between the adherend metals may be provided to bond the adherend metals forming the laminate.
• the primer composition or anaerobically curing adhesive composition can be permeated into the laminate by spraying the primer composition or anaerobically curing adhesive composition from the side of the laminate or by impregnating the laminate with the primer composition or anaerobically curing adhesive composition. It is also possible to insert an injection nozzle between the metal adherends and directly inject the primer composition or anaerobically curing adhesive composition between the metal adherends. When applying the primer composition or anaerobically curing adhesive composition between the metal adherends, it is desirable to physically fix the laminate from the outside.
• the method for producing an adhesive laminate includes the steps of (1) preparing a laminate in which at least two or more metal substrates are laminated, (2) providing a primer composition between the metal substrates of the laminate, and (3) providing an anaerobic curing adhesive composition between the metal substrates of the laminate.
• the method for producing an adhesive laminate includes a step (1) of preparing a laminate by laminating a metal substrate having at least one surface coated with a primer composition, and a step (2) of applying an anaerobic curing adhesive composition between the metal substrates of the laminate.
• an adhesive laminate using electromagnetic steel sheets as the adherend metal When manufacturing an adhesive laminate using electromagnetic steel sheets as the adherend metal, a commonly used method is to continuously or intermittently feed a hoop material while sequentially laminating the adherend metal obtained by punching. Using any of the above adhesive laminate manufacturing methods, it is possible to continuously laminate and adhere electromagnetic steel sheets from the hoop material.
• an adhesive laminate of magnetic steel sheets can be manufactured by a manufacturing method for an adhesive laminate including the steps of (1) applying a primer composition to one side of a hoop material, (2) applying an anaerobic curing adhesive composition to the side of the hoop material not coated with the primer composition, (3) punching the hoop material to produce a metal substrate of a predetermined shape, and (4) stacking the obtained metal substrates in sequence.
• the step (5) of applying press processing oil to at least one side of the hoop material may be carried out before punching.
• the diluent contained in the primer composition is a press processing oil
• the primer composition as the press processing oil.
• the process of applying press processing oil to the hoop material can be omitted.
• the process of applying the press processing oil and the process of applying the primer composition can be carried out in a single process, making it possible to efficiently manufacture an adhesive laminate of electromagnetic steel sheets.
• the mass ratio of the press processing oil in the diluent is preferably 70 mass% or more, more preferably 90 mass% or more, and may be 100 mass%.
• UMA-1 alicyclic bifunctional urethane methacrylate having a structural unit based on isophorone diisocyanate, maximum value of tan ⁇ : ⁇ 10° C. (1 Hz 2° C./min)
• M-401B a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, ARONIX (registered trademark) M-401B manufactured by Toagosei Co., Ltd.
• CHP Cumene hydroperoxide, Percumyl H manufactured by NOF Corporation Saccharin: Fujifilm Wako Pure Chemical Industries, Ltd.
• HEMA 2-hydroxyethyl methacrylate
• IBXMA isobornyl methacrylate
• AA acrylic acid
• EDTA-2Na ethylenediaminetetraacetic acid disodium salt, Fujifilm Wako Pure Chemical Industries, Ltd.
• ⁇ Tensile shear test> The shear strength was measured by pulling the test piece at 10 mm/min. at 150°C using a Strograph 20-C manufactured by Toyo Seiki Seisakusho Co., Ltd., and the measurement results are shown in Table 1 as "shear strength @ 150°C". The higher the shear strength value at 150°C, the better the adhesive strength at high temperatures.
• Tables 1 and 2 The numerical values of each raw material in Tables 1 and 2 are in mass %.
• “>trifunctional (mol)/bifunctional (mol)” represents the molar ratio of the content of the trifunctional or higher polyfunctional ethylenically unsaturated compound to the content of the bifunctional ethylenically unsaturated compound.
• "bifunctional (mol)/CHP (mol)” represents the molar ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the radical polymerization initiator (cumene hydroperoxide).
• the anaerobic curing adhesive composition of Comparative Example 1 contains less than 2% by mass of bifunctional ethylenically unsaturated compounds, and also contains less than 2% by mass of trifunctional or higher polyfunctional ethylenically unsaturated compounds.
• Comparative Example 1 has a lower shear strength at 150°C than Examples 1 to 16.
• Comparative Example 2 contains no polyfunctional ethylenically unsaturated compounds.
• Comparative Example 2 has a lower shear strength at 150°C than Examples 1 to 16.
• Comparative Example 3 contains more than 30% by mass of bifunctional ethylenically unsaturated compounds. Comparative Example 3 has a lower shear strength at 150°C than Examples 1 to 16.
• Comparative Example 4 contains more than 2% by mass of radical polymerization initiator. Comparative Example 4 has a lower shear strength at 150°C than Examples 1 to 16.
• the anaerobic curing adhesive compositions of Examples 1 to 8 have a ratio of >3 functionality (mol)/CHP (mol) of 4 or less, and have higher shear strength at 150°C than the anaerobic curing adhesive compositions of Examples 9 and 11 to 16.
• the anaerobic curing adhesive compositions of Examples 1 to 8 have a content of 3% or more by mass of a polyfunctional ethylenically unsaturated compound having three or more functionalities, and have higher shear strength at 150°C than the anaerobic curing adhesive composition of Example 10.
• the present invention can provide, for example, an anaerobic curing adhesive composition for use in high temperature environments, an anaerobic curing adhesive composition for preventing loosening of screws, an anaerobic curing adhesive composition for fittings, and the like. It also provides an anaerobic curing adhesive composition that can provide an adhesive laminate that contributes to high performance and high reliability of motor rotors and stators. Therefore, it is extremely effective and can be used in a wide range of products and technical fields, making it industrially useful.

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• 2023
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