WO2024038816A1 - Composition d'agent adhésif - Google Patents

Composition d'agent adhésif Download PDF

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Publication number
WO2024038816A1
WO2024038816A1 PCT/JP2023/029133 JP2023029133W WO2024038816A1 WO 2024038816 A1 WO2024038816 A1 WO 2024038816A1 JP 2023029133 W JP2023029133 W JP 2023029133W WO 2024038816 A1 WO2024038816 A1 WO 2024038816A1
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Prior art keywords
adhesive composition
acid
polyester resin
parts
component
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PCT/JP2023/029133
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English (en)
Japanese (ja)
Inventor
拓也 芝
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東洋紡株式会社
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Publication of WO2024038816A1 publication Critical patent/WO2024038816A1/fr

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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
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition

Definitions

  • the present invention relates to adhesive compositions. More specifically, the present invention relates to an epoxy adhesive with excellent adhesiveness and curability. More specifically, the present invention relates to a structural adhesive composition used for bonding structures such as vehicles such as automobiles.
  • Epoxy adhesives have excellent properties such as mechanical properties, water resistance, chemical resistance, and heat resistance, so they have been used in a wide range of fields such as paints, molding materials, heat dissipation materials, and adhesives, and are widely used in industry. It has become an indispensable material.
  • Epoxy adhesives are usually thermosetting resins containing an epoxy resin, a curing agent, and a catalyst, and when heated, the oxirane ring reacts with the curing agent and forms a cured product through polyaddition. It is known that such thermosetting resins are superior in mechanical properties, corrosion resistance, adhesiveness, etc. compared to various materials. Due to these characteristics, epoxy adhesives are widely used for joining structures such as vehicles such as automobiles and trains, and aircraft. Such adhesives are called structural adhesives.
  • An object of the present invention is to provide an epoxy adhesive that has excellent adhesion to a base material, good toughness, and heat resistance.
  • the present invention was made against the background of such problems of the prior art. As a result of extensive studies, the present inventors have discovered that the above-mentioned problems can be solved by the means shown below, and have arrived at the present invention. That is, the present invention consists of the following configuration.
  • polyester resin (E) contains an epoxy resin (A), a curing agent (B), a curing catalyst (C), a thixotropic agent (D), and a polyester resin (E), wherein the polyester resin (E) is a component (a ) as a structural unit, and the content of the polyester resin (E) is 1 to 30 parts by mass based on 100 parts by mass of the epoxy resin (A).
  • the component (a) having a phenolic hydroxyl group is a component having one or more phenolic hydroxyl groups and one or more carboxylic acid groups in one molecule.
  • the adhesive composition of the present invention can be suitably used as a structural adhesive.
  • the adhesive composition of the present invention comprises an epoxy resin (A), a curing agent (B), a curing catalyst (C), a thixotropic agent (D), and a polyester having as constituent units a component (a) having a phenolic hydroxyl group.
  • the epoxy resin (A) used in the adhesive composition of the present invention is not particularly limited as long as it is an epoxy compound having two or more oxirane rings.
  • Examples of the epoxy resin (A) used in the present invention include bisphenol A, bisphenol F, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, and bisphenol.
  • Bisphenol-type epoxy resins made by glycidyl etherification of bisphenol compounds such as Z; monocyclic aromatic glycidyl ether compounds made by glycidyl etherification of polyhydric aromatic alcohols such as catechol, resorcinol, and hydroquinone; naphthalene, biphenyl, tetramethylbiphenyl, and bisphenol.
  • Polycyclic aromatic epoxy resin obtained by glycidyl etherification of polycyclic aromatic compounds such as fluorene, biscresol fluorene, and tetraphenylolethane; Novolak obtained by epoxidizing novolac-type compounds such as phenol novolac, cresol novolak, and bisphenol A novolac.
  • glycidylamine type epoxy resin which is glycidyl etherified aromatic amino compound such as aniline, o-methylaniline, p-aminophenol, m-phenylenediamine; triglycidyl isocyanurate, triphenyl glycidyl ether methane type epoxy resin , xylylene type epoxy resin, tetrakisphenol ethane type epoxy resin, naphthalene type epoxy resin, and other polyfunctional epoxy resins; alkylene glycidylated alkylene oxide adducts such as ethylene oxide adducts of bisphenol A and propylene oxide adducts of bisphenol A Oxide glycidyl compounds; 1,4-butanediol, 1,6-hexanediol, 1,12-dodecanediol, cyclohexanedimethanol, 2,2-dimethylpropanediol, trimethylolprop
  • the curing agent (B) used in the adhesive composition of the present invention is not particularly limited as long as it reacts with the epoxy resin (A), and specific examples include dicyandiamide; adipic acid dihydrazide, isophthalic acid dihydrazide, dibasic Hydrazides such as acid dihydrazide; Bisphenol compounds such as bisphenol A, bisphenol F, and bisphenol E; Catechol compounds such as catechol, resorcinol, and methylcatechol; Biphenol compounds such as biphenol and tetramethylbiphenol; Cresol compounds; hydroquinone compounds such as hydroquinone; liquid phenolic compounds such as trisdimethylaminomethylphenol; phenol novolak, cresol novolak, bisphenol A novolak, xylylene novolak, triphenylmethane novolak, biphenyl novolak, dicyclopentadienephenol novolak , Novolak compounds such as terpenephenol novol
  • the preferred content of the curing agent (B) in the adhesive composition of the present invention varies depending on the type of curing agent.
  • a curing agent that has a catalytic effect on the epoxy resin (A) such as dicyandiamide
  • it is preferably 1 to 15 parts by mass, more preferably 3 to 10 parts by mass, per 100 parts by mass of the epoxy resin (A). Department. By setting it within the above range, curability and crosslinking properties are exhibited, and toughness becomes good.
  • the ratio of the active hydrogen group value in the curing agent (B) to the epoxy value of the epoxy resin (A) is 0.
  • An amount in the range of .9 to 1.1 is preferable from the viewpoint of curability.
  • the ratio is more preferably in the range of 1.0 to 1.1, and even more preferably in the range of 1.05 to 1.1. This is because when the epoxy groups are in excess of the active hydrogen groups, a branching reaction occurs and the heat resistance of the cured product is further improved.
  • the curing catalyst (C) used in the adhesive composition of the present invention is not particularly limited as long as it can promote the reaction between the epoxy resin (A) and the curing agent (B).
  • the curing catalyst (C) used in the adhesive composition of the present invention is not particularly limited as long as it can promote the reaction between the epoxy resin (A) and the curing agent (B).
  • Tertiary amines Tertiary amines; alcohol amines such as dimethylaminomethanol and dimethylaminoethanol; ether amines such as bis(2-dimethylaminoethyl) ether; 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) ); Amine adducts; 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, N-benzyl- 2-Methylimidazole, N-benzyl-2-phenylimidazole, 2,4-dimethylimidazole, imidazole, 1-methylimidazole, 2-methylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenyl-4,5-dihydroxy
  • the preferable content of the curing catalyst (C) in the adhesive composition of the present invention is from 0.5 to 20 parts by mass, based on 100 parts by mass of the epoxy resin (A).
  • the amount is within the above range, preferably 0.5 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, curability and stability will be good from the viewpoint of catalyst activity and reaction rate.
  • the thixotropic agent (D) used in the present invention is not limited as long as it has the effect of imparting thixotropic properties to the epoxy adhesive.
  • fumed silicas such as hydrophilic fumed silica and hydrophobic fumed silica; fine particles such as carbon black and various metal powders; wallas night, mica, talc, kaolin, barium sulfate, and calcium carbonate. , magnesium hydroxide, clay, and other inorganic fillers with a high aspect ratio.
  • hydrophobic fumed silica is preferred because it can provide appropriate thixotropic properties and has high hydrophobicity.
  • the content of the thixotropic agent (D) in the adhesive composition of the present invention is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, and more preferably 1 to 15 parts by weight, based on 100 parts by weight of the epoxy resin (A). Preferably it is 1 to 10 parts by mass.
  • the content is within the above range, the viscosity range during application and curing of the adhesive is maintained appropriately, and workability is improved, which is preferable.
  • the polyester resin (E) used in the present invention has a component (a) having a phenolic hydroxyl group (hereinafter also simply referred to as component (a)) as a structural unit.
  • component (a) a phenolic hydroxyl group
  • good toughness can be imparted to the adhesive composition.
  • the component (a) having a phenolic hydroxyl group is not particularly limited as long as it is a compound having a phenolic hydroxyl group, but from the viewpoint of reactivity during polyester polymerization, it is preferable to further have a carboxyl group or an alcoholic hydroxyl group.
  • Examples of such compounds include 5-hydroxyisophthalic acid, p-hydroxybenzoic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylacetic acid, 6-hydroxy-2-naphthoic acid, and 4,4-bis(p- Examples include a component (a1) having a phenolic hydroxyl group and a carboxy group such as hydroxyphenylvaleric acid, and a component (a2) having a phenolic hydroxyl group and an alcoholic hydroxyl group such as p-hydroxyphenethyl alcohol.
  • the amount of the component (a) having a phenolic hydroxyl group in the polyester resin (E) is preferably 1 mol% or more when the total amount of polycarboxylic acid components constituting the polyester resin (E) is 100 mol%. , more preferably 1.2 mol% or more.
  • the amount of component (a) having a phenolic hydroxyl group is at least the lower limit, the compatibility with the epoxy resin improves, and as a result, the toughness of the adhesive composition improves.
  • the amount of component (a) having a phenolic hydroxyl group is preferably at most 10 mol%, more preferably at most 8 mol%, and still more preferably at most 5 mol%.
  • the other structural units of the polyester resin (E) are not particularly limited as long as it has the component (a), and for example, it may be a polyester resin mainly consisting of a polycarboxylic acid component and a polyol component.
  • the polycarboxylic acid is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, and diphenic acid.
  • aromatic dicarboxylic acids having a sulfonic acid group such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5(4-sulfophenoxy)isophthalic acid, and their metal salts
  • aromatic dicarboxylic acids having sulfonic acid groups such as ammonium salts, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and their acid anhydrides, etc.
  • Aliphatic dicarboxylic acids such as alicyclic dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and dimer acid can be mentioned. These can be used alone or in combination of two or more.
  • the polyol component is not particularly limited, but is preferably an aliphatic glycol, an alicyclic glycol, an aromatic-containing glycol, or an ether bond-containing glycol.
  • aliphatic glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3,-propanediol, 1,5- Pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol (DMH), hydroxypivalic acid neopentyl glycol ester, dimethylolheptane, 2,2,4-trimethyl-1,3-pentanediol, and the like.
  • Examples of alicyclic glycols include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecanediol, tricyclodecanedimethylol, spiroglycol, hydrogenated bisphenol A, and hydrogenated bisphenol A.
  • Examples include ethylene oxide adducts and propylene oxide adducts.
  • Examples of ether bond-containing glycols include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, neopentyl glycol ethylene oxide adduct, and neopentyl glycol propylene oxide adduct. Can be mentioned.
  • aromatic-containing glycols include bisphenols such as para-xylene glycol, meta-xylene glycol, orthoxylene glycol, ethylene oxide adducts of 1,4-phenylene glycol, and ethylene oxide adducts and propylene oxide adducts of bisphenol A.
  • examples include glycols obtained by adding one to several moles of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of the following. These can be used alone or in combination of two or more.
  • aliphatic glycols are preferred, such as ethylene glycol, 2-methyl-1,3,-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, Or 1,6-hexanediol is more preferred.
  • a trifunctional or higher functional component may be copolymerized with the polycarboxylic acid component and/or the polyol component.
  • a trifunctional or higher functional component may be copolymerized with the polycarboxylic acid component and/or the polyol component.
  • the total polycarboxylic acid component and the total polyol component are each 100 mol%, it is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and preferably 5 mol% or less, and 3 More preferably, it is less than mol%.
  • trifunctional or higher functional polycarboxylic acid components include trimellitic acid, trimesic acid, ethylene glycol bis(anhydrotrimellitate), glycerol tris(anhydrotrimellitate), trimellitic anhydride, and pyromellitic anhydride.
  • PMDA oxydiphthalic dianhydride
  • BTDA 3,3',4,4'-benzophenonetetracarboxylic dianhydride
  • BPDA 3,3',4,4'-diphenyltetracarboxylic dianhydride
  • DSDA 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride
  • 6FDA 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride
  • 2,2 Examples include compounds such as '-bis[(dicarboxyphenoxy)phenyl]propane dianhydride (BSAA).
  • examples of trifunctional or higher functional polyols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and the like.
  • An acid value may be introduced into the polyester resin (E).
  • the compatibility with the epoxy resin (A) can be adjusted by adjusting the amount of acid value.
  • Examples of the method of introducing an acid value include a method of introducing a carboxylic acid into a polyester resin by acid addition after polymerization. If monocarboxylic acids, dicarboxylic acids, or trifunctional or higher-functional polycarboxylic acid compounds are used for acid addition, the molecular weight may decrease due to transesterification, so it is recommended to use a compound having at least one carboxylic acid anhydride group. preferable.
  • carboxylic anhydrides examples include succinic anhydride, maleic anhydride, orthophthalic acid, 2,5-norbornenedicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride (PMDA), and oxydiphthalic dianhydride.
  • ODPA 3,3',4,4'-benzophenonetetracarboxylic dianhydride
  • BTDA 3,3',4,4'-benzophenonetetracarboxylic dianhydride
  • BPDA 3,3',4,4'-diphenyltetracarboxylic dianhydride
  • DSDA 3,3 ',4,4'-diphenylsulfonetetracarboxylic dianhydride
  • 6FDA 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride
  • BSAA 2,2'-bis[(dicarboxyphenoxy ) phenyl]propane dianhydride
  • the glass transition temperature of the polyester resin (E) is preferably 0°C or lower, more preferably -20°C or lower, even more preferably -40°C or lower. If the glass transition temperature is below the upper limit, embrittlement of the crystalline polyester is suppressed in the temperature range during use, and good toughness is maintained.
  • the melting point is preferably 0 to 100°C.
  • the temperature is more preferably 10 to 80°C, and even more preferably 20 to 50°C.
  • phase separation from the epoxy resin (A) is promoted by the driving force of crystallization, and toughness is improved.
  • the number average molecular weight of the polyester resin (E) is not particularly limited, but is preferably 1000 or more, more preferably 3000 or more. Further, it is preferably less than 100,000, more preferably less than 50,000. When the number average molecular weight is within the above range, the adhesive composition has good flexibility and toughness.
  • the content of the polyester resin (E) is preferably 1 to 30 parts by mass, more preferably 2 to 27 parts by mass, even more preferably 3 to 25 parts by mass, based on the epoxy resin (A). Part by mass.
  • the adhesive composition of the present invention may further contain calcium oxide (F).
  • calcium oxide (F) By containing calcium oxide (F), foaming during curing can be suppressed.
  • Calcium oxide (F) used in the present invention is not particularly limited depending on the presence or absence of surface treatment, particle size, etc., as long as it has calcium oxide as a main component.
  • the content of calcium oxide (F) in the adhesive composition of the present invention is 0.5 to 10 parts by weight, more preferably 1 to 10 parts by weight, and even more preferably 3 parts by weight, based on 100 parts by weight of the epoxy resin (A). ⁇ 10 parts by mass. By being within the above range, it can be expected that foaming during curing will be suppressed, and the toughness of the cured product will be good.
  • the adhesive composition of the present invention contains an epoxy resin (A), a curing agent (B), a curing catalyst (C), a thixotropic agent (D), and a polyester resin (E), where the polyester resin (E) is phenol. It has a component (a) having a hydroxyl group as a structural unit. Moreover, calcium oxide (F) may be included. In addition to these, it may further contain elastomers, core-shell rubbers, coupling agents, inorganic fillers, spacers, various additives, and the like.
  • Elastomers are used to modify adhesives, and may have effects such as improving peel strength and impact strength.
  • rubber-modified epoxy resins such as NBR (acrylonitrile-butadiene rubber), SBR (styrene-butadiene rubber), polybutadiene, and terminal carboxylic acid-modified acrylonitrile-butadiene; for example, Adeka Resin EPR series (manufactured by ADEKA), Hypox RA840 and RA1340, etc.
  • Hypox series (manufactured by CVC), etc.; urethane-modified epoxy resins having a urethane bond in the molecule and two or more oxirane rings; not particularly limited as long as it has the above composition, but for example, Adekal Resin Adeka Resin EPR series such as EPR1630, Hypox series (manufactured by CVC) such as Hypox UA10, etc.; Liquid rubber such as NBR, SBR, and polybutadiene; Silicone resin; Crosslinked rubber fine particles such as crosslinked NBR and crosslinked BR; Urethane rubber; Acrylonitrile-butadiene rubber with terminal carboxylic acid or amino terminal (CTBN, ATBN); NBR rubber with carboxylic acid in the main chain; polybutadiene with terminal carboxylic acid; liquid polysulfide; various urethane prepolymers; polyether sulfone, polyamide, polyether Examples include fine particles of engineering plastic resins such as imide, acrylic, polyester,
  • Core-shell rubber is used to modify adhesives and temporarily fix parts using physical crosslinking, and may have effects such as improving peel strength and impact strength. Examples include Kane Ace MX153, MX154, MX-257, MX-960, MX-136, MX-217 (all manufactured by Kaneka), Gantz Pearl (manufactured by Aica Kogyo), and the like. Note that core-shell rubber refers to particles that are made of a rubber component and have at least a two-layer structure of a core layer and a hard shell layer.
  • a rubber-like substance such as a polymer formed by polymerizing a conjugated diene such as polybutadiene and/or a lower alkyl acrylate, a polymer copolymerized with a monomer that can be copolymerized with these, or polysiloxane. Composed of rubber, etc.
  • the core layer is preferably made of a substance with a glass transition temperature of ⁇ 20° C. or lower from the viewpoint of improving impact resistance at low temperatures and peel strength.
  • a component that has high affinity with the epoxy resin and does not exhibit rubber elasticity is preferable.
  • a polymer formed by polymerizing methyl methacrylate and/or styrene monomers, or a polymer copolymerized with a monomer copolymerizable with these may be used as graft polymerization. It is preferable from the viewpoints of properties and affinity with epoxy resins.
  • the shell layer is preferably made of a substance having a glass transition point of 50° C. or higher from the viewpoint of adhesiveness.
  • Coupling agents are used to improve adhesion to base materials, fillers, resins, etc., and may have effects such as improving shear strength and peel strength by improving interfacial strength.
  • Inorganic fillers are used for purposes such as filling and improving mechanical properties, and may have effects such as improving mechanical strength and imparting thixotropic properties.
  • chlorite chlorite, bentonite, montmorillonite, barite, dolomite, quartz, glass, feldspar, diatomaceous earth, mica, kaolin, alumina, graphite, fibers such as carbon fiber and glass fiber, crystalline silica, amorphous silica, fused silica, fumed silica , silica such as pyrogenic silica, precipitated silica, and ground (fine powder) silica, iron oxide, zinc oxide, titanium oxide, barium oxide, titanium dioxide, hollow glass beads, polymer hollow beads, and the like. These may be used alone or in combination of two or more.
  • the spacer is used to adjust the thickness of the adhesive.
  • examples include glass beads, fibers, resin beads, and inorganic fillers with hardness and particle size above a certain level. These may be used alone or in combination of two or more.
  • the particle diameter of the spacer is preferably 1 to 200 ⁇ m, more preferably 10 to 150 ⁇ m. If the particle diameter of the spacer is less than 1 ⁇ m, it may be difficult to control the thickness of the bonded body, and if it exceeds 200 ⁇ m, the stress in the bonded body may become too large.
  • Examples of the shape of the spacer include spherical particles and fibrous particles. Among these, spherical particles are preferred because particle size can be easily controlled.
  • the amount used is preferably 0.2 to 1.5 parts by mass, more preferably 0.5 to 1 part by mass, per 100 parts by mass of the epoxy resin (A).
  • additives include, for example, plasticizers, reactive diluents, storage stabilizers, anti-aging agents, antioxidants, pigments, dyes, coloring agents, coupling agents, leveling agents, adhesion promoters, and flame retardants.
  • antistatic agents conductivity imparting agents, lubricants, sliding properties imparting agents, ultraviolet absorbers, surfactants, dispersants, dispersion stabilizers, antifoaming agents, dehydrating agents, crosslinking agents, rust preventives, solvents, etc. can be blended.
  • the adhesive composition of the present invention can be manufactured by mixing the above-mentioned components.
  • Examples of the mixing method include methods of mixing using a disper, double planetary mixer, revolution mixer, homogenizer, three rolls, kneader, kneader, and the like.
  • the method for applying the adhesive composition of the present invention include a method of applying the adhesive composition filled in a syringe or the like using a dispenser, a method of spraying, a gun, a brush coating, and the like.
  • the coating temperature of the adhesive composition is preferably 30 to 60°C.
  • the curing temperature of the adhesive composition is preferably 120 to 220°C, more preferably 140 to 200°C.
  • the curing time is preferably 20 to 120 minutes, more preferably 30 to 90 minutes, even more preferably 30 to 60 minutes.
  • the laminate of the present invention is composed of an adhesive layer in which the adhesive composition of the present invention is placed between base materials 1 and 2 and cured.
  • the base material 1 and the base material 2 are metals such as iron, aluminum, and steel; fiber-reinforced plastics such as CFRP (carbon fiber reinforced plastic) and GFRP (glass fiber reinforced plastic); PET (polyethylene terephthalate) and PBT ( Examples include engineering plastic resins such as polybutylene terephthalate), PC (polycarbonate), PI (polyimide), and PA (polyamide); glass, and the like. Since the laminate bonded with the adhesive composition of the present invention has excellent toughness and heat resistance, it can be applied to vehicles such as automobiles, for example.
  • ⁇ Number average molecular weight of polyester resin A sample (polyester resin) was dissolved or diluted in tetrahydrofuran so that the sample concentration was approximately 0.5% by mass, and the sample was filtered through a polytetrafluoroethylene membrane filter with a pore size of 0.5 ⁇ m and used as a measurement sample. .
  • the number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by gel permeation chromatography using tetrahydrofuran as a mobile phase and a differential refractometer as a detector. The flow rate was 1 mL/min, and the column temperature was 30°C. The columns used were Showa Denko KF-802, 804L, and 806L.
  • Monodisperse polystyrene was used as a molecular weight standard. However, if the sample did not dissolve in tetrahydrofuran, N,N-dimethylformamide was used instead of tetrahydrofuran. Low molecular weight compounds (oligomers, etc.) with a number average molecular weight of less than 1000 were not counted and were omitted.
  • ⁇ Tensile shear strength> A base material (Al6061 (aluminum alloy) (3.2 mm x 25 mm x 100 mm, manufactured by Engineering Test Piece Co., Ltd.)) was degreased with acetone and treated with an aqueous sodium hydroxide solution and an aqueous nitric acid solution. :1999, the tensile shear strength was measured. An adhesive composition was applied to a substrate so that the thickness of the adhesive layer was 0.1 mm, and the adhesive composition was cured at 170° C. for 30 minutes to prepare a test piece. The measurement conditions were 25° C. and a tensile speed of 10 mm/min. Evaluation criteria ⁇ : Tensile shear strength is 25 MPa or more ⁇ : Tensile shear strength is 20 MPa or more and less than 25 MPa ⁇ : Tensile shear strength is less than 20 MPa
  • T-Peel (T-peel strength)> A base material (Al6061 (aluminum alloy) (0.5 mm x 25 mm x 200 mm, manufactured by Engineering Test Piece)) was degreased with acetone and treated with an aqueous sodium hydroxide solution and an aqueous nitric acid solution. -3:1999, T-Peel measurement was carried out. An adhesive composition was applied to a substrate so that the thickness of the adhesive layer was 0.1 mm, and the adhesive composition was cured at 170° C. for 30 minutes to prepare a test piece. The measurement conditions were 25° C. and a tensile speed of 100 mm/min. Evaluation criteria ⁇ : T-Peel is 75N/25mm or more ⁇ : T-Peel is less than 75N/25mm
  • polyester resin (E1)> In a reaction vessel equipped with a stirrer, a thermometer, and an outflow condenser, 100 mol parts of adipic acid, 140 mol parts of 3-methyl-1,5-pentanediol, 2.0 mol parts of p-hydroxybenzoic acid, and tetraethylbenzoic acid were added. Butyl titanate was charged in an amount of 0.10 mol part, the temperature was gradually raised to 250°C, and the esterification reaction was carried out while distilled water was removed from the system.
  • the initial polymerization is carried out while gradually reducing the pressure to 10 mmHg, and the temperature is raised to 250 ° C., and the late polymerization is further carried out at 1 mmHg or less until a predetermined torque is reached, resulting in a number average molecular weight of 10,000, A polyester resin (E1) having a glass transition point of -65°C was obtained.
  • Each measurement evaluation item followed the method described above.
  • Polyester resins (E2) to (E5), ( E8) was produced.
  • Table 1 shows the physical properties of each polyester resin.
  • polyester resin (E6) ⁇ Production example of polyester resin (E6)>
  • 100 mol parts of adipic acid, 140 mol parts of 3-methyl-1,5-pentanediol, 2.0 mol parts of p-hydroxybenzoic acid, and tetraethylbenzoic acid were added.
  • Butyl titanate was charged in an amount of 0.10 mol part, the temperature was gradually raised to 250°C, and the esterification reaction was carried out while distilled water was removed from the system.
  • Polyester resin (E7) was produced in the same manner as in the production example of polyester resin (E6) except that the amount of 1,2-cyclohexanedicarboxylic anhydride added was changed to 3.6 parts by mole. Table 1 shows the physical properties of the produced polyester resin (E7).
  • Example 1 100 parts by mass of jER-828 as the epoxy resin (A), 59 parts by mass of BPA as the curing agent (B), 3 parts by mass of HX3742 as the curing catalyst (C), 3 parts by mass of R805 as the thixotropic agent (D). And 19 parts by mass of polyester resin (E1) as polyester resin (E) were mixed using an autorotation-revolution mixer to obtain adhesive composition 1. The tensile shear strength, T-Peel and tan ⁇ of the obtained adhesive composition 1 were measured. The results are shown in Table 2.
  • Example 2 An adhesive composition was prepared in the same manner as in Example 1, except that the types and amounts of each component of the adhesive composition were changed as shown in Table 2. The tensile shear, T-Peel and tan ⁇ of each of the obtained adhesive compositions were measured. The results are shown in Table 2.
  • jER-828 Bisphenol A epoxy resin, manufactured by Mitsubishi Chemical BPA: Bisphenol A, manufactured by Mitsubishi Chemical DICY: Dicyandiamide, manufactured by Mitsubishi Chemical HX3742: Imidazole adduct type catalyst, manufactured by Asahi Kasei 2PHZ: 2-phenyl-4,5-dihydroxymethylimidazole , Shikoku Kasei DCMU: 3-(3,4-dichlorophenyl)-1,1-dimethylurea, Tokyo Kasei R805: Hydrophobic fumed silica, Nippon Aerosil RY200: Hydrophobic fumed silica, Nippon Aerosil CTBN modification
  • the adhesive compositions of Examples 1 to 7 had good results in tensile shear strength, T-Peel, and tan ⁇ , that is, good adhesion, toughness, and heat resistance. It has been shown.
  • the polyester resin did not have a component having a phenolic hydroxyl group as a constituent unit, and the toughness was poor.
  • CTBN-modified epoxy was used in place of the polyester resin, but the sample became brittle, making it impossible to evaluate T-Peel and tan ⁇ .
  • the content of polyester resin was too high, resulting in a decrease in heat resistance.
  • Comparative Example 7 the content of polyester resin was too high, so the sample became brittle, and various evaluations could not be performed.
  • the epoxy composition used in the present invention is useful as an adhesive, and such an adhesive can be suitably used as an adhesive with excellent adhesive properties, toughness, heat resistance, etc., and therefore will greatly contribute to the industrial world. It is expected.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention a pour objet de fournir un agent adhésif à base d'époxy qui tout en présentant une adhérence excellente vis-à-vis d'un substrat présente une ténacité satisfaisante, et présente également une résistance à la chaleur. Plus précisément, l'invention concerne une composition d'agent adhésif qui contient une résine époxy (A), un agent de durcissement (B), un catalyseur de durcissement (C), un agent thixotropique (D) et un polyester (E). Ledit polyester (E) possède en tant qu'unité constitutive un composant ayant un groupe hydroxyle phénolique, et représente une teneur de 1 à 30 parties en masse pour 100 parties en masse de la résine époxy (A). Enfin, l'invention concerne un stratifié qui possède une couche d'adhésif constituée par durcissement de la composition d'agent adhésif.
PCT/JP2023/029133 2022-08-17 2023-08-09 Composition d'agent adhésif WO2024038816A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002302663A (ja) * 2001-02-05 2002-10-18 Toyobo Co Ltd 接着剤用ポリエステル及びそれを用いた接着剤組成物
JP2015514140A (ja) * 2012-03-21 2015-05-18 ダウ グローバル テクノロジーズ エルエルシー ウォッシュオフ耐性のあるエポキシ接着剤組成物および予備ゲル化接着剤
JP2015187271A (ja) * 2008-12-26 2015-10-29 東洋紡株式会社 接着剤用樹脂組成物、これを含有する接着剤、接着シート及びこれを接着層として含むプリント配線板
WO2019188641A1 (fr) * 2018-03-30 2019-10-03 三菱ケミカル株式会社 Composition adhésive, feuille adhésive et couche adhésive
JP2021088649A (ja) * 2019-12-03 2021-06-10 ナガセケムテックス株式会社 熱硬化性樹脂組成物
JP2022078847A (ja) * 2020-11-13 2022-05-25 共同印刷株式会社 酸素吸収用樹脂、酸素吸収用組成物、酸素吸収用接着剤、酸素吸収用積層体、及び酸素吸収用フィルム

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002302663A (ja) * 2001-02-05 2002-10-18 Toyobo Co Ltd 接着剤用ポリエステル及びそれを用いた接着剤組成物
JP2015187271A (ja) * 2008-12-26 2015-10-29 東洋紡株式会社 接着剤用樹脂組成物、これを含有する接着剤、接着シート及びこれを接着層として含むプリント配線板
JP2015514140A (ja) * 2012-03-21 2015-05-18 ダウ グローバル テクノロジーズ エルエルシー ウォッシュオフ耐性のあるエポキシ接着剤組成物および予備ゲル化接着剤
WO2019188641A1 (fr) * 2018-03-30 2019-10-03 三菱ケミカル株式会社 Composition adhésive, feuille adhésive et couche adhésive
JP2021088649A (ja) * 2019-12-03 2021-06-10 ナガセケムテックス株式会社 熱硬化性樹脂組成物
JP2022078847A (ja) * 2020-11-13 2022-05-25 共同印刷株式会社 酸素吸収用樹脂、酸素吸収用組成物、酸素吸収用接着剤、酸素吸収用積層体、及び酸素吸収用フィルム

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