WO2023033074A1 - Composition adhésive - Google Patents

Composition adhésive Download PDF

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Publication number
WO2023033074A1
WO2023033074A1 PCT/JP2022/032854 JP2022032854W WO2023033074A1 WO 2023033074 A1 WO2023033074 A1 WO 2023033074A1 JP 2022032854 W JP2022032854 W JP 2022032854W WO 2023033074 A1 WO2023033074 A1 WO 2023033074A1
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Prior art keywords
component
adhesive composition
components
mixture
group
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PCT/JP2022/032854
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English (en)
Japanese (ja)
Inventor
海理 角▲高▼
均 栗木
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住友精化株式会社
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Publication of WO2023033074A1 publication Critical patent/WO2023033074A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds

Definitions

  • the present invention relates to adhesive compositions.
  • Adhesive compositions used in the industrial field are required to have stable adhesion performance in addition to high adhesive strength to objects to be adhered such as metal materials.
  • Stable adhesion performance specifically means that the failure mode when breaking by applying an external force after bonding is cohesive failure, and that the failure mode is interfacial failure. There is a problem that the adhesion performance is not stable because the external force when peeling occurs at the interface with the object varies greatly.
  • Patent Document 1 discloses an adhesive composition containing an epoxy resin, a curing agent, and a filler, in which a mixture of calcium carbonate and talc is used as the filler. is used, and the ratio of talc in the filler is set to 2 to 10% by weight.
  • Patent Document 2 discloses an adhesive composition containing an adhesive resin, core-shell polymer particles, and polymer particles. These improve adhesion performance by using two kinds of special core-shell polymer particles of several tens to hundreds of nano-size and particles larger than the core-shell polymer.
  • a main object of the present invention is to provide an adhesive composition that achieves both high adhesive strength and improved cohesive failure rate.
  • thermosetting resin [referred to as component (A)], thermoplastic resin particles [referred to as component (B)], and a curing agent and / or
  • an adhesive composition containing a curing accelerator [collectively referred to as component (C)
  • the curing agent is referred to as component (C-1) and the curing accelerator is referred to as component (C-2)]
  • the predetermined condition (I) Breaking energy G per unit area of a cured product of a mixture containing the above components (A), (B), and (C) that satisfies ⁇ (III), and further consisting of components (A) and (C)
  • the adhesive composition has high adhesive strength and It has been found that the cohesive failure rate is improved. Based on these findings, the present invention was achieved through further intensive studies.
  • thermosetting resin [referred to as component (A)], thermoplastic resin particles [referred to as component (B)], and, a curing agent and/or curing accelerator [collectively referred to as component (C), the curing agent being component (C-1) and the curing accelerator being component (C-2)];
  • Condition (I) The value obtained by subtracting the exothermic start temperature of the mixture of components (A) and (C) from the melting point of component (B) is -10°C to 60°C.
  • Condition (II) The tensile modulus of the cured mixture of the components (A) and (C) and the tensile modulus of the cured mixture of the components (A), (B) and (C) The difference is 0.3 GPa or more.
  • Condition (III) Tensile strength of a test piece for measurement prepared from a film made of component (B) and a cured product of a mixture of components (A) and (C), measured by the following method. is 4 MPa or more, and the strain energy per unit volume is 100 kJ/m 3 or more.
  • the details of the compounding ratio of each component and the measurement conditions of the condition (III) when measuring the above conditions (I) to (III) are as follows. ⁇ Blending ratio> The functional group equivalent (mol) ratio of component (C-1) to component (A) is 1:1, and component (C-2) is 3 parts by mass with respect to 100 parts by mass of component (A). do.
  • Component (B) is 30 parts by mass with respect to a total of 100 parts by mass of components (A) and (C).
  • ⁇ Measurement of condition (III)> A film of component (B) having a length of 3 mm, a width of 1.5 mm, and a thickness of 1 mm is placed in the longitudinal center of a groove having a length of 90 mm, a width of 3 mm, and a depth of 1 mm.
  • a mixture consisting of the components (A) and (C) is added to the above, and the mixture is heated at 60 ° C. for 60 minutes, heated at 100 ° C. for 60 minutes, and heated at 150 ° C. for 120 minutes in succession.
  • the mixture is cured in the mold to obtain a test piece for measurement with the cured mixture of components (A) and (C) placed adjacent to and on both sides of the film.
  • a tensile test is performed on the test piece for measurement under conditions of a distance between grips of 25 mm and a test speed of 0.5 mm/min to determine the tensile strength. From the obtained stress-strain curve shown in FIG. 2, the strain energy per unit volume is obtained.
  • Section 2. The adhesive composition according to item 1, wherein component (A) is an epoxy resin.
  • the adhesive composition according to item 1 or 2 wherein the content of component (A) is 7 to 95% by mass.
  • the adhesive composition according to any one of items 1 to 4 which is used for bonding any of structural materials, composite materials, electric/electronic materials, substrate materials, laminate materials, coating materials, and paints.
  • Item 6. A cured product of the adhesive composition according to any one of Items 1 to 5.
  • Item 7. A step of applying or pouring the adhesive composition according to any one of Items 1 to 5 onto the surface of an object to be adhered; curing the adhesive composition; A method of making an adhesive layer, comprising: Item 8.
  • a method of manufacturing an adhesive laminate comprising: Item 9.
  • a method of manufacturing an adhesive laminate comprising:
  • the adhesive composition of the present invention is suitable for adhesive applications in which adhesive compositions are used in various industrial fields, such as structural materials, composite materials, electrical and electronic materials, substrate materials, laminate materials, coating materials, and paints. It can be used preferably.
  • the adhesive composition of the present invention is an adhesive composition having a member as an adherend made of a metal material such as iron, stainless steel, aluminum alloy, or a resin material such as engineering plastic or carbon fiber reinforced plastic. can be preferably used as
  • a numerical value connected with "-" means a numerical range including the numerical values before and after "-" as lower and upper limits. If multiple lower limits and multiple upper limits are listed separately, any lower limit and upper limit can be selected and connected with "-".
  • Component (A) includes thermosetting resins such as epoxy resins, acrylic resins, and silicone resins. These thermosetting resins include epoxy resin-based adhesives, acrylic resin-based adhesives, and silicone resin-based adhesives. A known resin can be used as an agent or the like, and epoxy resin is preferable from the viewpoint of adhesiveness, insulating properties, and mechanical properties.
  • the component (A) resin contained in the adhesive composition of the present invention may be of one type or two or more types. Moreover, the component (A) may be liquid or solid, and is preferably liquid because it is easy to handle.
  • Any epoxy resin that has an epoxy group and can be cured may be used as the epoxy resin, and examples thereof include monoepoxy compounds and polyepoxy compounds.
  • monoepoxy compounds include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, para-butylphenyl glycidyl ether, para-xylyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl hexoate. , glycidyl benzoate, and the like.
  • polyepoxy compounds include bisphenol-type epoxy resins, epoxy resins obtained by glycidylating polyhydric phenol compounds, novolac-type epoxy resins, aliphatic ether-type epoxy resins, ether-ester-type epoxy resins, ester-type epoxy resins, Examples include amine-type epoxy resins and alicyclic epoxy resins.
  • bisphenol type epoxy resins include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, Epoxy resins obtained by glycidylating bisphenols such as tetrabromobisphenol A, tetrachlorobisphenol A and tetrafluorobisphenol A can be mentioned.
  • epoxy resins obtained by glycidylating polyhydric phenol compounds include epoxy resins obtained by glycidylating dihydric phenol compounds such as biphenol, dihydroxynaphthalene, and 9,9-bis(4-hydroxyphenyl)fluorene, and 1 , 1,1-tris(4-hydroxyphenyl)methane and other trisphenol compounds, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane and other tetrakisphenol compounds.
  • An epoxy resin etc. are mentioned.
  • novolak-type epoxy resins include epoxy resins obtained by glycidylating novolac compounds such as phenol novolak type, cresol novolak type, bisphenol A novolak type, brominated phenol novolak type, and brominated bisphenol A novolak type.
  • aliphatic ether-type epoxy resins include epoxy resins obtained by glycidylating polyhydric alcohols such as glycerin and polyethylene glycol.
  • ether ester type epoxy resins include epoxy resins obtained by glycidylating hydroxycarboxylic acids such as paraoxybenzoic acid.
  • ester-type epoxy resins include epoxy resins obtained by glycidylating polycarboxylic acids such as phthalic acid and terephthalic acid.
  • amine-type epoxy resins include epoxy resins obtained by glycidylating amine compounds such as 4,4'-diaminodiphenylmethane and m-aminophenol.
  • alicyclic epoxy resins include 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate, 1,2-epoxy-4-vinylcyclohexane, bis(3,4-epoxycyclohexylmethyl ) adipate, limonene diepoxide, 3,4-epoxycyclohexylmethanol and the like.
  • epoxy resins polyepoxy compounds are preferable, bisphenol type epoxy resins and amine type epoxy resins are more preferable, and bisphenol A type epoxy resins and bisphenol F type epoxy resins are particularly preferably used.
  • the amount of component (A) is preferably 7 to 95% by mass, more preferably 10 to 90% by mass, still more preferably 30% by mass, based on the total adhesive composition. ⁇ 80% by mass.
  • Component (B) is thermoplastic resin particles containing a resin having at least one selected from the group consisting of hydroxy groups, carboxy groups, carboxylic anhydride groups, amino groups, amido groups and glycidyl groups.
  • a resin having at least one selected from the group consisting of hydroxy groups, carboxy groups, carboxylic anhydride groups, amino groups, amido groups and glycidyl groups it is preferable to contain at least one of carboxy group, carboxylic anhydride group, amino group and glycidyl group.
  • the type of thermoplastic resin constituting component (B) it is sufficient that it has these reactive functional groups, and representative thermoplastic resins include polyolefin resin, nylon resin, polyester resin, and polyvinyl alcohol resins, thermoplastic polyurethane resins, and the like.
  • polyolefin-based resins examples include copolymer resins of olefins and other monomers, partially saponified copolymer resins of olefins and other monomers, acid-modified polymers of olefins, and the like.
  • Examples of olefins that constitute copolymer resins of olefins and other monomers include ethylene, propylene, and styrene. Further, as other monomers, among the monomers copolymerizable with the olefins, for example, ⁇ , ⁇ -unsaturated carboxylic acid, ⁇ , ⁇ -unsaturated carboxylic acid anhydride, ⁇ , ⁇ -unsaturated carboxylic acid Metal salts and ⁇ , ⁇ -unsaturated carboxylic acid esters and the like can be mentioned.
  • Examples of ⁇ , ⁇ -unsaturated carboxylic acids include (meth)acrylic acid.
  • (meth)acrylic acid means "methacrylic acid” and "acrylic acid”.
  • Examples of ⁇ , ⁇ -unsaturated carboxylic acid anhydrides include maleic anhydride and the like, and examples of metal salts of ⁇ , ⁇ -unsaturated carboxylic acids include sodium salts and magnesium salts of (meth)acrylic acid. can be mentioned.
  • examples of ⁇ , ⁇ -unsaturated carboxylic acid esters include hydroxy(meth)acrylate and glycidyl(meth)acrylate. These olefins and other monomers may be used alone or in combination of two or more.
  • copolymer resins of olefins and other monomers include ethylene/(meth)acrylic acid copolymers, ethylene/maleic anhydride copolymers, propylene/maleic anhydride copolymers; Ethylene/(meth)acrylic acid ester copolymer such as ethylene/glycidyl (meth)acrylate copolymer; Ethylene/(meth)acrylic acid ester/ such as ethylene/(meth)acrylate/maleic anhydride copolymer Examples include maleic anhydride copolymers and metal salt resins thereof.
  • partially saponified copolymer resins of olefins and other monomers include partially saponified copolymer resins of olefins and vinyl esters, and copolymer resins of olefins and ⁇ , ⁇ -unsaturated carboxylic acid esters.
  • a partially saponified product of coalesced resin can be mentioned.
  • partially saponified products of copolymer resins of olefins and other monomers include partially saponified ethylene/vinyl acetate copolymers, partially saponified ethylene/methyl methacrylate copolymers, ethylene/ A partially saponified ethyl methacrylate copolymer, a partially saponified ethylene/methyl acrylate copolymer, a partially saponified ethylene/ethyl acrylate copolymer, and the like can be mentioned.
  • acid-modified polymers of olefins include acid-modified polyolefins such as maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, and maleic anhydride-modified styrene-ethylene-butylene-styrene (SEBS) copolymers. .
  • acid-modified polyolefins such as maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, and maleic anhydride-modified styrene-ethylene-butylene-styrene (SEBS) copolymers.
  • SEBS maleic anhydride-modified styrene-ethylene-butylene-styrene
  • nylon-based resins examples include -[NH(CH 2 ) 5 CO]-, -[NH(CH 2 ) 4 NHCO(CH 2 ) 4 CO]-, -[NH(CH 2 ) 6 NHCO(CH 2 ) 4 CO]-, -[NH(CH 2 ) 6 NHCO(CH 2 ) 8 CO]-, -[NH(CH 2 ) 10 CO]- and -[NH(CH 2 ) 11 CO]-
  • a nylon resin having at least one selected from among structural units can be mentioned. Specific examples thereof include nylon 6, nylon 46, nylon 66, nylon 610, nylon 11, nylon 12, copolymers thereof, and nylon elastomers which are copolymers of polyesters and polyalkylene ether glycols. be done.
  • the polyolefin resin, nylon resin, polyester resin, polyvinyl alcohol resin, and thermoplastic polyurethane resin may be used alone or in combination of two or more.
  • Preferred component (B) among these is ethylene/(meth)acrylic acid copolymer, ethylene/glycidyl methacrylate copolymer, and maleic anhydride-modified polyethylene, from the viewpoint of easily obtaining flexibility than component (A). and thermoplastic resin particles including nylon elastomers.
  • the volume average particle size of component (B) according to the present invention is, for example, 1 ⁇ m to 100 ⁇ m, preferably 2 to 30 ⁇ m. If it is smaller than 1 ⁇ m, it is difficult to handle, and the viscosity increases in the step of mixing with the component (A), which may impair workability. On the other hand, if it is larger than 100 ⁇ m, it tends to separate when mixed with the component (A), which may result in poor dispersion stability.
  • the volume average particle size of component (B) is the volume average particle size determined by the electrical detection zone method (pore electrical resistance method).
  • a specific device for measuring the volume average particle diameter by the pore electrical resistance method is, for example, an electrical detection type particle size distribution measuring device (trade name “Coulter Multisizer” manufactured by Beckman Coulter, Inc.).
  • the aperture diameter can be selected so as to cover the particle diameters of the particles to be measured.
  • an aperture size smaller than 100 ⁇ m can be selected, and particles having a particle size larger than the measurement range for which an aperture diameter of 100 ⁇ m is suitable can be measured. Aperture diameters larger than 100 ⁇ m can sometimes be chosen.
  • the shape of the component (B) according to the present invention is not particularly limited as long as workability is not impaired, and it is preferably solid, particularly particulate, and its shape includes spherical, irregular, scale-like, and the like.
  • a spherical shape is preferable from the viewpoint of easy dispersion in the adhesive composition and suppression of increase in viscosity.
  • Component (B) according to the present invention contains inorganic particles such as alumina and silica, metal powders such as iron, copper, nickel, and cobalt, and organic substances such as ultraviolet absorbers and heat stabilizers in or on the surface of the particles. You can also let
  • the compounding amount of component (B) is preferably 3 to 300 parts by mass, more preferably 5 to 200 parts by mass, per 100 parts by mass of component (A). , more preferably 10 to 80 parts by mass.
  • the curing agent as component (C-1) reacts with component (A), which is a thermosetting resin, to give a cured product.
  • Component (C-1) may be used alone or in combination of two or more. When two or more components (C-1) are mixed and used, the mixture of the mixed curing agents is regarded as one component (C-1).
  • component (C-1) examples include amine-based curing agents, amide-based curing agents, acid anhydride-based curing agents, phenol-based curing agents, mercaptan-based curing agents, isocyanate-based curing agents, active ester-based curing agents, and cyanate. Examples include ester-based curing agents.
  • amine-based curing agents include chain aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; isophoronediamine, bis(4-aminocyclohexyl)methane, bis(aminomethyl)cyclohexane, alicyclic amines; aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diethyltoluenediamine, and diethyldiaminodiphenylmethane;
  • chain aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine
  • isophoronediamine bis(4-aminocyclohexyl)methane, bis(aminomethyl)cyclohexane, alicyclic amines
  • aromatic amines such as metaphenylenediamine, diamino
  • amide-based curing agents examples include dicyandiamide and its derivatives, and polyamide resins (polyaminoamide, etc.).
  • acid anhydride curing agents examples include aliphatic acid anhydrides such as maleic anhydride and dodecenyl succinic anhydride; aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride; methyl anhydride alicyclic acid anhydrides such as nadic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride;
  • phenol-based curing agents include phenol novolak resin, cresol novolak resin, biphenyl novolak resin, triphenylmethane phenol resin, naphthol novolak resin, phenol biphenylene resin, phenol aralkyl resin, biphenyl aralkyl phenol resin, and modified polyphenylene ether.
  • phenol novolak resin cresol novolak resin
  • biphenyl novolak resin triphenylmethane phenol resin
  • naphthol novolak resin phenol biphenylene resin
  • phenol aralkyl resin phenol aralkyl resin
  • biphenyl aralkyl phenol resin biphenyl aralkyl phenol resin
  • modified polyphenylene ether examples include resins and compounds having a benzoxazine ring.
  • Mercaptan-based curing agents include, for example, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate) , tetraethylene glycol bis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate ), trimethylolethane tris(3-mercaptobutyrate), polysulfide polymer and the like.
  • isocyanate-based curing agents examples include hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, lysine diisocyanate, isophorone diisocyanate and norbornane diisocyanate.
  • the active ester curing agent is a compound having one or more ester groups that react with (A) the thermosetting resin in one molecule, and includes phenyl esters, naphthyl esters, thiophenyl esters, N-hydroxyamine esters, heterocyclic Hydroxy compound esters and the like are included.
  • cyanate ester curing agents include bisphenol type cyanate resins such as novolac type cyanate resins, bisphenol A type cyanate resins, bisphenol E type cyanate resins, and tetramethylbisphenol F type cyanate resins.
  • the component (C-1) is at least one selected from the group consisting of amine-based curing agents, acid anhydride-based curing agents, amide-based curing agents, and phenol-based curing agents. is preferably used, and an amine-based curing agent and an acid anhydride-based curing agent are more preferable.
  • the amount of component (C-1) to be blended is usually based on 1 equivalent of reactive functional groups (eg, epoxy groups) in component (A) which is a thermosetting resin. It is preferable to adjust the blending amount so that the equivalent weight of the reactive functional group in -1) is 0.1 to 5 equivalents.
  • the equivalent weight of the reactive functional group in component (C-1) is more preferably 0.3 to 3 equivalents, still more preferably 0.5 to 2 equivalents.
  • Component (C-2) is a component that accelerates the curing of component (A), which is a thermosetting resin.
  • component (A) which is a thermosetting resin.
  • component (C-2) and the component (C-1) in combination, the curing reaction rate can be increased and the strength of the resulting cured product can be increased.
  • Component (C-2) may be used alone or in combination of two or more. When two or more types of components (C-2) are mixed and used, the mixture of the mixed curing accelerators is regarded as one component (C-2).
  • component (C-2) examples include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 1-benzyl-2- imidazole compounds such as methylimidazole; secondary amines such as piperidine; DBU (1,8-diazabicyclo(5,4,0)-undecene-7), DBN (1,5-diazabicyclo(4,3,0)- nonene-5), tertiary amines such as 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 4-dimethylaminopyridine; triphenylphosphine , phosphorus-based compounds such as tetraphenylphosphonium tetraphenylborate, Lewis acid compounds, cationic polymerization initiators,
  • the component (C-2) it is preferable to use at least one selected from the group consisting of imidazole compounds, tertiary amines, phosphorus compounds, and cationic polymerization initiators. .
  • the amount of component (C-2) blended is preferably 0.01 to 10 parts by mass, more preferably 0, per 100 parts by mass of component (A). .1 to 5.0 parts by mass, more preferably 0.5 to 5.0 parts by mass.
  • the total content of component (A), component (B), and component (C) is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass. % or more, more preferably 70 mass % or more, and may be 100 mass %.
  • components (A), (B) and (C) satisfy the following conditions (I) to (III).
  • Component (C-1) is adjusted to have a functional group equivalent (molar) ratio of 1:1 with component (A).
  • Component (C-2) is 3 parts by weight per 100 parts by weight of component (A).
  • Component (B) is 30 parts by mass with respect to a total of 100 parts by mass of components (A) and (C).
  • Condition (I) is that the value obtained by subtracting the exothermic start temperature of the mixture of components (A) and (C) from the melting point of component (B) is -10°C to 60°C.
  • Condition (I) relates to the thermal performance of component (B), which is a thermoplastic resin particle. Specifically, it is the temperature difference between the melting point (or endothermic peak top temperature) of component (B) and the exothermic start temperature of the mixture of components (A) and (C). When the temperature difference is ⁇ 10 to 60° C., the interaction between the molecules near the interface between the thermosetting resin component (A) and the thermoplastic resin particles (B) becomes active. .
  • the lower limit of the temperature difference is preferably -5°C, more preferably -2°C.
  • the upper limit is preferably 55°C, more preferably 50°C.
  • the melting point (or endothermic peak top temperature) and exothermic start temperature are measured by the following method.
  • the temperature is measured using a differential scanning calorimeter (DSC6220, Hitachi High-Tech Science Co., Ltd.) at a heating rate of 5° C./min.
  • the exothermic start temperature is defined as the point (Ta) at which the amount of heat (mW/mg) in 1 mg of the sample is plotted at each measurement temperature during temperature rise, that is, the point (Ta) at which the so-called DSC curve begins to depart from the baseline.
  • Condition (II) is the tensile modulus of the cured mixture of component (A) and component (C), and the tensile elasticity of the cured mixture of component (A), component (B) and component (C).
  • the difference in modulus is 0.3 GPa or more.
  • Condition (II) is a condition indicating the difference in tensile modulus depending on the presence or absence of component (B), which is a thermoplastic resin particle.
  • component (B) which is a thermoplastic resin particle.
  • a preferable lower limit of the difference in tensile elastic modulus is preferably 0.6 GPa, more preferably 0.8 GPa, and a preferable upper limit is 2.5 GPa.
  • Tensile stress ( ⁇ ) and strain ( ⁇ ) were measured by performing a tensile test on each of the obtained cured product test pieces under the conditions of a distance between grips of 25 mm and a test speed of 0.5 mm/min. find the rate.
  • the tensile modulus is calculated by a method conforming to JIS K7161, specifically from the gradient of a straight line at micro strain (formula 1).
  • Condition (III) is measured by the following method, and the tensile strength of a test piece for measurement prepared from a cured product of a film made of component (B) and a mixture of components (A) and (C) is It is 4 MPa or more, and the strain energy per unit volume is 100 kJ/m 3 or more.
  • Condition (III) relates to the strength of the interface between component (A), which is a thermosetting resin, and component (B), which is thermoplastic resin particles, and the film. It is considered that the interface between component (A) and component (B) interacts because the tensile strength is 4 MPa or more.
  • the strain energy per unit volume of 100 kJ/m 3 or more strengthens the interface interaction between the component (A) and the component (B).
  • the lower limit of tensile strength is preferably 5 MPa, more preferably 6 MPa, and the upper limit is preferably 50 MPa, more preferably 20 MPa.
  • the lower limit of strain energy per unit volume is preferably 150 kJ/m 3 , more preferably 200 kJ/m 3 , and the upper limit is preferably 20000 kJ/m 3 , more preferably 5000 kJ/m 3 .
  • a film of component (B) having a length of 3 mm, a width of 1.5 mm, and a thickness of 1 mm is placed in the longitudinal center of a groove having a length of 90 mm, a width of 3 mm, and a depth of 1 mm.
  • the mixture consisting of the components (A) and (C) was put in, heated at 60 ° C. for 60 minutes, heated to 100 ° C. at 2 ° C./min, heated at 100 ° C. for 60 minutes, and further heated to 2.5 ° C.
  • the mixture is cured in the mold by increasing the temperature at 150° C./min and continuously heating at 150° C.
  • a test piece for measurement is obtained on which the cured mixture of C) is arranged.
  • a tensile test is performed on the test piece for measurement under conditions of a distance between grips of 25 mm and a test speed of 0.5 mm/min to determine the tensile strength. From the obtained stress-strain curve shown in FIG. 2, the strain energy per unit volume is obtained. The strain energy per unit volume is the area enclosed from the starting point of the tensile test to the breaking point. calculate.
  • the integrated value is calculated by calculating the minimum rectangular area obtained by the minimum tensile stress within the strain width for each strain width of 0.0001 [mm / mm] from the start of tension, and calculating the total area up to the breaking point. It is calculated by summing the areas of the rectangles.
  • a film made of component (B) is prepared by the following method.
  • a film is formed by pressing for 30 seconds at a pressure of 0.2 MPa with a hot press (for example, a manual hydraulic vacuum heat press (manufactured by Imoto Seisakusho)) at a temperature of 25° C. or more above the melting point of component (B).
  • a hot press for example, a manual hydraulic vacuum heat press (manufactured by Imoto Seisakusho)
  • a hot press for example, a manual hydraulic vacuum heat press (manufactured by Imoto Seisakusho)
  • a hot press for example, a manual hydraulic vacuum heat press (manufactured by Imoto Seisakusho)
  • the melting point of the component (B) is 97° C.
  • it is formed into a film by pressing under the conditions of a temperature of 130° C. and a pressure of 0.2 MPa for 30 seconds.
  • the melting point of component (B) is 175° C.
  • the film is formed by pressing under
  • the adhesive composition of the present invention has a component (A), ( The ratio of the breaking energy G 1c per unit area of the cured product of the mixture consisting of B) and (C), i.e. is 2.5 to 6.0 times.
  • the lower limit of the ratio of the fracture energy G 1c is preferably 3 times, and the upper limit is preferably 5 times.
  • the mass ratio of each component in the adhesive composition of the present invention is as follows: Component (A): Component (B): Component (C- 1): Component (C-2) satisfies the relationship of 1: (0.03 to 3): (0 to 2): (0 to 0.1) (however, component (C-1) and component ( It is preferable that the mass ratio of C-2) is not 0 at the same time.
  • Fracture energy G 1c (fracture toughness value K 1c ) 2 / tensile elastic modulus E (Equation 2)
  • a mixture consisting of component (A) and component (C) is put into a mold (length 90 mm, width 20 mm, depth 3 mm), heated at 60 ° C. for 60 minutes, and heated to 100 ° C. at 2 ° C./min, After heating at 100° C. for 60 minutes and further increasing the temperature to 150° C. at 2.5° C./min, the mixture is cured in the mold by performing a continuous heat treatment of heating at a temperature of 150° C. for 120 minutes. Create a product sheet.
  • the obtained cured product sheet was cut into a size of 60 mm in length, 3 mm in width (B), and 10 mm in thickness (W) to obtain a strip-shaped cured product test piece.
  • the central portion in the longitudinal direction is mechanically processed to a depth of 5 mm in the thickness direction.
  • a scratch having a depth of 0.1 mm in the thickness direction is given with a razor to the tip of the mechanically processed specimen of the cured product.
  • Total crack length (a) 5.1 mm.
  • P Q Load (N)
  • S Distance between fulcrums (40mm)
  • B Width of cured product test piece (3 mm)
  • W Thickness of cured product test piece (10 mm)
  • a total crack length (5.1 mm)
  • the cured mixture of components (A), (B) and (C) preferably has a breaking energy G 1c per unit area of 500 to 20000 J/m 2 , more preferably 700 to 8000 J/m 2 , more preferably 900 to 5000 J/m 2 .
  • the breaking energy G 1c per unit area of the cured mixture of components (A) and (C) is preferably 200 to 3,500 J/m 2 , more preferably 250 to 1,500 J/m 2 , still more preferably 300. ⁇ 1000 J/m 2 .
  • the adhesive composition of the present invention may contain other additives, if necessary, as long as the objects and effects of the present invention are not impaired.
  • Additives include, for example, organic fillers not included in component (B), thermoplastic resins, rubbers, elastomers, composite particles, inorganic fillers, conductive particles, carbon black, antioxidants, inorganic phosphors, and lubricants. , UV absorber, heat and light stabilizer, antistatic agent, polymerization inhibitor, antifoaming agent, solvent, anti-aging agent, radical inhibitor, adhesion improver, flame retardant, surfactant, storage stability improver, Ozone anti-aging agents, thickeners, plasticizers, radiation shielding agents, nucleating agents, coupling agents, conductivity imparting agents, phosphorus-based peroxide decomposers, pigments, metal deactivators, physical property modifiers, etc. be done.
  • the content of the additive is 90% by mass or less.
  • the adhesive composition of the present invention can be produced by mixing component (A), component (B), component (C) and, if necessary, other additives.
  • the mixing method is not particularly limited as long as it is a method that allows each component to be uniformly mixed.
  • the adhesive composition of the present invention has a low viscosity, it can be prepared without adding a solvent. , acetone, cyclohexanone, methylcyclohexane, cyclohexane, etc.) may be added.
  • a cured product can be obtained by curing the adhesive composition of the present invention.
  • the curing method depends on the type of curable resin, but can be carried out, for example, by heating the composition.
  • the curing temperature is usually room temperature (25° C.) to 250° C.
  • the curing time can be usually set in the range of 30 seconds to 1 week.
  • the curing temperature is 40 ° C. ⁇
  • the temperature is 200° C.
  • the curing time is preferably set to 1 minute to 12 hours.
  • the adhesive composition of the present invention can be suitably used as an adhesive for structural materials, composite materials, electric/electronic materials, substrate materials, and laminate materials, and by being mixed in coating materials, paints, and the like.
  • Adhesives for structural materials include, for example, adhesives for bonding metal materials, polymer materials, inorganic materials, etc. used in automobiles, vehicles (bullet trains, trains), aircraft, the space industry, and the like.
  • adhesives for electrical/electronic materials, substrate materials, and laminate materials include adhesives for interlayers of multilayer substrates, semiconductors, and mounting, sealants, and underfills.
  • the cured product of the adhesive composition of the present invention is obtained by curing the above-described adhesive composition of the present invention.
  • a method for curing the adhesive composition of the present invention is not particularly limited, but as described above, a method of heating the adhesive composition of the present invention can be used.
  • the adhesive layer of the present invention can be produced by a production method comprising the steps of applying or pouring the adhesive composition of the present invention onto the surface of an object to be adhered, and curing the adhesive composition. can.
  • the method for curing the adhesive composition of the present invention is as described above.
  • An adhesive laminate can be obtained by passing through the step of disposing the adhesive composition of the present invention between the substrate and the adherend described above.
  • the method for curing the adhesive composition of the present invention is as described above.
  • thermosetting resin Thermosetting resin> The following thermosetting resins A-1 and A-2 were used as component (A), respectively.
  • A-1 A bisphenol F type epoxy resin (jER806; manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 167) was used as component A-1.
  • A-2 A bisphenol A type epoxy resin (jER828; manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186) was used as component A-2.
  • thermoplastic resin particles > The following thermoplastic resin particles B-1 to B-6 were used as component (B).
  • thermoplastic resin particles As a resin having a carboxyl group, an ethylene/acrylic acid copolymer (volume average particle size: 10 ⁇ m, melting point: 97° C., Flowbeads EA209 manufactured by Sumitomo Seika Co., Ltd.) was used as thermoplastic resin particles B-1.
  • thermoplastic resin particles B-2
  • 12 nylon volume average particle size: 20 ⁇ m, melting point: 175° C.
  • ORGASOL 2002D manufactured by Arkema was used as thermoplastic resin particles B-2.
  • Thermoplastic resin particles B-3 160 g of ethylene/glycidyl methacrylate copolymer resin (GMA content: 19% by mass), 224 g of deionized water, and ethylene oxide/propylene oxide as an emulsifier were placed in a pressure-resistant autoclave having an internal volume of 1 liter equipped with a turbine-type stirring blade with a diameter of 50 mm. 16 g of a polymer (weight-average molecular weight: 15,500, ethylene oxide content: 80% by mass) was introduced and sealed. Next, the temperature inside the autoclave was raised to 150° C. while stirring at 500 rpm.
  • thermoplastic resin particles B-3 had a volume average particle diameter of 13 ⁇ m and a melting point of 88°C.
  • Thermoplastic resin particles B-4 160 g of maleic anhydride-modified polyethylene resin (maleic anhydride content: 0.5% by mass), 224 g of deionized water, and ethylene oxide/propylene as an emulsifier were placed in a 1-liter pressure-resistant autoclave equipped with a turbine-type stirring blade with a diameter of 50 mm. 16 g of an oxide copolymer (weight average molecular weight: 15,500, ethylene oxide content: 80% by mass) was introduced and sealed. Next, the temperature inside the autoclave was raised to 160° C. while stirring at 500 rpm.
  • thermoplastic resin particles B-4 had a volume average particle diameter of 25 ⁇ m and a melting point of 120°C.
  • Thermoplastic resin particles B-5 160 g of 12 nylon/polyalkylene ether glycol copolymer resin, 224 g of deionized water, ethylene oxide/propylene oxide copolymer (weight average molecular weight 15 , 500 and an ethylene oxide content of 80% by mass) was charged and sealed. Next, the temperature inside the autoclave was raised to 180° C. while stirring at 500 rpm. After further stirring for 30 minutes while maintaining the internal temperature at 180° C., the content was cooled to room temperature to obtain an aqueous dispersion of 12 nylon/polyalkylene ether glycol copolymer.
  • thermoplastic resin particles B-5 rice field.
  • the thermoplastic resin particles B-5 obtained here had a volume average particle diameter of 11 ⁇ m and a melting point of 140°C.
  • Component (C-1) Curing agent> As component (C-1), the following curing agent (C-1a) and curing agent (C-1b) were used, respectively.
  • [Curing agent C-1a] An acid anhydride-based curing agent (Rikacid MH700; a liquid alicyclic acid anhydride containing 4-methylhexahydrophthalic anhydride as a main component, manufactured by Shin Nippon Rika Co., Ltd.) was used as a curing agent (C-1a).
  • [Curing agent C-1b] An amine-based curing agent (Kayahard AA; diethyldiaminodiphenylmethane, manufactured by Nippon Kayaku Co., Ltd.) was used as the curing agent (C-1b).
  • C-2a An imidazole-based curing accelerator (Curesol 1B2MZ; 1-benzyl-2-methylimidazole, manufactured by Shikoku Kasei Co., Ltd.) was used as component (C-2a).
  • Curing accelerator C-2b An imidazole-based curing accelerator (Curesol 2E4MZ; 2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei Co., Ltd.) was used as component (C-2b).
  • Adhesive composition (1) Prepared so that the functional group equivalent is equivalent to the component (A-1) 38.4 parts by mass (functional group equivalent: 0.23) so that the composition shown in Table 1 is obtained by the following procedure.
  • Component (C-1a) 37.3 parts by mass (functional group equivalent: 0.23), Component (C-2a) 1.2 parts by mass (3 parts by mass per 100 parts by mass of epoxy resin), Component (B -1) Weigh 23.1 parts by mass in a plastic container, stir at room temperature with Awatori Rentaro (ARE-310, manufactured by Shinky Corporation) at 2000 rpm for 1 minute, and at 2200 rpm After defoaming for 1 minute, an adhesive composition (1) was prepared.
  • Awatori Rentaro ARE-310, manufactured by Shinky Corporation
  • Adhesive compositions (2)-(14) Adhesive compositions (2) to (14) were prepared by mixing and stirring component (A), component (B) and component (C) so as to have the compositions shown in Table 1, respectively.
  • the measured values of conditions (I), (II) and (III) in Examples 2 to 4 were the values measured in Example 1. Also for Comparative Examples 2 and 4, the measured values in Comparative Example 1 were used.
  • Component (C-1) is adjusted to have a functional group equivalent (molar) ratio of 1:1 with component (A).
  • Component (C-2) is 3 parts by weight per 100 parts by weight of component (A).
  • Component (B) is 30 parts by mass with respect to a total of 100 parts by mass of components (A) and (C).
  • each component was prepared in the same manner as in the preparation of the adhesive composition described above.
  • a mixture consisting of components (A) and (C) in the above blending ratio was prepared, and the resulting mixture was measured using a differential scanning calorimeter (DSC6220, Hitachi High-Tech Science Co., Ltd.) at a heating rate of 5 ° C./min.
  • the exothermic start temperature was measured at .
  • the exothermic start temperature was defined as the point at which the so-called DSC curve, which is a curve obtained by plotting the amount of heat (mW/mg) in 1 mg of sample at each measurement temperature during heating, begins to depart from the baseline.
  • melting point-exothermic start temperature was calculated from the obtained exothermic start temperature and melting point. Table 1 shows the results.
  • the cured product was cut to prepare a strip-shaped cured product test piece (length 80 mm, width 5 mm, thickness 2 mm).
  • Tensile stress ( ⁇ ) and strain ( ⁇ ) were measured by performing a tensile test on each of the obtained cured product test pieces under the conditions of a distance between grips of 25 mm and a test speed of 0.5 mm/min. asked for a rate.
  • the tensile modulus was calculated by a method conforming to JIS K7161, specifically from the linear gradient at micro strain (Equation 1).
  • the tensile elastic modulus of the cured mixture of components (A), (B) and (C) was similarly measured by a tensile test to calculate the difference in tensile elastic modulus. Table 1 shows the results.
  • the mixture was heated at 60°C for 60 minutes, heated at 2°C/min to 100°C, heated at 100°C for 60 minutes, further heated at 2.5°C/min to 150°C, and then heated at 150°C to 120°C.
  • the mixture is cured in the mold by successively heating the mixture for a minute to leave the cured mixture of components (A) and (C) adjacent to both sides of the film formed from component (B).
  • An arranged measuring specimen was obtained.
  • This test piece for measurement was subjected to a tensile test under the conditions of a distance between grips of 25 mm and a test speed of 0.5 mm/min to determine the tensile strength. From the obtained stress-strain curve shown in FIG. 2, the strain energy per unit volume was obtained.
  • the strain energy per unit volume was obtained by calculating the integrated value of the tensile stress from the starting point of the tensile test to the breaking point using the strain as a variable.
  • the integrated value is calculated by calculating the minimum rectangular area obtained by the minimum tensile stress within the strain width for each strain width of 0.0001 [mm / mm] from the start of tension, and calculating the total area up to the breaking point. Calculated by summing the areas of the rectangles. Table 1 shows the results.
  • a mixture of components (A) and (C) is put into a mold (length 90 mm, width 20 mm, depth 3 mm), heated at 60° C. for 60 minutes, and heated to 100° C. at 2° C./min. The temperature is raised, heated at 100° C. for 60 minutes, further heated at 2.5° C./min to 150° C., and heated at 150° C. for 120 minutes, thereby curing the mixture in the mold and curing.
  • a product sheet was created.
  • the resulting cured sheet was 60 mm long, 3 mm wide (B), and 10 mm thick (W), and was mechanically processed to a depth of 5 mm in the central portion in the longitudinal direction.
  • the fracture toughness values (K 1C (MPa ⁇ m 1/2 )) of mixtures consisting of components (A), (B) and (C), respectively, are and the ratio of the above fracture energy G 1c was calculated.
  • Table 1 shows the results.
  • the cured product of the mixture of components (A), (B) and (C) had a breaking energy G 1c per unit area of 1904 J/m 2 .
  • the breaking energy G 1c per unit area of the cured product of the mixture of (A) and (C) was 373 J/m 2 and the ratio was 5.1.
  • Each of the adhesive compositions (1) to (14) was applied to a pretreated aluminum plate (JIS H4000 A1050P size 3 mm ⁇ 25 mm ⁇ 100 mm) so that the adhesive part was a rectangle of 12.5 mm ⁇ 25 mm.
  • Another aluminum plate is attached to the surface, heated at 60°C for 60 minutes, heated at 2°C/min to 100°C, heated at 100°C for 60 minutes, and further heated at 2.5°C/min to 150°C. It was cured by heating continuously at 150° C. for 120 minutes to obtain a tensile shear adhesion test piece.
  • the pretreatment means a treatment method in which the substrate is immersed in an organic solvent and an alkaline bath at 70° C. in addition to sandblasting.
  • the resulting tensile shear adhesion test piece was subjected to a tensile shear adhesion test using a tensile tester (AGS-X, manufactured by Shimadzu Corporation) under the conditions of a distance between grips of 100 mm and a test speed of 2 mm/min. .
  • the tensile shear adhesive strength (MPa) to the aluminum plate was calculated from the measured value (N) of the maximum breaking strength after the test and the area (mm 2 ) of the adhesive portion.

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

Abstract

La présente invention concerne une composition adhésive qui a atteint un bon équilibre entre une force de liaison élevée et une amélioration du rapport de rupture cohésive.　La présente invention concerne une composition adhésive qui contient une résine thermodurcissable (désignée ci-après par composant (A)), des particules de résine thermoplastique (désignées ci-après par composant (B)), et un durcisseur et/ou un accélérateur de durcissement (désignés ci-après composant (C) dans l'ensemble, tandis que l'agent de durcissement est indépendamment appelé composant (C-1) et l'accélérateur de durcissement étant indépendamment appelé composant (C-2)). Le composant (B) contient une résine qui présente au moins un groupe étant choisi dans le groupe constitué par un groupe hydroxy, un groupe carboxy, un groupe anhydride d'acide carboxylique, un groupe amino, un groupe amide et un groupe glycidyle ; par rapport à cette composition adhésive, le rapport de l'énergie de rupture G1c par unité de surface d'un produit durci d'un mélange qui est composé des composants (A), (B) et (C) à l'énergie de rupture G1c par unité de surface d'un produit durci d'un mélange qui est composé des composants (A) et (C) est de 2,5 à 6 fois tel que calculé par la formule ((énergie de rupture G1c) = (valeur de ténacité K1c)2/(module d'élasticité en traction E)) ; et les composants (A), (B) et (C) satisfont les conditions décrites ci-dessous. Condition (I) : La valeur obtenue par soustraction de la température de début exothermique d'un mélange qui est constitué des composants (A) et (C) à partir du point de fusion du composant (B) est de -10 °C à 60 °C (II) : La différence entre le module d'élasticité en traction d'un produit durci d'un mélange qui est constitué des composants (A) et (C) et le module d'élasticité en traction d'un produit durci d'un mélange qui est constitué des composants (A), (B) et (C) est d'au moins 0,3 GPa. Condition (III) : Une pièce test pour la mesure préparée à partir d'un film qui est formé du composant (B) et un produit durci d'un mélange qui est constitué des composants (A) et (C) présente une résistance en traction d'au moins 4 MPa et une énergie de déformation par unité de volume d'au moins 100 kJ/m3 tel que déterminé par le procédé décrit ci-dessous.
PCT/JP2022/032854 2021-08-31 2022-08-31 Composition adhésive WO2023033074A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5682865A (en) * 1979-11-09 1981-07-06 Ciba Geigy Ag Epoxy resin heatthardenable adhesive agent and method
JPH06313157A (ja) * 1993-04-30 1994-11-08 Yokohama Rubber Co Ltd:The 接着剤組成物
WO2015093281A1 (fr) * 2013-12-16 2015-06-25 住友精化株式会社 Agent adhésif de résine époxy
WO2020235588A1 (fr) * 2019-05-20 2020-11-26 住友精化株式会社 Composition adhésive

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5682865A (en) * 1979-11-09 1981-07-06 Ciba Geigy Ag Epoxy resin heatthardenable adhesive agent and method
JPH06313157A (ja) * 1993-04-30 1994-11-08 Yokohama Rubber Co Ltd:The 接着剤組成物
WO2015093281A1 (fr) * 2013-12-16 2015-06-25 住友精化株式会社 Agent adhésif de résine époxy
WO2020235588A1 (fr) * 2019-05-20 2020-11-26 住友精化株式会社 Composition adhésive

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