WO2019189238A1 - Composition adhésive - Google Patents

Composition adhésive Download PDF

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Publication number
WO2019189238A1
WO2019189238A1 PCT/JP2019/012966 JP2019012966W WO2019189238A1 WO 2019189238 A1 WO2019189238 A1 WO 2019189238A1 JP 2019012966 W JP2019012966 W JP 2019012966W WO 2019189238 A1 WO2019189238 A1 WO 2019189238A1
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WIPO (PCT)
Prior art keywords
polymer particles
core
weight
adhesive composition
shell
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PCT/JP2019/012966
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English (en)
Japanese (ja)
Inventor
秀輔 吉原
岸　肇
松田　聡
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株式会社カネカ
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Priority to JP2020510949A priority Critical patent/JP7184874B2/ja
Publication of WO2019189238A1 publication Critical patent/WO2019189238A1/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
    • C09J11/08—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/70—Wind energy
    • Y02E10/72—Wind turbines with rotation axis in wind direction

Definitions

  • the present invention relates to an adhesive composition containing an adhesive resin and core-shell polymer particles.
  • structural adhesives have been used in various fields.
  • a method of strengthening the joining of structural members has been attempted as a technique for achieving both weight reduction and rigidity improvement of a vehicle body, and as one of the joining methods, joining by using an adhesive and spot welding in combination.
  • the technology (weld bond method) is drawing attention.
  • an adhesive to be applied to the joining site an epoxy resin-based thermosetting adhesive (structural adhesive) is widely used, and is cured by heating after spot welding.
  • a strength member is arranged in the longitudinal direction of the center of the blade, and a member formed of a composite material is bonded with an adhesive along the shape of the blade surface and the back surface of the blade so as to sandwich the strength member.
  • Patent Document 2 discloses a structural adhesive composition excellent in flowing water pressure resistance, which contains an epoxy resin, core-shell rubber particles in a dispersed form in which primary particles and secondary aggregates are mixed, and a curing agent. Is disclosed. This document does not describe fatigue resistance. In the adhesive composition described in this document, it is necessary to mix the secondary aggregates of the core-shell type rubber particles with the primary particles. Therefore, it is difficult to control the particle size of the aggregates and the content of the aggregates, It is considered that the physical properties of the adhesive are not stable.
  • Patent Document 3 discloses an epoxy resin composition that can be used as a structural adhesive, and includes an epoxy resin, core-shell rubber particles, and a hollow polymer. This document does not describe fatigue resistance. In addition, when a hollow polymer is used, it is considered that the hollow polymer is destroyed by an impact received when the components are mixed and mixed, and it is difficult to disperse the hollow polymer as primary particles.
  • the present invention has been made in view of the above situation, and an object of the present invention is to provide an adhesive composition that is excellent in fatigue resistance and that undergoes cohesive failure at the time of fatigue failure.
  • the present inventors have determined that, in addition to the nanometer-order core-shell polymer particles blended to improve the toughness of the adhesive, polymer particles having a particle size larger than the core-shell polymer particles at a specific ratio.
  • the adhesive layer has high toughness and induces cracks inside the adhesive layer during fatigue failure.
  • the present inventors have found that a highly reliable adhesive composition that greatly improves fatigue resistance and undergoes cohesive failure at the time of fatigue failure can be obtained. That is, the present invention includes the following 1) to 7).
  • Adhesive composition 1) containing an adhesive resin, a core-shell polymer particle (A) having a volume average particle diameter of 10 to 300 nm, and a polymer particle (B) having a volume average particle diameter of 400 nm to 10000 nm;
  • the weight ratio of (B) is 1: 2 to 2: 1, and each of the core-shell polymer particles (A) and the polymer particles (B) is dispersed as primary particles in the adhesive composition.
  • Adhesive composition 2) The adhesive composition according to 1), wherein the polymer particles (B) are polymer particles having no hollow structure. 3) The adhesive composition according to 1) or 2), wherein the polymer particles (B) are core-shell polymer particles.
  • the core layer of the core-shell polymer particle (A) or the core layer of the polymer particle (B) is selected from the group consisting of (i) a diene monomer and a (meth) acrylic acid ester monomer.
  • a rubber elastic body composed of 50% by weight or more of at least one monomer and less than 50% by weight of another copolymerizable vinyl monomer, (ii) a polysiloxane rubber-based elastic body, (iii) Crosslinked aromatic vinyl, or (iv) a mixture of two or more of (i) to (iii) above, and the other copolymerizable vinyl monomer is an aromatic vinyl compound or a vinyl cyanide compound
  • an adhesive composition that is excellent in fatigue resistance and that undergoes cohesive failure at the time of fatigue failure.
  • a conceptual diagram showing a state of cohesive failure in which cracks are generated inside the adhesive layer when an adhesive containing only polymer particles (B) having a large particle size is used.
  • the conceptual diagram which shows the state of the cohesive failure which the crack produced inside the adhesive bond layer when using the adhesive agent which mix
  • the side view which shows this test piece and spacer in the process of manufacturing the shearing-bonding test piece used by evaluation of an Example and a comparative example Side view showing a shear adhesion test piece used in the evaluation of Examples and Comparative Examples
  • the adhesive composition of the present invention contains an adhesive resin, a core-shell polymer particle (A) having a volume average particle diameter of 10 to 300 nm, and a polymer particle (B) having a volume average particle diameter of 400 nm to 10000 nm,
  • the weight ratio of polymer particles (A): polymer particles (B) is 1: 2 to 2: 1, and the core-shell polymer particles (A) and the polymer particles (B) are dispersed as primary particles in the adhesive composition. It is characterized by being formed.
  • the adhesive resin which is a matrix resin in the adhesive composition of the present invention can be selected from various resins exhibiting adhesiveness regardless of thermoplasticity and curability, and is not particularly limited. Examples include vinyl acetate copolymer resin, polyolefin resin, polyamide resin, synthetic rubber, acrylic resin, polyurethane resin, etc.
  • vinyl acetate copolymer resin polyolefin resin, polyamide resin, synthetic rubber, acrylic resin, polyurethane resin, etc.
  • curable resin phenol resin, epoxy resin, polyurethane curable resin, urea resin, melamine resin, acrylic reaction Examples thereof include resins. From the viewpoints of adhesiveness, applicability, heat resistance, etc., an epoxy resin is preferable.
  • the epoxy resin may generally be a compound having two or more epoxy groups.
  • bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AD type, bisphenol Bifunctional glycidyl ether type such as epoxy compound having bisphenyl group such as AF type and biphenyl type, epoxy compound such as polyalkylene glycol type and alkylene glycol type, epoxy compound having naphthalene ring, epoxy compound having fluorene group Epoxy resin, phenol novolak type, orthocresol novolak type and other novolak type epoxy resin, polyfunctional glycidyl ether, tetraphenylol ethane type and other polyfunctional type glycidyl ether type epoxy resin, die -Glycidyl ester type epoxy resins of synthetic fatty acids such as acids, N, N, N ', N'-tetraglycidyldiaminodiphenylmethane (TGDDM),
  • An epoxy resin can be suitably selected according to the use etc. of an adhesive composition, and only 1 type may be used and it may be used in combination of 2 or more type.
  • Bisphenol A-type epoxy resins and bisphenol F-type epoxy resins are particularly preferable in terms of facilitating the adjustment of the viscosity of the adhesive composition.
  • Bisphenol A type epoxy resin is a polycondensation compound of bisphenol A and epichlorohydrin.
  • the bisphenol A skeleton enhances heat resistance and also improves toughness and tensile shear bond strength. Furthermore, the ether group in the skeleton improves chemical resistance, and the methylene chain increases flexibility.
  • This bisphenol A type epoxy resin those ranging from liquid to solid can be used depending on the molecular weight, but those which are liquid to semi-solid at room temperature are preferred, and liquids are particularly preferred. This is because the handling property and the application workability of the composition become easy.
  • the epoxy equivalent is preferably in the range of 180 to 300 g / eq.
  • an epoxy equivalent means the gram number of the resin containing 1 gram equivalent of an epoxy group (unit: g / eq).
  • a modified epoxy resin such as urethane-modified epoxy resin or dimer acid modification
  • the epoxy resin the structure is not particularly limited as long as it has a urethane bond and two or more epoxy groups in the molecule. From the point that it can be introduced into the molecule, a resin obtained by reacting a urethane bond-containing compound having an isocyanate group with a hydroxy group-containing epoxy compound is preferable. These epoxy resins can be used alone or in combination of two or more.
  • the adhesive composition of the present invention may contain an appropriate curing agent depending on the type of adhesive resin.
  • the curing agent used in combination with the adhesive resin only needs to have an active group capable of reacting with an epoxy group.
  • curing agents include imidazole compounds such as dicyandiamide, 4,4′-diaminodiphenylsulfone, and 2-n-heptadecylimidazole, adipic acid dihydrazide, stearic acid dihydrazide, isophthalic acid dihydrazide, and dibasic acid hydrazide.
  • Organic acid hydrazide compounds such as isophthalic acid dihydrazide, urea compounds such as N, N-dialkylurea derivatives and N, N-dialkylthiourea derivatives, acid anhydrides such as tetrahydrophthalic anhydride, semicarbazide, cyanoacetamide, diamino Amine compounds such as diphenylmethane, tertiary amine, polyamine, isophoronediamine, m-phenylenediamine, aminotriazole such as 3-amino-1,2,4-triazole, N-aminoethylpiperazine, melamines, acetog Guanamines such as anamin and benzoguanamine, guanidines, dimethylureas, boron trifluoride complex compounds, boron trichloride complex compounds, liquid phenols such as trisdimethylaminomethylphenol, polythiols, triphenylphosphine, keti
  • the blending amount is preferably in the range of 5 to 30 parts by weight with respect to 100 parts by weight of the adhesive resin.
  • the blending amount of the curing agent is 5 parts by weight or more, the curing rate of the adhesive composition is high, and the curing reaction proceeds sufficiently to improve physical properties such as adhesive strength.
  • a preferable amount of the curing agent is in the range of 7 to 30 parts by weight.
  • the adhesive composition of the present invention contains core-shell polymer particles (A) having a smaller particle size compared to the polymer particles (B). By mix
  • the volume average particle size of the core-shell polymer particles (A) is 10 nm to 300 nm, more preferably 30 nm to 250 nm, still more preferably 60 nm to 200 nm, and most preferably 80 nm to 150 nm.
  • the volume average particle diameter of the core-shell polymer particles (A) is less than 10 nm or larger than 300 nm, the effect of toughening the adhesive composition by the core-shell polymer particles (A) is reduced.
  • the volume average particle size (Mv) of the core-shell polymer particles (A) is measured using a Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.) while being dispersed in an aqueous latex or resin composition. Value.
  • the aqueous latex is diluted with deionized water and the sample concentration is adjusted so that the Signal Level is in the range of 0.6 to 0.8.
  • the refractive index of water and the refractive index of the polymer particles to be measured were input, and the measurement time was 600 seconds.
  • the resin composition When measuring the volume average particle diameter of the particles in the resin composition, the resin composition is diluted with methyl ethyl ketone and the sample concentration is adjusted so that the signal level is in the range of 0.6 to 0.8.
  • the refractive index of methyl ethyl ketone and the refractive index of the polymer particles to be measured were input, and the measurement time was 600 seconds.
  • the description regarding the measurement of the above volume average particle diameter is applied also to the measurement of the volume average particle diameter of a polymer particle (B).
  • the core-shell polymer particle (A) is a core-shell polymer particle in which a shell layer is formed by graft polymerization of a graft copolymerizable monomer (a monomer for shell formation) to a crosslinked polymer to be a core layer, It has a structure having a core layer made of a cross-linked polymer existing inside and at least one shell layer covering the periphery or part of the cross-linked polymer by graft polymerization on the surface of the core layer. From the point that the viscosity of the adhesive composition of the present invention is kept low and easy to handle, the core-shell polymer particles are stably dispersed in the adhesive composition, and the toughening effect of the adhesive composition is enhanced.
  • the weight ratio of the core layer to the shell layer is preferably in the range of 50/50 to 99/1 in terms of the value of core layer / shell layer (weight ratio of monomers forming the polymer of each layer) / 40 to 95/5 is more preferable, and 70/30 to 90/10 is still more preferable.
  • the core layer is preferably composed of a crosslinked polymer and does not substantially dissolve in the solvent. Therefore, the gel content of the core layer is preferably 60% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, and particularly preferably 95% by weight or more.
  • the core layer comprises (i) 50% by weight or more of at least one monomer selected from the group consisting of diene monomers and (meth) acrylate monomers, and other copolymerizable vinyls.
  • Rubber elastic body composed of less than 50% by weight of monomer, (ii) polysiloxane rubber-based elastic body, (iii) cross-linked aromatic vinyl, or (iv) two kinds of (i) to (iii) above It is preferable to consist of a mixture of the above.
  • the other copolymerizable vinyl monomer is selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound, an unsaturated carboxylic acid derivative, a (meth) acrylic acid amide derivative, and a maleimide derivative. It is preferable that it is a seed or more.
  • (meth) acryl means acryl and / or methacryl.
  • diene monomer examples include butadiene, isoprene, chloroprene and the like, and butadiene is particularly preferable.
  • (meth) acrylic acid ester monomer examples include butyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, and the like, and butyl acrylate and 2-ethylhexyl acrylate are particularly preferable. These may be used alone or in combination of two or more.
  • the amount of one or more monomers selected from the group consisting of diene monomers and (meth) acrylic acid ester monomers is preferably 50% by weight or more based on the total weight of the core layer. Preferably it is 60 weight% or more. When the amount of the monomer used is less than 50% by weight, the toughening effect exhibited by the core-shell polymer particles may be reduced.
  • the core layer may be a homopolymer or a copolymer obtained by polymerizing one or more monomers selected from the group consisting of a diene monomer and a (meth) acrylic acid ester monomer. However, it may be a copolymer of a diene monomer and / or a (meth) acrylate monomer and a vinyl monomer copolymerizable therewith.
  • a copolymerizable vinyl monomer one kind selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, unsaturated carboxylic acid derivatives, (meth) acrylic acid amide derivatives, and maleimide derivatives. The above monomers are mentioned.
  • Examples of the aromatic vinyl compound include styrene, ⁇ -methylstyrene, and vinyl naphthalene.
  • Examples of the vinyl cyanide compound include (meth) acrylonitrile and substituted acrylonitrile.
  • Examples of the unsaturated carboxylic acid derivative include (meth) acrylic acid, itaconic acid, crotonic acid, maleic anhydride and the like.
  • Examples of the (meth) acrylamide derivative include (meth) acrylamide (including N-substituted product).
  • Examples of the maleimide derivative include maleic imide (including N-substituted product). These may be used alone or in combination of two or more.
  • the amount of these copolymerizable vinyl monomers used is preferably less than 50% by weight, more preferably less than 40% by weight, based on the weight of the entire core layer.
  • the core layer may be a cross-linked aromatic vinyl.
  • the crosslinked body include a copolymer of an aromatic vinyl compound and a crosslinking monomer.
  • the aromatic vinyl compound include unsubstituted vinyl aromatic compounds such as styrene and 2-vinylnaphthalene; substituted vinyl aromatic compounds such as ⁇ -methylstyrene; 3-methylstyrene, 4-methylstyrene, 2,4 -Ring alkylated vinyl aromatic compounds such as dimethyl styrene, 2,5-dimethyl styrene, 3,5-dimethyl styrene, 2,4,6-trimethyl styrene; ring alkoxyl such as 4-methoxy styrene and 4-ethoxy styrene Vinyl aromatic compounds; ring halogenated aromatic compounds such as 2-chlorostyrene and 3-chlorostyrene; ring ester-substituted vinyl aromatic compounds such as 4-acetoxystyrene;
  • the polymer constituting the core layer is obtained by copolymerizing a crosslinking monomer in order to adjust the degree of crosslinking.
  • a crosslinking monomer examples include divinylbenzene, butanediol di (meth) acrylate, triallyl (iso) cyanurate, allyl (meth) acrylate, diallyl itaconate, diallyl phthalate, and the like.
  • the amount of the crosslinkable monomer used is 0.2 to 7% by weight, preferably 0.5 to 5% by weight, more preferably 1 to 3% by weight, based on the total weight of the core-shell polymer particles. If the amount used exceeds 7% by weight, the toughening effect and stress relaxation effect of the core-shell polymer particles may be reduced.
  • the core layer may include a polysiloxane rubber-based elastic body.
  • a polysiloxane rubber-based elastic body for example, a polysiloxane rubber composed of alkyl or aryl disubstituted silyloxy units such as dimethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy and the like can be used.
  • the polysiloxane rubber-based elastic body may be crosslinked by using a polyfunctional alkoxysilane compound partly at the time of polymerization, or by radically reacting a silane compound having a vinyl reactive group, if necessary. What introduced the structure is more preferable.
  • the glass transition temperature of the core layer (hereinafter sometimes simply referred to as “Tg”) is preferably 0 ° C. or lower in order to enhance the toughness and stress relaxation effect of the obtained adhesive composition, and ⁇ 20 ° C.
  • Tg glass transition temperature of the core layer
  • the following is more preferable, ⁇ 40 ° C. or lower is further preferable, and ⁇ 60 ° C. or lower is particularly preferable.
  • the polymer constituting the shell layer in the core-shell polymer particle is a (meth) acrylic acid ester monomer, aromatic vinyl monomer, vinyl cyanide monomer, unsaturated carboxylic acid derivative, (meth) acrylamide derivative And (co) polymers obtained by polymerizing one or more selected from the group consisting of maleimide derivatives.
  • the shell layer of the core-shell polymer particles (A) can effectively prevent the core-shell polymer particles (A) from reaggregating and deteriorating the dispersion state when the adhesive composition is cured.
  • It preferably has a group.
  • the reactive group for example, at least one group selected from the group consisting of an epoxy group, a carboxyl group, a hydroxyl group, an amino group, and a carbon-carbon double bond is preferable.
  • the shell layer having a reactive group is a (meth) acrylic acid ester monomer, an aromatic vinyl monomer, a vinyl cyanide monomer, an unsaturated carboxylic acid derivative, a (meth) acrylamide derivative, and / or It is preferably composed of a copolymer obtained by copolymerizing a maleimide derivative and one or more kinds of vinyl monomers having a reactive group as described above.
  • the reactive group which the shell layer of a core shell polymer particle (A) has includes an epoxy group.
  • Examples of the (meth) acrylic acid ester monomers include (meth) acrylic such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. Examples include acid alkyl esters. Examples of aromatic vinyl monomers include alkyl-substituted styrenes such as styrene and ⁇ -methylstyrene, and halogen-substituted styrenes such as bromostyrene and chlorostyrene. Examples of the vinyl cyanide monomer include (meth) acrylonitrile and substituted (meth) acrylonitrile.
  • Examples of the unsaturated carboxylic acid derivative include (meth) acrylic acid, itaconic acid, crotonic acid, maleic anhydride and the like.
  • Examples of the (meth) acrylamide derivative include (meth) acrylamide (including N-substituted product).
  • Examples of the maleimide derivative include maleic imide (including N-substituted product).
  • Examples of the monomer having a reactive group include (meth) acrylic acid esters having a reactive side chain such as 2-hydroxyethyl (meth) acrylate, 2-aminoethyl (meth) acrylate, (meth ) Glycidyl acrylate, etc .;
  • Examples of the vinyl ether having a reactive group include glycidyl vinyl ether and allyl vinyl ether.
  • the shell layer of the core-shell polymer particles (A) is made of, for example, an aromatic vinyl monomer (especially styrene) 0 to 50% by mass (preferably 5 to 40% by mass), a vinyl cyanide monomer. (Especially acrylonitrile) 0-50% by mass (preferably 1-30% by mass, more preferably 10-25% by mass), (meth) acrylic acid ester monomer (especially methyl methacrylate) 0-50% by mass ( Preferably 5 to 45% by mass) and a monomer having a reactive group (particularly glycidyl methacrylate) 0 to 50% by mass (preferably 5 to 30% by mass, more preferably 10 to 25% by mass). It is preferable to comprise a layer-forming monomer (100% by mass in total).
  • the production method of the core-shell polymer particles is not particularly limited, and can be produced by a known method such as emulsion polymerization, suspension polymerization, microsuspension polymerization, and the like. Among these, the production method by multistage emulsion polymerization is particularly preferable.
  • emulsifying (dispersing) agents used in emulsion polymerization include alkyl or aryl sulfonic acids such as dioctyl sulfosuccinic acid and dodecylbenzene sulfonic acid, alkyl or aryl ether sulfonic acids, alkyl or aryl sulfuric acids such as dodecyl sulfuric acid, Alkyl or aryl ether sulfuric acid, alkyl or aryl substituted phosphoric acid, alkyl or aryl ether substituted phosphoric acid, N-alkyl or aryl sarcosine acid such as dodecyl sarcosine acid, alkyl or aryl carboxylic acid such as oleic acid or stearic acid, alkyl or aryl Alkali metal salts or ammonium salts of various acids such as ether carboxylic acids; Nonionic emulsifiers or dispersants such as alkyl or
  • the emulsifier is preferably an anionic emulsifier from the viewpoint of polymerization stability, more preferably an anionic emulsifier of an alkali metal salt, and still more preferably an anionic emulsifier of a sodium salt and / or a potassium salt.
  • emulsifying (dispersing) agents may be used as little as possible within the range that does not hinder the dispersion stability in the preparation process of the aqueous latex containing the core-shell polymer particles.
  • it may be extracted and removed to a residual amount that does not affect the physical properties of the produced adhesive composition. For this reason, it is more preferable that the emulsifying (dispersing) agent has water solubility.
  • the core-shell polymer particles (A) are dispersed in the form of primary particles.
  • the dispersion in the state of primary particles means that, for example, the value of volume average particle diameter (Mv) / number average particle diameter (Mn) of the particles measured in the adhesive composition is 3 or less. Can be confirmed. This value is preferably 2.5 or less, more preferably 2 or less, and even more preferably 1.5 or less.
  • the volume average particle diameter (Mv) / number average particle diameter (Mn) of the particles measured in the adhesive composition exceeds 3, the adhesive composition contains a lot of secondary aggregates. As a result, the physical properties of the adhesive are not stable, for example, it is difficult to develop high fatigue resistance.
  • volume average particle diameter (Mv) / number average particle diameter (Mn) is the volume average of particles in the adhesive composition according to the above description using Microtrac UPA (manufactured by Nikkiso Co., Ltd.).
  • the particle diameter (Mv) and the number average particle diameter (Mn) are measured, respectively, and the volume average particle diameter (Mv) is divided by the number average particle diameter (Mn).
  • the content of the core-shell polymer particles (A) in the adhesive composition of the present invention is preferably 0.5 to 20 parts by weight, more preferably 3 to 15 parts by weight with respect to 100 parts by weight of the adhesive composition. More preferably, it is 5 to 10 parts by weight.
  • the content of the core-shell polymer particles (A) is less than 0.5 parts by weight, the toughening effect of the adhesive composition by the core-shell polymer particles (A) is reduced. At the time of fracture, cracks propagate at the interface between the adhesive layer and the substrate, and the fatigue resistance may be reduced.
  • polymer particles (B) In the adhesive composition of this invention, the polymer particle (B) with a larger particle size is contained with a core-shell polymer particle (A) compared with this.
  • the polymer particle (B) is a particle whose shape does not substantially change in the adhesive composition and after curing, and changes depending on the blending ratio and curing conditions, for example, an island part of a sea-island structure generated by polymer alloy. Such a formulation does not correspond to the polymer particles (B).
  • the polymer particles (B) are preferably polymer particles that do not have a hollow structure (that is, polymer particles that do not have cavities containing liquid and / or gas inside the particles).
  • the particles are not easily destroyed even when subjected to an impact when the components are blended and mixed, and it is easy to disperse as primary particles.
  • the polymer particles (B) as described above, control of the particle diameter and control of the content of the particles are facilitated, and the physical properties of the adhesive are stabilized.
  • the volume average particle diameter of the polymer particles (B) is 400 nm to 10000 nm, more preferably 500 nm to 8000 nm, still more preferably 1000 nm to 6000 nm, and most preferably 2000 nm to 4000 nm.
  • the volume average particle diameter of the polymer particles (B) can be measured in the same manner as the volume average particle diameter of the core-shell polymer particles (A) described above.
  • the polymer particle (B) according to the present invention is a particle composed of a polymer because it is suitable for relieving repeated stress during long-term use.
  • the shape of the particles is not particularly limited, and may be any shape such as a spherical shape or a flat plate shape.
  • the type of polymer constituting the polymer particles (B) is not particularly limited, and examples thereof include rubbers, acrylic resins, polyolefins, polystyrenes, urethanes, polyesters, polyamides, polyimides, polysiloxanes, fluorine-containing resins, and core-shell polymers. It is done.
  • the polymer particle (B) is a polyolefin, polysiloxane, fluorine-containing resin, or core-shell polymer particle because it is easy to design to ensure separation at the interface between the matrix resin and the polymer particle (B). preferable.
  • Specific examples of the polyolefin include polyethylene and polypropylene, and specific examples of the fluorine-containing resin include polytetrafluoroethylene.
  • the core-shell polymer particles which is a preferred embodiment of the polymer particles (B) are the same as the details of the core-shell polymer particles (A), and thus description thereof is omitted.
  • the polymer particles (B) are peeled from the matrix resin at the time of fatigue failure, in the core-shell polymer particles that are a preferred embodiment of the polymer particles (B), the shell layer is separated from the matrix resin. It is preferable that there is no reactive group that reacts, or the amount is small even if it has.
  • the content of the monomer unit having a reactive group contained in the polymer constituting the shell layer of the core-shell polymer particle is 0 to 5 parts by weight with respect to 100 parts by weight of the polymer particle (B). It is preferably 0 to 4 parts by weight, more preferably 0 to 3 parts by weight, and most preferably 0 to 2 parts by weight.
  • the reactive group and the monomer having the reactive group are the same as described above.
  • the polymer particles (B) are dispersed in the form of primary particles in the same manner as the core-shell polymer particles (A).
  • the primary dispersion means that the volume average particle diameter (Mv) / number average particle diameter (Mn) of the particles measured in the adhesive composition is 3. This can be confirmed by the following.
  • the preferred range and calculation method of volume average particle size (Mv) / number average particle size (Mn) are the same as those described above for the core-shell polymer particles (A).
  • the content of the polymer particles (B) in the adhesive composition of the present invention is preferably 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, with respect to 100 parts by weight of the adhesive composition.
  • the amount is more preferably 3 to 6 parts by weight, and particularly preferably 4 to 5 parts by weight.
  • the content of the polymer particles (B) is less than 1 part by weight, the effect obtained by the addition of the polymer particles (B) is reduced.
  • the adhesive composition of the core-shell polymer particles (A) is used. The adhesive composition may become so brittle that the toughening effect of the product is not exhibited, and the fatigue resistance may be reduced.
  • the amount of the polymer particles (B) is relatively larger than 1: 2
  • the adhesive composition becomes brittle, and the fatigue resistance is lowered.
  • the amount of the core-shell polymer particles (A) is relatively larger than 2: 1, cracks propagate at the interface between the adhesive layer and the base material at the time of fatigue failure, resulting in interface failure, and fatigue resistance characteristics are reduced. To do.
  • the fracture surface of the test piece after the shear adhesion fatigue test is visually confirmed, and an area of 40% or more of the fracture surface
  • the case where the adhesive remains on the surface of the metal substrate is evaluated as cohesive failure (CF), and the case where it is less than 40% is evaluated as interfacial failure (AF).
  • CF cohesive failure
  • AF interfacial failure
  • the fatigue-breaked surface is observed with a reflection electron image of a scanning electron microscope, and each pixel of the obtained image is divided into monochrome 255 gradations to express the distribution of lightness.
  • binarizing 0 to 218 as an adhesive and gradations from 219 to 255 as an adherend and calculating the ratio of the area where the adhesive layer remains.
  • a thixotropic agent may be blended in the adhesive composition of the present invention in order to improve handling properties.
  • a thixotropic agent is not particularly limited, and examples thereof include carbon black such as ketjen black, silica, fine calcium carbonate, sepiolite and the like.
  • a thixotropic agent can be used 1 type or in combination of 2 or more types.
  • the blending amount is preferably 10 parts by weight or less with respect to 100 parts by weight of the adhesive resin from the viewpoint of application workability and adhesive strength.
  • the thixotropic agent it is preferable to use solid particles having an average particle diameter measured by a laser diffraction / scattering method within a range of 0.01 ⁇ m to 0.1 ⁇ m. If the average particle size is less than 0.01 ⁇ m, the viscosity of the adhesive composition may be increased and handling properties may be deteriorated. On the other hand, if the average particle size exceeds 0.1 ⁇ m, application workability and adhesive strength may be reduced. Because.
  • the adhesive composition of the present invention can also be blended with a filler for adjusting the viscosity of the composition and improving mechanical properties to the extent that the effects of the present invention are not impaired.
  • a filler is not particularly limited, for example, calcium carbonate, talc, magnesia, calcium silicate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, alumina, zircon, graphite, barium sulfate, clay, mica, Kaolin, wollastonite, mica, feldspar, syenite, chlorite, talc, bentonite, montmorillonite, barite, dolomite, quartz, diatomite, calcium silicate, aluminum silicate, barium carbonate, magnesium carbonate , Zinc carbonate, textile fiber, glass fiber, aramid pulp, boron fiber, carbon fiber, phosphate, crystalline silica, amorphous silica, fused silica, fumed silica, calcined silica, precipitated
  • the average particle diameter measured by a laser diffraction / scattering method is preferably in the range of 0.05 ⁇ m to 500 ⁇ m. If the average particle size is less than 0.05 ⁇ m, the viscosity of the adhesive composition may be increased and the handleability may deteriorate, and if it exceeds 500 ⁇ m, the filler tends to settle and the uniformity of the composition may decrease. There is sex.
  • various additives such as a catalyst, a curing accelerator, a plasticizer, a reactive diluent, a reaction retarding agent, an antioxidant, an antioxidant, a pigment, Dyes, colorants, coupling agents, leveling agents, thixotropic agents, adhesion imparting agents, flame retardants, antistatic agents, conductivity imparting agents, lubricants, slidability imparting agents, UV absorbers, surfactants, A dispersant, a dispersion stabilizer, an antifoaming agent, a dehydrating agent, a crosslinking agent, a rust preventive agent, a solvent and the like can be blended.
  • the adhesive composition of the present invention can be prepared by uniformly mixing and stirring these blended components with a known mixing and dispersing machine such as a planetary mixer, a disper, a Henschel mixer, a kneader and the like. Also, after preparing a mixture of the adhesive resin and the core-shell polymer particles (A) and a mixture of the adhesive resin and the polymer particles (B), respectively, the both mixtures are mixed to prepare the adhesive composition of the present invention. May be. Further, in order to disperse each of the core-shell polymer particles (A) and the polymer particles (B) as primary particles in the adhesive composition, the core-shell polymer particles (A) and / or the polymer particles (B) are dispersed. This can be achieved by dissolving the adhesive resin and then distilling off the dispersion medium (or solvent) from the dispersion.
  • a known mixing and dispersing machine such as a planetary mixer, a disper, a Henschel mixer, a knea
  • the adhesive composition of the present invention thus prepared is applied to an adherend by a known method such as spraying, gunning, brushing or the like.
  • a known method such as spraying, gunning, brushing or the like.
  • spot welding after application welding bond method
  • the adhesive composition of the present invention has high fatigue resistance and adhesion reliability, it can be used, for example, in automobiles, vehicles (bullet trains, trains), wind power generators, civil engineering, architecture, electronics, ships, aircraft, space industry, etc. It can be used as an adhesive for structural members. At this time, high joint strength to the structural part can be ensured by the combined use (weld bond method) such as spot welding using an electrode or the like. In addition, it can be used as an adhesive for general office work, medical use, and electronic materials.
  • volume average particle diameter (Mv) The volume average particle diameter (Mv) of the polymer particles dispersed in the aqueous latex or resin composition was measured using Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.). The aqueous latex diluted with deionized water and the resin composition diluted with methyl ethyl ketone were used as measurement samples. For measurement, enter the refractive index of water or methyl ethyl ketone, and the refractive index of each polymer particle, and adjust the sample concentration so that the measurement time is 600 seconds and the Signal Level is in the range of 0.6 to 0.8. went.
  • a glass reactor 180 parts by weight of deionized water, 0.002 parts by weight of disodium ethylenediaminetetraacetate (EDTA), 0.001 part by weight of ferrous sulfate heptahydrate, sodium formaldehyde sulfoxylate (SFS) 0 .04 parts by weight and 0.5 parts by weight of sodium dodecylbenzenesulfonate (SDBS) were charged, and the temperature was raised to 45 ° C. while stirring in a nitrogen stream.
  • EDTA disodium ethylenediaminetetraacetate
  • FSS sodium formaldehyde sulfoxylate
  • SDBS sodium dodecylbenzenesulfonate
  • a monomer mixture of 98 parts by weight of n-butyl acrylate (BA), 2 parts by weight of allyl methacrylate (ALMA) and 0.02 parts by weight of cumene hydroperoxide (CHP) was added dropwise over 5 hours.
  • 1 part by weight of SDBS in an aqueous solution having a concentration of 5% by weight was continuously added over 5 hours.
  • Stirring was continued for 1 hour after completion of the monomer mixture addition to complete the polymerization, and an acrylic rubber latex (R-1) containing acrylic rubber particles was obtained.
  • the volume average particle diameter of the acrylic rubber particles contained in the obtained latex was 100 nm.
  • 0.025 parts by weight of PHP was added after 3, 5, and 7 hours from the start of polymerization.
  • 0.0006 part by weight of EDTA and 0.003 part by weight of ferrous sulfate heptahydrate were added after 4, 6 and 8 hours from the start of polymerization.
  • the residual monomer was removed by devolatilization under reduced pressure to complete the polymerization, and a polybutadiene rubber latex (R-2) containing polybutadiene rubber particles was obtained.
  • the volume average particle diameter of the polybutadiene rubber particles contained in the obtained latex was 80 nm.
  • a glass reactor having a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer and emulsifier addition device, 173 parts by weight of deionized water, 0.3 part by weight of SDBS, and 1% aqueous sodium nitrite solution After adding 0.008 part by weight and adjusting to 30 ° C. in a nitrogen atmosphere, the emulsified monomer solution obtained above was charged. Thereafter, the temperature was raised to 65 ° C., and a monomer mixture of 83 parts by weight of BA and 4.15 parts by weight of ALMA was continuously added over 210 minutes.
  • aqueous latex L-1 containing core-shell polymer particles.
  • the volume average particle size of the core-shell polymer particles contained in the obtained aqueous latex was 110 nm.
  • aqueous latex L-2
  • the volume average particle size of the core-shell polymer particles contained in the obtained aqueous latex was 110 nm.
  • aqueous latex (L-3) containing core-shell polymer particles.
  • the volume average particle size of the core-shell polymer particles contained in the obtained aqueous latex was 3000 nm.
  • aqueous latex (L-4) containing core-shell polymer particles After 0.15 parts by weight of SDBS was added three times at 60 minute intervals, a mixture of 30 parts by weight of MMA and 0.08 parts by weight of TBP was continuously added over 180 minutes. 0.04 part by weight of TBP was added, and stirring was further continued for 30 minutes to complete the polymerization, thereby obtaining an aqueous latex (L-4) containing core-shell polymer particles.
  • the volume average particle diameter of the core-shell polymer particles contained in the obtained aqueous latex was 500 nm.
  • MEK a 1: 1 mixture of bisphenol A type diglycidyl ether (DGEBA, manufactured by Mitsubishi Chemical), which is an epoxy resin, jER828 and jER1001 is used so that the weight ratio of the core-shell polymer particles and the epoxy resin mixture is 25:75.
  • DGEBA bisphenol A type diglycidyl ether
  • MEK was distilled off under reduced pressure to obtain an epoxy resin composition (M-1) in which the core-shell polymer particles (A) were dispersed as primary particles.
  • Examples 1 to 5 and Comparative Examples 1 to 5 Rotate the epoxy resin, the core-shell polymer particle (A) -dispersed epoxy resin composition, the polymer particle (B) -dispersed epoxy resin composition, and the curing agent along the blending amounts described in the “mixing ratio” column of Table 1.
  • -It mixed with the revolution mixer made by Shinkey Co., Ltd.
  • the blending amount is based on weight. It was confirmed by Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.) that the core-shell polymer particles (A) and the polymer particles (B) were dispersed as primary particles in the obtained adhesive composition.
  • the compounding amounts of the epoxy resin, the core-shell polymer particles (A), and the polymer particles (B) with respect to 100 parts by weight of each adhesive composition are as described in the “Composition composition” column of Table 1.
  • Table 1 shows the results of the number of fracture cycles and the type of fracture measured or specified by conducting a fatigue test using each adhesive composition.
  • Epoxy resin bisphenol A type epoxy resin (jER828 and jER1001, manufactured by Mitsubishi Chemical Corporation).
  • Curing agent Diaminodiphenyl sulfone (DDS) (SumiCure S, manufactured by Sumitomo Chemical Co., Ltd.)
  • the core-shell polymer particles (A) and the polymer particles (B) are dispersed as primary particles at an appropriate blending ratio in the epoxy resin composition, and the number of fracture cycles in the fatigue test is In many cases, the fatigue resistance is greatly improved, and the failure mode at the time of fatigue failure is cohesive failure (CF), which indicates that an adhesive composition having high reliability was obtained.
  • CF cohesive failure
  • Comparative Example 1 is an epoxy resin composition containing neither the core-shell polymer particles (A) nor the polymer particles (B).
  • the core-shell polymer particles (A) are dispersed in the epoxy resin composition.
  • the polymer particles (B) are not included.
  • Comparative Examples 2 and 3 as compared with Comparative Example 1, the number of fracture cycles in the fatigue test was not improved, and the failure mode at the time of fatigue failure was interface failure (AF) as in Comparative Example 1. This is presumably because, as shown in FIG. 1, resistance was large for cracks to propagate in the adhesive layer, and interface fracture was induced.
  • Comparative Example 4 is an epoxy resin composition that does not contain core-shell polymer particles (A) and in which polymer particles (B) are dispersed, and Comparative Example 5 includes both core-shell polymer particles (A) and polymer particles (B).
  • Comparative Example 5 includes both core-shell polymer particles (A) and polymer particles (B).
  • the fracture mode at the time of fatigue fracture was cohesive fracture (CF), but the number of fracture cycles in the fatigue test was not improved. It is considered that the toughness of the adhesive layer was not improved because the core-shell polymer particles (A) were not included or the blending ratio was small.
  • Examples 6 and 7 and Comparative Examples 6 and 7 According to the blending amount described in the column of “Mixing ratio” in Table 2, the epoxy resin, the core-shell polymer particles (A) dispersed epoxy resin composition, the polymer particles (B), and the curing agent are rotated and revolved (( And an adhesive composition was obtained.
  • the blending amount is based on weight. It was confirmed by Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.) that the core-shell polymer particles (A) and the polymer particles (B) were dispersed as primary particles in the obtained adhesive composition.
  • the compounding amounts of the epoxy resin, the core-shell polymer particles (A), and the polymer particles (B) with respect to 100 parts by weight of each adhesive composition are as described in the “Composition composition” column of Table 2.
  • Table 2 shows the results of the number of fracture cycles and the type of fracture measured or specified by conducting a fatigue test using each adhesive composition.
  • Example 6 the materials constituting the polymer particles (B) were changed, but in the epoxy resin composition, the core-shell polymer particles (A) and the polymer particles (B) were mixed at an appropriate blending ratio.
  • CF cohesive fracture
  • Comparative Example 6 is an epoxy resin composition using polymer particles (B) having a volume average particle diameter as large as 17 ⁇ m
  • Comparative Example 7 is a blending ratio of polymer particles (B) to core-shell polymer particles (A). Is a low epoxy resin composition.
  • the number of fracture cycles in the fatigue test was not improved, and the fracture mode at the time of fatigue fracture was also interface fracture (AF).
  • Adhesive layer 11 11 'Base material 12 12' Spacer (aluminum plate) 13 13 'Spacer (Nitoflon tape) 14 Adhesive composition 15 Adhesive layer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne une composition adhésive qui contient une résine adhésive, des particules polymères type cœur-écorce (A) qui présentent un diamètre de particule moyen en volume de 10 à 300 nm, et des particules polymères (B) qui présentent un diamètre de particule moyen en volume de 400 à 10 000 nm, et qui est configurée de sorte que le rapport en poids des particules polymères type cœur-écorce (A) aux particules polymères (B) est de 1:2 à 2:1, et les particules polymères type cœur-écorce (A) et les particules polymères (B) sont dispersées dans la composition adhésive sous la forme des particules primaires, respectivement.
PCT/JP2019/012966 2018-03-28 2019-03-26 Composition adhésive WO2019189238A1 (fr)

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JP2012177013A (ja) * 2011-02-25 2012-09-13 Adeka Corp エポキシ樹脂組成物及び絶縁接着剤
JP2015501853A (ja) * 2011-11-09 2015-01-19 サイテク・テクノロジー・コーポレーシヨン 構造用接着剤およびその接合への適用
WO2015064561A1 (fr) * 2013-10-29 2015-05-07 株式会社カネカ Composition de résine durcissable contenant des particules fines de polymère et ayant une stabilité améliorée au stockage
JP2015108077A (ja) * 2013-12-05 2015-06-11 アイシン化工株式会社 構造用接着剤組成物
JP2015529266A (ja) * 2012-09-07 2015-10-05 ダウ グローバル テクノロジーズ エルエルシー 強化エポキシ樹脂配合物

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WO2009051067A1 (fr) 2007-10-18 2009-04-23 Hitachi Chemical Company, Ltd. Composition adhésive, matériau de connexion de circuit utilisant la composition adhésive, procédé pour connecter un élément de circuit et corps de connexion de circuit
JP6389820B2 (ja) 2012-09-06 2018-09-12 アラーガン、インコーポレイテッドＡｌｌｅｒｇａｎ，Ｉｎｃｏｒｐｏｒａｔｅｄ ヒアルロン酸／コラーゲン系真皮充填剤組成物およびそれを作製するための方法
JP6700563B2 (ja) 2015-02-20 2020-05-27 株式会社スリーボンド 多成分型の接着剤、その反応物の製造方法および積層体の製造方法
JP2016185632A (ja) 2015-03-27 2016-10-27 東レ株式会社 積層ポリエステルフィルム
JP6722477B2 (ja) 2015-04-09 2020-07-15 株式会社カネカ 剥離接着性および耐衝撃剥離接着性の改善されたポリマー微粒子含有硬化性樹脂組成物
JP6808931B2 (ja) * 2015-11-27 2021-01-06 日本ゼオン株式会社 非水系二次電池接着層用組成物、非水系二次電池用接着層、及び非水系二次電池

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5955540A (en) * 1994-02-22 1999-09-21 The Dow Chemical Company Process for the preparation of multimodal ABS polymers
JP2012177013A (ja) * 2011-02-25 2012-09-13 Adeka Corp エポキシ樹脂組成物及び絶縁接着剤
JP2015501853A (ja) * 2011-11-09 2015-01-19 サイテク・テクノロジー・コーポレーシヨン 構造用接着剤およびその接合への適用
JP2015529266A (ja) * 2012-09-07 2015-10-05 ダウ グローバル テクノロジーズ エルエルシー 強化エポキシ樹脂配合物
WO2015064561A1 (fr) * 2013-10-29 2015-05-07 株式会社カネカ Composition de résine durcissable contenant des particules fines de polymère et ayant une stabilité améliorée au stockage
JP2015108077A (ja) * 2013-12-05 2015-06-11 アイシン化工株式会社 構造用接着剤組成物

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