Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/10—Adhesives in the form of films or foils without carriers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4014—Nitrogen containing compounds
  • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
• • 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
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • 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
  • C09J2400/00—Presence of inorganic and organic materials
  • C09J2400/20—Presence of organic materials
  • C09J2400/26—Presence of textile or fabric
• • 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
  • C09J2463/00—Presence of epoxy resin
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2852—Adhesive compositions
  • Y10T428/287—Adhesive compositions including epoxy group or epoxy polymer

Definitions

• the present invention relates to an adhesive. More specifically, the present invention relates to an adhesive capable of firmly adhering dissimilar materials at the time of laminating dissimilar materials (particularly, adhering dissimilar metals).
• a cured product of a resin composition containing an epoxy resin as a main component is excellent in many points such as dimensional stability, mechanical strength, electrical insulation, heat resistance, water resistance, and chemical resistance, and has a vehicle structure. It is used as a structural adhesive for panels and the like.
• the use of adhesives is increasing in combination with rivet joining and spot welding, and the adhesives used are generally structural adhesives with high adhesive strength, which are high. Those with shear adhesion strength are selected.
• Patent Document 1 describes that the impact resistance and peel strength of a cured product obtained by adding a rubber-modified epoxy resin and a reactive reinforcing agent are improved, and Patent Document 2 describes that an epoxy resin and polymer fine particles are used. It is described that high adhesive strength can be achieved while maintaining high elastic coefficient by adding.
• the present invention provides an epoxy-based adhesive capable of coagulating and breaking without interfacial peeling even when bonding different materials while maintaining the adhesive strength under such a background.
• an adhesive containing the curing agent (B) in a specific composition ratio it was found that this problem can be solved. That is, conventionally, when both the bisphenol A type epoxy resin (A1) and the bisphenol F type epoxy resin (A2) are used, the bisphenol F type epoxy resin (A2) is used in order to improve the elastic coefficient of the cured product and raise the glass transition temperature.
• the content ratio of bisphenol A type epoxy resin (A1) to bisphenol F type epoxy resin (A2) is set to a specific amount or less.
• the present invention provides the following [1] to [15].
• An epoxy-based adhesive containing an epoxy resin (A) and a curing agent (B).
• the epoxy resin (A) contains a bisphenol A type epoxy resin (A1), a bisphenol F type epoxy resin (A2), and a rubber-modified epoxy resin (A3).
• An epoxy-based adhesive characterized in that the content ratio [(A1) / (A2)] of the bisphenol A type epoxy resin (A1) to the bisphenol F type epoxy resin (A2) is less than 2.7.
• the epoxy-based adhesive according to any one of [1] to [9], which is used for adhering dissimilar materials.
• An adhesive sheet comprising the epoxy-based adhesive according to any one of [1] to [9].
• An adhesive sheet for adhering different materials which comprises the epoxy-based adhesive according to [10].
• It contains an epoxy resin (A) and a curing agent (B), and contains a bisphenol A type epoxy resin (A1), a bisphenol F type epoxy resin (A2), and a rubber-modified epoxy resin (A3) as the epoxy resin (A).
• the epoxy-based adhesive of the present invention can be coagulated and broken without interfacial peeling when adhering different materials while maintaining the adhesive strength. Therefore, it is possible to provide an adhesive having good adhesiveness.
• epoxy resin is generally used as the name of one category of thermosetting resin, or the name of a chemical substance category of a compound having one or more epoxy groups in a molecule. Although it is used, it is used in the latter sense in the present invention. Further, in the present invention, as long as the compound has one or more epoxy groups in the molecule, not only the polymer having a specific degree of polymerization but also the monomer is included in the definition of the epoxy resin.
• molecular weight as used herein means a number average molecular weight unless otherwise specified.
• normal temperature means 25 ° C.
• solid at 25 ° C.” means that the softening point is 25 ° C. or higher, or the viscosity at 25 ° C. is 1000 Pa ⁇ s or higher.
• the epoxy adhesive of the present invention uses an epoxy resin (A) as a curing component, and as the epoxy resin (A), a bisphenol A type epoxy resin (A1), a bisphenol F type epoxy resin (A2), and a bisphenol F type epoxy resin (A2). It contains a rubber-modified epoxy resin (A3) as an essential component.
• the content ratio [(A1) / (A2)] of the bisphenol A type epoxy resin (A1) to the bisphenol F type epoxy resin (A2) needs to be less than 2.7. Yes, preferably less than 2.5, particularly preferably less than 1.5, still more preferably less than 1.0, particularly preferably less than 0.9, more preferably less than 0.8.
• the content ratio [(A1) / (A2)] is 2.7 or more, the fracture mode becomes interface peeling and the effect of the present invention is not sufficiently exhibited, which is not preferable.
• the lower limit of the content ratio is not particularly limited, but is, for example, 0.01 or more.
• Examples of the commercially available bisphenol A type epoxy resin (A1) used in the present invention include EPON825, jER826, jER827, jER828, jER834, jER1001 (all manufactured by Mitsubishi Chemical Co., Ltd.), Epicron 850 (manufactured by DIC), and the like. Epototo YD-128 (manufactured by Nippon Steel & Sumitomo Metal Corporation), DER-331, DER-332 (above, manufactured by Dow Chemical Japan), Bakelite EPR154, Bakelite EPR162, Bakelite EPR172, Bakelite EPR173, Bakelite EPR173, Bakelite AG) and the like. Among these, jER828 and jER1001 are preferable in terms of the elastic modulus of the cured product of the epoxy adhesive and the glass transition temperature.
• the bisphenol A type epoxy resin (A1) may be used alone or in combination of two or more.
• the number average molecular weight of the bisphenol A type epoxy resin (A1) is preferably 200 to 100,000, particularly preferably 200 to 80,000, and even more preferably 200 to 60,000. If the number average molecular weight is too low, the viscosity tends to decrease too much, and the workability as an adhesive tends to decrease. If the number average molecular weight is too high, the solubility in other monomers decreases and the viscosity increases too much. Workability tends to decrease.
• the "number average molecular weight" is a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method.
• the epoxy equivalent of the bisphenol A type epoxy resin (A1) is preferably 20000 or less, particularly preferably 10000 or less, and further preferably 6000 or less. If the epoxy equivalent is too high, the solubility in other monomers tends to decrease, and the workability tends to decrease at the time of compounding.
• the lower limit of the epoxy equivalent is not particularly limited, but is, for example, 50 or more.
• epoxy equivalent is a value measured according to JIS-K7236: 2001.
• the softening point of the bisphenol A type epoxy resin (A1) is preferably 160 ° C. or lower, particularly preferably 140 ° C. or lower, and even more preferably 120 ° C. or lower. If the softening point is too high, the viscosity at room temperature after blending increases, and the workability as an adhesive tends to decrease.
• the lower limit of the softening point is not particularly limited, but is, for example, ⁇ 50 ° C. or higher.
• a "softening point” is a value measured according to JIS-K7234: 2008 (ring ball method).
• Examples of the bisphenol F type epoxy resin (A2) used in the present invention include commercially available jER806, jER807, jER4005P, jER4007P, jER4010P, jER1750 (all manufactured by Mitsubishi Chemical Corporation), Epicron 830 (manufactured by DIC), and Epototo YD. -170, Epototo YD-175 (above, manufactured by Nippon Steel & Sumitomo Metal Corporation), Bakelite EPR169 (manufactured by Bakelite AG), GY281, GY282, GY285 (above, manufactured by Huntsman Advanced Materials) and the like.
• jER806, jER807, and jER4005P are preferable because they are excellent in adhesion after curing of the epoxy adhesive.
• the bisphenol F type epoxy resin (A2) may be used alone or in combination of two or more.
• the number average molecular weight of the bisphenol F type epoxy resin (A2) is preferably 200 to 100,000, particularly preferably 200 to 80,000, and even more preferably 200 to 60,000. If the number average molecular weight is too low, the viscosity tends to decrease too much, and the workability as an adhesive tends to decrease. If the number average molecular weight is too high, the solubility in other monomers decreases and the viscosity increases too much. Workability tends to decrease.
• the epoxy equivalent of the bisphenol F type epoxy resin (A2) is preferably 20000 or less, particularly preferably 10000 or less, and further preferably 6000 or less. If the epoxy equivalent is too high, the solubility in other monomers tends to decrease, and the workability tends to decrease at the time of compounding.
• the lower limit of the epoxy equivalent is not particularly limited, but is, for example, 50 or more.
• the softening point of the bisphenol F type epoxy resin (A2) is preferably 160 ° C. or lower, particularly preferably 140 ° C. or lower, and even more preferably 120 ° C. or lower. If the softening point is too high, the viscosity at room temperature after blending increases, and the workability as an adhesive tends to decrease.
• the lower limit of the softening point is not particularly limited, but is, for example, ⁇ 50 ° C. or higher.
• the rubber-modified epoxy resin (A3) used in the present invention is, for example, an epoxy terminal adduct of an epoxy resin and at least one non-crosslinked liquid rubber having an epoxide-reactive group (for example, an amino group or a carboxy group). be.
• the rubber-modified epoxy resin (A3) may be used alone or in combination of two or more.
• the epoxy resin used as a raw material for the rubber-modified epoxy resin (A3) is not particularly limited, and for example, a bisphenol type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, a glycidylamine type epoxy resin, a ring type epoxy resin, and the like. Examples thereof include a dicyclopentadiene type epoxy resin, a phenol novolac type epoxy resin, and an orthocresol novolac type epoxy resin.
• the non-crosslinked liquid rubber used as a raw material for the rubber-modified epoxy resin (A3) is preferably a homopolymer of a conjugated diene or a copolymer of a conjugated diene, particularly a diene / nitrile copolymer.
• the conjugated diene rubber is preferably butadiene or isoprene, with butadiene being particularly preferred.
• the preferred nitrile monomer is acrylonitrile.
• the preferred copolymer is a butadiene-acrylonitrile copolymer.
• the glass transition temperature (Tg) of the non-crosslinked liquid rubber is preferably 20 ° C. or lower, more preferably 10 ° C. or lower, still more preferably 0 ° C. or lower.
• the lower limit of the glass transition temperature is not particularly limited, but is, for example, ⁇ 100 ° C. or higher.
• the "glass transition temperature" is represented by the temperature of the inflection point of the obtained DSC curve obtained by measuring the DSC curve of the sample using a differential scanning calorimeter.
• the non-crosslinked liquid rubber preferably has an average of 1.5 to 2.5 epoxide-reactive end groups per molecule, more preferably 1.8 to 2.2 per molecule.
• the number average molecular weight of the crosslinked liquid rubber is preferably 500 to 10000, more preferably 1000 to 58000.
• a carboxy group-terminated butadiene nitrile rubber (CTBN) -modified epoxy resin and a nitrile butadiene rubber (NBR) -modified epoxy resin are preferable, and a carboxy group-terminated butadiene nitrile rubber (CTBN) -modified epoxy resin is more preferable.
• CTBN carboxy group-terminated butadiene nitrile rubber
• Examples of commercially available products include ADEKA's ADEKA RESIN EPR series (EPR-1415-1, EPR-2000, EPR-2007, EPR-1630), Momentive's EPON Resin 58005 and EPON Resin 58006, and CVC's Hyperx series (Hypox RA).
• ADEKA resin EPR series manufactured by ADEKA is preferable, and EPR-1630 is more preferable, because the adhesion and the elastic modulus after curing are excellent.
• the number average molecular weight of the rubber-modified epoxy resin (A3) is preferably 200 to 200,000, particularly preferably 200 to 100,000, and even more preferably 200 to 80,000. If the number average molecular weight is too low, the viscosity tends to decrease too much, and the workability as an adhesive tends to decrease. If the number average molecular weight is too high, the solubility in other monomers decreases and the viscosity increases too much. Workability tends to decrease.
• the epoxy equivalent of the rubber-modified epoxy resin (A3) is preferably 10,000 or less, particularly preferably 7,000 or less, and further preferably 5,000 or less. If the epoxy equivalent is too high, the softening component does not disperse in the cured product, so that when stress is generated, the stress concentrates on that portion, and the adhesive strength tends to decrease.
• the lower limit of the epoxy equivalent is not particularly limited, but is, for example, 50 or more.
• the softening point of the rubber-modified epoxy resin (A3) is preferably 200 ° C. or lower, particularly preferably 180 ° C. or lower, and further preferably 160 ° C. or lower. If the softening point is too high, the viscosity at room temperature after blending increases, and the workability as an adhesive tends to decrease.
• the lower limit of the softening point is not particularly limited, but is, for example, ⁇ 50 ° C. or higher.
• the aromatic ring-containing epoxy resin (A4) which is solid at room temperature (however, excluding the bisphenol A type epoxy resin (A1), the bisphenol F type epoxy resin (A2), and the rubber-modified epoxy resin (A3)).
• the bisphenol A type epoxy resin (A1), the bisphenol F type epoxy resin (A2), and the rubber-modified epoxy resin (A3) Is preferable in terms of low water absorption, elasticity of the cured product, and glass transition temperature.
• a phenol aralkyl type epoxy resin commercially available, "YX7700” manufactured by Mitsubishi Chemical Co., Ltd.
• a biphenyl type epoxy resin Examples of commercially available products include "YX4000" manufactured by Mitsubishi Chemical Corporation.
• the aromatic ring-containing epoxy resin (A4) which is solid at room temperature, may be used alone or in combination of two or more.
• the number average molecular weight of the aromatic ring-containing epoxy resin (A4) which is solid at room temperature, is preferably 200 to 100,000, particularly preferably 200 to 80,000, and even more preferably 200 to 60,000. If the number average molecular weight is too low, the viscosity tends to decrease too much, and the workability as an adhesive tends to decrease. If the number average molecular weight is too high, the solubility in other monomers decreases and the viscosity increases too much. Workability tends to decrease.
• the epoxy equivalent of the aromatic ring-containing epoxy resin (A4) which is solid at room temperature, is preferably 10,000 or less, particularly preferably 7,000 or less, and further preferably 5,000 or less. If the epoxy equivalent is too high, the solubility in other monomers tends to decrease, and the workability tends to decrease at the time of compounding.
• the lower limit of the epoxy equivalent is not particularly limited, but is, for example, 50 or more.
• the softening point of the aromatic ring-containing epoxy resin (A4) which is solid at room temperature, is preferably 160 ° C. or lower, particularly preferably 140 ° C. or lower, and even more preferably 120 ° C. or lower. If the softening point is too high, the viscosity at room temperature after compounding tends to increase, and the workability as an adhesive tends to decrease.
• the lower limit of the softening point is not particularly limited, but is, for example, ⁇ 50 ° C. or higher.
• the content of the epoxy resin (A) used in the present invention is preferably 30 to 100% by mass, more preferably 40 to 100% by mass, and particularly preferably 50 to 100% by mass with respect to the entire epoxy adhesive. be.
• the content of the bisphenol A type epoxy resin (A1) is preferably 0.01 to 70 with respect to the entire epoxy resin (A) (the total content of all the epoxy resins (A) contained in the epoxy adhesive). It is by mass%, more preferably 0.1 to 60% by mass, and particularly preferably 1 to 50% by mass.
• the content of the bisphenol F type epoxy resin (A2) is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and particularly preferably 10 to 50% by mass with respect to the entire epoxy resin (A). ..
• the content is calculated by dividing the composition into mass ratios. For example, when the content of the composition of 1: 1 bisphenol A type epoxy (A1) and bisphenol F type epoxy (A2) is 10% by mass, (A1) is 5% by mass and (A2) is 5% by mass. calculate.
• the content of the rubber-modified epoxy resin (A3) is preferably 0.01 to 60% by mass, more preferably 1 to 50% by mass, and particularly preferably 5 to 40% by mass with respect to the entire epoxy resin (A). be.
• the content of the rubber-modified epoxy resin (A3) is preferably 0.01 to 55% by mass, more preferably 1 to 45% by mass, and particularly preferably 1 to 45% by mass with respect to the entire curing component other than the curing agent (B). It is 5 to 40% by mass.
• the content of the aromatic ring-containing epoxy resin (A4) that is solid at room temperature is preferably 0 to 80% by mass, more preferably 1 to 70% by mass, and particularly preferably 5 to 5 to the total content of the epoxy resin (A). It is 60% by mass.
• the content ratio [(A1) / (A3)] of the bisphenol A type epoxy resin (A1) to the rubber-modified epoxy resin (A3) is preferably less than 3.0, particularly preferably less than 2.5, and further. It is preferably less than 2.0, and particularly preferably less than 1.5. If the content ratio [(A1) / (A3)] is too high, the fracture form tends to be interfacial peeling, which is not preferable.
• the lower limit of the content ratio is not particularly limited, but is, for example, 0.01 or more.
• the content of the bisphenol A type epoxy resin (A1) is smaller than the content of the bisphenol F type epoxy resin (A2), and the content of the bisphenol A type epoxy resin (A1) is the rubber-modified epoxy resin (A1). It is also preferable that the content is less than 1.5 times the content of A3).
• the epoxy adhesive of the present invention may further contain other epoxy resins other than (A1) to (A4).
• Specific examples thereof include alcohol type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, and dicyclo.
• examples thereof include various epoxy resins such as pentadiene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, polyfunctional phenol type epoxy resin, and aliphatic epoxy resin.
• the epoxy resin (A) used in the present invention preferably contains 50% by mass or more of an epoxy resin that is solid at room temperature with respect to the entire epoxy resin (A), particularly preferably 55% by mass or more, still more preferably 60. It is mass% or more.
• the upper limit of the content of the epoxy resin which is solid at room temperature is not particularly limited, but is, for example, 100% by mass or less.
• examples of the curing agent (B) used in the present invention include amines, acid anhydrides (carboxylic acid anhydrides), phenols (novolac resins and the like), mercaptans, Lewis acid amine complexes, onium salts, imidazoles and the like. Specific examples include Chapter 3 of "Review Epoxy Resin Volume 1 (Epoxy Resin Technology Association, First Edition, published in November 2003)" and “Review Epoxy Resin Recent Progress I (Epoxy Resin Technology Association)”. , First edition, published in March 2009) ”Chapter 2 can be used. Of these, it is preferable to use amine from the viewpoint of adhesiveness.
• the curing agent (B) may be used alone or in combination of two or more.
• amine examples include aromatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone, aliphatic amines, imidazole derivatives, dicyandiamide, tetramethylguanidine, thiourea-added amines, and isomers and modified products thereof.
• aromatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone
• aliphatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone
• imidazole derivatives imidazole derivatives
• dicyandiamide tetramethylguanidine
• thiourea-added amines examples include isomers and modified products thereof.
• dicyandiamide is particularly preferable because it is excellent in pot life of the matrix resin composition.
• the content of the curing agent (B) used in the present invention is preferably 0.01 to 30% by mass, more preferably 0.1 to 25% by mass, and particularly preferably 1 with respect to the entire epoxy resin (A). It is about 20% by mass.
• the epoxy-based adhesive of the present invention may contain polymer fine particles (C) having a core-shell structure.
• the polymer fine particles (C) having a core-shell structure mean a known general core-shell type polymer, that is, polymer particles having different molecular structures in the central portion (core portion) and the outer peripheral portion (shell portion).
• Examples of the components constituting the core portion of the polymer fine particles (C) having a core-shell structure include butadiene rubber (BR), acrylic rubber (ACM), silicone rubber (Si), butyl rubber (IIR), and nitrile rubber (NBR). Examples thereof include styrene-butadiene rubber (SBR), isoprene rubber (IR), and ethylene propylene rubber (EPR). Of these, butadiene rubber is preferable.
• the component constituting the shell portion of the polymer fine particles (C) having a core-shell structure is graft-polymerized on the core portion described above and covalently bonded to the polymer constituting the core component.
• components constituting the shell portion include acrylic acid ester-based monomers, methacrylic acid ester-based monomers, and aromatic vinyl monomers.
• the polymer fine particles (C) having a core-shell structure are, for example, commercially available Kaneka ACE series (B-11A, B-22, B-561, FM-21, M-701, M-711, M-300) manufactured by Kaneka Corporation. , FM-40, M-210, Pa-20, PA101, MR-01, MX-153, MX257, MX154, MX-960, MX-136, MX-965, MX-217, MX227M75, MX-334M75, MX -416, MX-451, etc.), Metabrene manufactured by Mitsubishi Chemical Corporation (Metabren C, Metabren E, Metabren W, Metabren S, etc.) and the like.
• the one with a rubber core is preferable from the viewpoint of flexibility and adhesion.
• the polymer fine particles (C) may be used as they are in the form of particles or may be dispersed in another solution or resin, but are dispersed in an epoxy resin from the viewpoint of being uniformly dispersed in other resins. More preferably, MX-153, MX-154, MX-136, and MX-267 are preferable.
• the polymer fine particles (C) having a core-shell structure may be used alone or in combination of two or more.
• the primary particle size of the polymer fine particles (C) having a core-shell structure used in the present invention is preferably 10 to 100,000 nm, preferably 15 to 50,000 nm, from the elastic modulus, elongation and shear strength of the cured product obtained from the epoxy resin. Is more preferable, and 20 to 10000 nm is particularly preferable.
• the primary particle size represents the volume average particle size of the primary particles, and can be measured using, for example, a nanotrack particle size distribution measuring device (manufactured by Nikkiso Co., Ltd.).
• the content ratio shall be calculated by adding (A1) and (A2) used for dispersion.
• the content of the polymer fine particles (C) having a core-shell structure is preferably 0 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 1 to 40% by mass, based on the entire epoxy adhesive excluding the curing agent (B). It is 2 to 30% by mass.
• the epoxy adhesive of the present invention may contain a curing accelerator (D) from the viewpoint of enhancing the curing activity of the curing agent (B).
• a curing accelerator (D) can be used in order to enhance the curing activity of the dicyandiamide or the like.
• the curing accelerator for dicyandiamide include 3-phenyl-1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU), and 2,4-diamino-6- (2).
• urea derivatives such as 2,4-bis (3,3-dimethylureido) toluene, imidazole derivatives and the like can be mentioned.
• urea derivatives are preferable, and 2,4-diamino-6- (2-methylimidazolyl- (1))-ethyl-s-triazine is more preferable.
• the content of the curing accelerator (D) used in the present invention is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, and particularly preferably to the whole of the curing agent (B). It is 0.1 to 20% by mass.
• the epoxy adhesive of the present invention has three components as the epoxy resin (A), a bisphenol A type epoxy resin (A1), a bisphenol F type epoxy resin (A2), and a rubber-modified epoxy resin (A3), and a curing agent ( It contains B) as an essential component, and more preferably contains polymer fine particles (C) having a core-shell structure and a curing accelerator (D). Further, in the present invention, other compounding components are used as necessary within a range that does not impair the effect of the present invention (for example, the content is within 5% by mass with respect to the entire epoxy adhesive). Can be done.
• dehydrating agents such as calcium oxide, colorants such as pigments and dyes, extender pigments, ultraviolet absorbers, antioxidants, stabilizers (antigelling agents), plasticizers, leveling agents, and erasing agents.
• dehydrating agents such as calcium oxide
• colorants such as pigments and dyes, extender pigments, ultraviolet absorbers, antioxidants, stabilizers (antigelling agents), plasticizers, leveling agents, and erasing agents.
• foaming agents silane coupling agents, antistatic agents, flame retardants, lubricants, thickeners, low shrinkage agents, organic fillers, inorganic fillers, thermoplastic resins, desiccants, dispersants and the like.
• the epoxy adhesive of the present invention is preferably solid at room temperature from the viewpoint of preventing dripping when considering adhesion in bonding different materials.
• the softening point of the epoxy adhesive is preferably 160 ° C. or lower, more preferably 140 ° C. or lower, and particularly preferably 120 ° C. or lower.
• the lower limit of the softening point is not particularly limited, but is, for example, 30 ° C. or higher.
• the viscosity of the adhesive of the present invention at 60 ° C. and 1 atm is preferably 0.01 to 20000 Pa ⁇ s, particularly preferably 0.01 to 10000 Pa ⁇ s, still more preferably 0.01 to 8000 Pa ⁇ s, and more preferably 0. It is 0.01 to 5000 Pa ⁇ s.
• the viscosity may be preferably 0.05 to 4000 Pa ⁇ s, 0.1 to 3000 Pa ⁇ s, 1 to 1000 Pa ⁇ s, and 10 to 800 Pa ⁇ s. If the viscosity is too high or too low, the coatability on the substrate when used as an adhesive tends to decrease.
• the viscosity was measured at 60 ° C. using a B-type rotational viscometer (Brookfield viscometer) according to JIS Z 8803.
• the epoxy adhesive of the present invention is suitably used for adhering dissimilar materials.
• the combination of different materials is not particularly limited, but for example, hot-rolled steel plate, cold-rolled steel plate, high-tensile steel plate, stainless steel plate, plated steel plate (zinc-plated steel plate, zinc-nickel steel plate, etc.), aluminum plate, aluminum alloy.
• Two combinations selected from various materials such as plates (aluminum-manganese alloy plate, aluminum-magnesium alloy plate, etc.), fiber reinforced plastic (FRP) plates such as carbon fiber and glass fiber, and carbon fiber reinforced plastic (CFRP) Can be mentioned.
• the epoxy adhesive of the present invention is suitably used for bonding dissimilar metals and CFRP.
• the dissimilar metals it is particularly preferable to use it for adhering metals such as iron and aluminum.
• the epoxy adhesive of the present invention can be produced by mixing each component.
• the mixing temperature is preferably 30 ° C. or higher, more preferably 40 ° C. or higher. Particularly preferably, it is 50 ° C. or higher. On the other hand, it is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and particularly preferably 120 ° C. or lower. If the mixing temperature is not less than the lower limit, mixing tends to be poor due to solidification of each component, and if it is more than the upper limit, the mixture tends to polymerize and gel during mixing.
• the mixing time is usually 1 minute or more, preferably 10 minutes or more, particularly preferably 20 minutes or more, usually 24 hours or less, preferably 18 hours or less, and particularly preferably 12 hours or less. If it is below the lower limit of the mixing time, uniform mixing tends to be impossible, and if it exceeds the upper limit, the mixture tends to polymerize and gel during mixing.
• various shearing forces generally used for mixing epoxy-based adhesives such as stirring, shaking, and kneading, can be used.
• This mixing method is variously selected depending on the physical characteristics of the adhesive, the amount of production, and the like.
• the state of the obtained epoxy adhesive may be a uniform state or a non-uniform state in which particles are dispersed. This state is variously selected depending on the use as an adhesive.
• the epoxy adhesive of the present invention is preferably a one-component adhesive from the viewpoint of handleability.
• the epoxy-based adhesive of the present invention cures the adhesive after applying the present invention to one or both of a plurality of members having different coefficients of linear expansion, sandwiching the adhesive between the dissimilar members, and adhering them together. Thereby, a laminated body in which the dissimilar members are bonded can be obtained.
• the curing conditions are not particularly limited, but for example, when a one-component adhesive is used, it is preferably heated to a temperature of 80 ° C. or higher, preferably 130 ° C. or higher, and more preferably 150 ° C. or higher. Can be cured within 60 minutes, more preferably within 30 minutes to obtain a laminated body in which dissimilar members are bonded.
• the epoxy-based adhesive of the present invention can be suitably used as an adhesive sheet containing the epoxy-based adhesive, and among them, an adhesive sheet for adhering dissimilar materials used for adhering dissimilar materials is particularly preferable.
• the adhesive sheet containing the epoxy-based adhesive of the present invention may have, for example, an adhesive layer obtained by using the epoxy-based adhesive on a base film, and the epoxy-based adhesive is used as a support. It may have an adhesive layer obtained by impregnating with.
• the adhesive layer containing the epoxy adhesive is provided on the base film
• a release-treated release film such as silicone or melamine
• a PET film, a polyethylene-based film, a polypropylene-based film, a fluorine-based film, a polyimide film, or the like that has been subjected to a mold release treatment can be used.
• the support when the support is impregnated with the epoxy adhesive, for example, a non-woven fabric, a porous material or the like can be used as the support, and the non-woven fabric is particularly preferable.
• the density of the support is 0 from the viewpoint of suppressing resin flow under pressure when a plurality of members are bonded together, holding the resin in a sheet-like adhesive, and improving the adhesiveness due to the rigidity of the adhesive layer. It is preferably 0.05 g / cm 3 or more, more preferably 0.08 g / cm 3 or more, and even more preferably 0.1 g / cm 3 or more.
• the content is preferably 1.0 g / cm 3 or less, preferably 0.9 g / cm 3 or less. More preferably, it is more preferably 0.8 g / cm 3 or less.
• the thickness of the adhesive layer in the adhesive sheet is preferably 0.1 to 2.0 mm.
• the thickness of the adhesive layer is preferably 0.2 mm or more, more preferably 0.3 mm or more, and further preferably 0.4 mm or more.
• the thickness of the adhesive layer is preferably 1.8 mm or less, more preferably 1.6 mm or less, and 1.4 mm or less. More preferred.
• the adhesive sheet can be obtained by molding an epoxy adhesive into a sheet shape.
• a method of forming into a sheet shape there is a method of laminating or applying the epoxy adhesive on the base film to obtain a laminate of the base film / epoxy adhesive / base film.
• Examples thereof include a method, an air knife coating method, a spin coating method, a roll coating method, a printing method, a dip method, a slide coating method, a curtain coating method, a die coating method, a casting method, a bar coating method, and an extrusion coating method.
• an impregnation step of impregnating the support with the epoxy adhesive may be performed.
• the impregnation method of the epoxy adhesive in the impregnation step a known method may be used.
• a base film / epoxy adhesive / support / epoxy adhesive / group obtained by providing the epoxy adhesive on the base film in the sheet forming step and the support are used.
• the method, the curtain coat method, etc. can be mentioned.
• the thickness of the support and the amount of the epoxy-based adhesive impregnated into the support are preferably adjusted so that the thickness of the adhesive layer is 0.1 to 2.0 mm.
• the laminate obtained by using the epoxy adhesive of the present invention can be used as structural members (panel parts, skeleton parts, undercarriage parts, etc.) of transportation equipment such as vehicles, aircraft, and ships, and in particular, structural panels. It is preferable to use it as a structural panel for a vehicle, and it is particularly useful as a structural panel for a vehicle.
• Epoxy resin 1 Bisphenol A type epoxy resin (A1-1) (Mitsubishi Chemical Corporation "jER1001" room temperature solid)
• Epoxy resin 2 Bisphenol F type epoxy resin (A2-1) (Mitsubishi Chemical Corporation "jER807" room temperature liquid)
• Epoxy resin 3 Bisphenol F type epoxy resin (A2-2) (Mitsubishi Chemical Corporation "jER4005P” room temperature solid)
• -Epoxy resin 5 Phenolic aralkyl type epoxy resin (A4-1) (Mitsubishi Chemical Corporation "Y
• Example 1 20 parts of epoxy resin 2, 10 parts of epoxy resin 3, 20 parts of epoxy resin 4, 40 parts of epoxy resin 5, and 10 parts of polymer fine particles 1 having a core-shell structure are mixed and then stirred at 90 ° C. until uniform. did. After placing in a constant temperature bath at 70 ° C. to raise the resin temperature to 70 ° C., further add 8 parts of the curing agent (B-1) and 2 parts of the curing accelerator (D-1), and stir until uniformly dispersed. I got the adhesive.
• the adhesive of Example 1 was solid at room temperature. The viscosity at 60 ° C. was 160 Pa ⁇ s.
• Example 2 After mixing 10 parts of epoxy resin 2, 10 parts of epoxy resin 3, 20 parts of epoxy resin 4, 40 parts of epoxy resin 5, and 20 parts of polymer fine particles 2 having a core-shell structure, the mixture is stirred at 90 ° C. until uniform. did. After placing in a constant temperature bath at 70 ° C. to raise the resin temperature to 70 ° C., further add 8 parts of the curing agent (B-1) and 2 parts of the curing accelerator (D-1), and stir until uniformly dispersed. I got the adhesive. The adhesive of Example 2 was solid at room temperature.
• Example 3 After mixing 10 parts of epoxy resin 2, 10 parts of epoxy resin 3, 20 parts of epoxy resin 4, 40 parts of epoxy resin 6, and 20 parts of polymer fine particles 2 having a core-shell structure, the mixture is stirred at 90 ° C. until uniform. did. After placing in a constant temperature bath at 70 ° C. to raise the resin temperature to 70 ° C., further add 8 parts of the curing agent (B-1) and 2 parts of the curing accelerator (D-1), and stir until uniformly dispersed. I got the adhesive. The adhesive of Example 3 was solid at room temperature.
• Example 4 After mixing 10 parts of epoxy resin 2, 10 parts of epoxy resin 3, 40 parts of epoxy resin 4, 30 parts of epoxy resin 5, and 10 parts of polymer fine particles 1 having a core-shell structure, the mixture is stirred at 90 ° C. until uniform. did. After placing in a constant temperature bath at 70 ° C. to raise the resin temperature to 70 ° C., further add 8 parts of the curing agent (B-1) and 2 parts of the curing accelerator (D-1), and stir until uniformly dispersed. I got the adhesive. The adhesive of Example 4 was solid at room temperature.
• Example 5 After mixing 10 parts of epoxy resin 2, 10 parts of epoxy resin 3, 20 parts of epoxy resin 4, 40 parts of epoxy resin 5, and 20 parts of polymer fine particles 1 having a core-shell structure, the mixture is stirred at 90 ° C. until uniform. did. After placing in a constant temperature bath at 70 ° C. to raise the resin temperature to 70 ° C., further add 8 parts of the curing agent (B-1) and 2 parts of the curing accelerator (D-1), and stir until uniformly dispersed. I got the adhesive. The adhesive of Example 5 was solid at room temperature.
• Example 6 After mixing 17 parts of epoxy resin 2, 25 parts of epoxy resin 4, 38 parts of epoxy resin 5, and 20 parts of polymer fine particles 1 having a core-shell structure, the mixture was stirred at 90 ° C. until uniform. After placing in a constant temperature bath at 70 ° C. to raise the resin temperature to 70 ° C., further add 8 parts of the curing agent (B-1) and 2 parts of the curing accelerator (D-1), and stir until uniformly dispersed. An epoxy resin composition for an adhesive was obtained. The adhesive of Example 6 was solid at room temperature.
• Example 7 After mixing 15 parts of epoxy resin 1, 5 parts of epoxy resin 2, 25 parts of epoxy resin 4, 40 parts of epoxy resin 5, and 15 parts of polymer fine particles 2 having a core-shell structure, the mixture is stirred at 90 ° C. until uniform. did. After placing in a constant temperature bath at 70 ° C. to raise the resin temperature to 70 ° C., further add 8 parts of the curing agent (B-1) and 2 parts of the curing accelerator (D-1), and stir until uniformly dispersed. An epoxy resin composition for an adhesive was obtained. The adhesive of Example 7 was solid at room temperature.
• Example 8 20 parts of epoxy resin 1, 20 parts of epoxy resin 2, 20 parts of epoxy resin 4, 20 parts of epoxy resin 5, and 20 parts of polymer fine particles 2 having a core-shell structure are mixed and then stirred at 90 ° C. until uniform. did. After placing in a constant temperature bath at 70 ° C. to raise the resin temperature to 70 ° C., further add 8 parts of the curing agent (B-1) and 2 parts of the curing accelerator (D-1), and stir until uniformly dispersed. An epoxy resin composition for an adhesive was obtained. The adhesive of Example 8 was solid at room temperature.
• Example 9 After mixing 25 parts of epoxy resin 1, 20 parts of epoxy resin 2, 15 parts of epoxy resin 4, 20 parts of epoxy resin 5, and 20 parts of polymer fine particles 2 having a core-shell structure, the mixture is stirred at 90 ° C. until uniform. did. After placing in a constant temperature bath at 70 ° C. to raise the resin temperature to 70 ° C., further add 8 parts of the curing agent (B-1) and 2 parts of the curing accelerator (D-1), and stir until uniformly dispersed. An epoxy resin composition for an adhesive was obtained. The adhesive of Example 9 was solid at room temperature.
• Comparative Example 1 After mixing 5 parts of epoxy resin 2, 20 parts of epoxy resin 4, 55 parts of epoxy resin 5, and 20 parts of polymer fine particles 1 having a core-shell structure, the mixture was stirred at 90 ° C. until uniform. After placing in a constant temperature bath at 70 ° C. to raise the resin temperature to 70 ° C., further add 8 parts of the curing agent (B-1) and 2 parts of the curing accelerator (D-1), and stir until uniformly dispersed. I got the adhesive. The adhesive of Comparative Example 1 was solid at room temperature.
• Table 1 shows the compositions of the adhesives obtained in Examples 1 to 9 and Comparative Examples 1 and 2.
• the content notation in Table 1 is a value rounded to the first decimal place, and is the content ratio of [(A1) / (A2)] and [(A1) / (A3)] shown in Table 1.
• the notation is a value calculated based on the content shown in Table 1 rounded to the third decimal place.
• Adhesive strength evaluation criteria Adhesive strength was evaluated based on tensile shear force and fracture morphology. The result of the tensile shear test uses the value of the maximum breaking point of the tensile tester, and when the tensile shear force is "15 MPa or more" and the fracture form is “aggregate fracture", it is ⁇ (Very good) and the tensile shear force is "15 MPa”. In the above, when the fracture form is "partially aggregate fracture", it is evaluated as ⁇ (Good), and when the tensile shear force is "15 MPa or less" or the fracture form is "interfacial peeling", it is evaluated as ⁇ (Poor).
• the adhesive surface of the Al test piece and the Fe test piece after peeling was visually and tactilely confirmed, and the area was cured to 60% or more of the area where the two test plates were bonded. If the adhesive adheres, it will coagulate and break, if the adhesive adheres to an area of 30% or more and less than 60% on one of the test plates, it will partially coagulate and break, on one of the test plates. If the adhesive adhered to an area of less than 30%, it was judged to be interface peeling.
• the adhesive layer obtained by curing the adhesives of Examples 1 to 9 has a tensile shear force of 15 MPa or more, and the fracture mode is cohesive fracture or partial cohesive fracture.
• the content ratio of the bisphenol A type epoxy resin (A1) to the bisphenol F type epoxy resin (A2) is set to a specific amount or less, so that the rigid skeleton of the bisphenol A type of (A1) is reduced and (A2). )
• the increase in the flexible skeleton of the bisphenol F type improved the adhesion and flexibility, and it is considered that the fracture form became agglomeration fracture or partial coagulation fracture while maintaining a high shearing force.
• the adhesive layer obtained by curing the adhesives of Comparative Examples 1 and 2 has flexibility and adhesiveness because the amount of the bisphenol A type epoxy resin (A1) added to the bisphenol F type epoxy resin (A2) is large. It is probable that all of them had peeled off the interface.
• Example 10 The adhesive obtained in Example 1 was applied as a base film on a PET film that had been mold-released with silicone, and impregnated into a glass fiber non-woven fabric (density 0.16 g / cm 3 , thickness 0.77 mm). Another base film was inserted from the other, and an adhesive sheet (adhesive sheet thickness 0.8 mm) was prepared using a laminator.
• the tensile shear force was measured according to the same method as above.
• the adhesive sheet using the adhesive of the present invention was excellent in tensile shear adhesive force.
• the epoxy resin composition for an adhesive of the present invention can be used for structural members (framework, panel parts, etc.) of transportation equipment such as vehicles, aircraft, and ships, and members such as buildings and building materials, and particularly for structural members for vehicles. It is useful.

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• 2021
  • 2021-12-08 JP JP2022568311A patent/JPWO2022124336A1/ja active Pending
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• 2023
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