Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • 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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
• • 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
  • 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
  • C08G59/50—Amines
  • C08G59/5046—Amines heterocyclic
  • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
  • C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
• • 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
  • C08G59/50—Amines
  • C08G59/5046—Amines heterocyclic
  • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
  • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
• • 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
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/062—Copolymers with monomers not covered by C08L33/06
  • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
• • 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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/062—Copolymers with monomers not covered by C09J133/06
  • C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
• • 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
  • C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
• • 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
  • C08G2170/00—Compositions for adhesives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
  • C08K2003/265—Calcium, strontium or barium carbonate

Definitions

• the present invention relates to a curable resin composition for structural bonding.
• structural adhesives have been used as a partial substitute for welding for the purpose of improving the fuel efficiency of automobiles and reducing the weight of automobile bodies in anticipation of lower fuel consumption.
• epoxy resins are widely used as main raw materials for structural adhesives that require high reliability because they exhibit excellent strength and durability due to their rigid structure.
• Japanese Patent Application Laid-Open No. 2017-132953 discloses a structural adhesive composition containing epoxy resin as a main component and having excellent adhesiveness and coating workability.
• a curable resin composition containing the following components (A) to (E).
• X to Y is used to include the numerical values (X and Y) described before and after it as lower and upper limits, and means “X or more and Y or less”.
• Concentration and % represent mass concentration and mass %, respectively, unless otherwise specified, and ratios are mass ratios unless otherwise specified.
• operations and measurements of physical properties and the like are performed under the conditions of room temperature (20 to 25° C.)/relative humidity of 40 to 55% RH.
• a and/or B is meant to include each of A, B and combinations thereof.
• a curable resin composition according to one aspect of the present invention contains the following components (A) to (E): (A) a compound having two or more glycidyl groups in one molecule (excluding component (B)); (B) a glycidyl group-containing acrylic polymer; (C) a tackifier having an OH value of 100 or more having a phenol skeleton; (D) an inorganic filler; and (E) a curing agent.
• the curable resin composition of the present invention maintains the resin strength and adhesive strength peculiar to epoxy resins, is flexible, and has a high toughness coefficient. is very useful as a structural adhesive.
• component (A) used in the present invention is a compound having two or more glycidyl groups in one molecule.
• the (B) component described later is not included in the (A) component.
• Component (A) is a major component for achieving high adhesive strength and resin strength as an adhesive. From the viewpoint of imparting flexibility, those that are liquid at 25°C are preferred.
• Specific examples of component (A) are not particularly limited, but include epoxy resins having an oxyalkylene skeleton, epoxy resins having both bisphenol and oxyalkylene skeletons, bisphenol-type epoxy resins, hydrogenated bisphenol-type epoxy resins, and naphthalene.
• the component (A) uses a combination of an epoxy resin having an oxyalkylene skeleton, an epoxy resin having both a bisphenol and an oxyalkylene skeleton, a bisphenol type epoxy resin and a hydrogenated bisphenol type epoxy resin.
• the component (A) preferably contains a bisphenol-type epoxy resin having a bisphenol skeleton in one molecule, from the viewpoint of achieving both elongation and resin strength.
• the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin and the like. Among them, it is more preferable to contain bisphenol A-type diglycidyl ether and/or bisphenol F-type diglycidyl ether, and more preferably to contain bisphenol A-type diglycidyl ether, from the viewpoint of achieving both elongation and resin strength.
• Epoxy resins having both a bisphenol skeleton and an oxyalkylene skeleton, which will be described later, are not included in the bisphenol-type epoxy resins.
• the component (A) contains an epoxy resin having an oxyalkylene skeleton and/or a hydrogenated bisphenol type epoxy resin, so that the elongation rate can be further improved.
• an epoxy resin having both a bisphenol skeleton and an oxyalkylene skeleton resin strength and toughness coefficient can be improved.
• the epoxy resin having an oxyalkylene skeleton has a skeleton of -(RO)- (R is an alkylene group, and the alkylene group may be linear or branched) in the main chain, and has an epoxy group. It is a compound having two or more. From the viewpoint of improving the elongation rate, the main chain preferably has a polyoxyalkylene skeleton consisting of repeating units of -(RO)-, and from the viewpoint of curability, the epoxy group is preferably at the end.
• Specific examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, pentyl glycol diglycidyl ether, hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polybutylene glycol.
• Examples include diglycidyl ether, polypentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, etc.
• polyethylene glycol diglycidyl ether polypropylene glycol diglycidyl ether, polytetramethylene Glycol diglycidyl ether is preferred, and polypropylene glycol diglycidyl ether is more preferred.
• the hydrogenated bisphenol type epoxy resin is a compound obtained by hydrogenating the aromatic ring of the bisphenol type epoxy resin.
• Specific examples include hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol B diglycidyl ether, hydrogenated bisphenol C diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, and hydrogenated bisphenol G diglycidyl ether.
• the epoxy resin having both a bisphenol skeleton and an oxyalkylene skeleton is a compound that has the above-mentioned oxyalkylene skeleton in addition to the bisphenol skeleton in one molecule and has a terminal glycidyl group.
• a cured product with a bisphenol skeleton and an oxyalkylene skeleton that is more flexible than an epoxy resin that has only a bisphenol skeleton, has superior resin strength than an epoxy resin that has only an oxyalkylene skeleton, and has excellent fracture toughness by combining both. can be obtained.
• bisphenol A oxyalkylene diglycidyl ether examples thereof include bisphenol A oxyalkylene diglycidyl ether, bisphenol F oxyalkylene diglycidyl ether, etc., but bisphenol A oxyalkylene diglycidyl ether is preferred from the viewpoint of improving resin strength and toughness coefficient, and bisphenol A ethylene oxide More preferred are diglycidyl ether, bisphenol A propylene oxide diglycidyl ether, and most preferred is bisphenol A propylene oxide diglycidyl ether.
• bisphenol A type diglycidyl ether examples include, for example, jER825, jER827, 828, jER828EL, jER828US, jER828XA, jER834 (manufactured by Mitsubishi Chemical Corporation), EPICLON840, EPICLON840-S, EPICLON850, EPICLON850-S, EPICLON EXA-850CRP.
• EPICLON850-LC manufactured by DIC Corporation
• ADEKA RESIN EP-4100 ADEKA RESIN EP-4100G
• ADEKA RESIN EP-4100E ADEKA RESIN EP-4100TX
• ADEKA RESIN EP-4300E ADEKA RESIN EP-4400
• EP-4520S EP-4530 (Stock manufactured by the company ADEKA) and the like, but are not limited to these.
• Examples of commercial products of bisphenol F type diglycidyl ether include jER806, jER806H, jER807 (manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON830-S, EPICLON835, EPICLON EXA-830CRP, EPICLON EXA-830LVP, EPICLON EXA-835LV ( DIC Corporation), ADEKA RESIN EP-4901, ADEKA RESIN EP-4901E (manufactured by ADEKA Corporation), etc., but not limited thereto.
• epoxy resins having an oxyalkylene skeleton include Epolite M-1230, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 200P, Epolite 400P (manufactured by Kyoeisha Chemical Co., Ltd.), Epogose EN, Epogose PT, Epogose AN, and Epogose. 2EH, Epogosei HD, CE-EP, S-EP (manufactured by Yokkaichi Gosei Co., Ltd.) and the like, but are not limited to these.
• epoxy resins having both bisphenol and oxyalkylene skeletons include EP-4000, EP-4000S, EP-4005 (manufactured by ADEKA Corporation), and Epolite 3002 (N) (manufactured by Kyoeisha Chemical Co., Ltd.). .
• the component (A) preferably has an epoxy equivalent of 100 to 500 g/eq, more preferably 130 to 400 g/eq, and 150 to 350 g/eq. is most preferred.
• the bisphenol type epoxy resin is added to 100% by mass of the component (A). , preferably 1 to 60% by mass, more preferably 5 to 40% by mass, and most preferably 7 to 20% by mass.
• the component (A) is composed of two or more different epoxy resins and contains an epoxy resin having an oxyalkylene skeleton and/or a hydrogenated bisphenol epoxy resin, from the viewpoint of improving the elongation rate, epoxy having an oxyalkylene skeleton
• the resin and/or hydrogenated bisphenol type epoxy resin is preferably contained in an amount of 10 to 90% by mass, more preferably 20 to 70% by mass, more preferably 30 to 60% by mass, based on 100% by mass of component (A). is most preferred.
• the component (A) is composed of two or more different epoxy resins and contains an epoxy resin having both a bisphenol skeleton and an oxyalkylene skeleton, from the viewpoint of improving fracture toughness, it has both a bisphenol skeleton and an oxyalkylene skeleton.
• the epoxy resin content is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and most preferably 20 to 40% by mass based on 100% by mass of component (A).
• component (B) used in the present invention is a glycidyl group-containing acrylic polymer. Since component (B) has a glycidyl group, it is possible to react with component (A) by component (E), which will be described later, and the elongation rate of the cured product can be greatly increased without reducing adhesive strength or resin strength. can be substantially improved. From the viewpoint of further improving the elongation rate, it is preferably liquid at 25°C.
• TEG-001 manufactured by Neagari Kogyo Co., Ltd.
• ARUFON UG-4010 manufactured by Toagosei Co., Ltd.
• the component (B) preferably has a weight average molecular weight of 1,000 to 100,000, more preferably 1,500 to 90,000, and most preferably 2,000 to 80,000.
• the weight average molecular weight in the present invention means the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography.
• the component (B) preferably has an epoxy equivalent of 500 to 20,000 g/eq, more preferably 500 to 10,000 g/eq, and 600 to 8,000 g/eq, from the viewpoint of improving adhesive strength, resin strength, and elongation. is most preferred. If it is 500 g/eq or more, the elongation rate can be improved, and if it is 20000 g/eq or less, the adhesive strength and resin strength will not be lowered.
• the content of component (B) is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and 20 to 50 parts by mass based on 100 parts by mass of component (A). is most preferred. If it is 5 parts by mass or more, the elongation rate can be improved, and if it is 100 parts by mass or less, there is no risk of lowering the adhesive strength and resin strength.
• Component (C) used in the present invention is a tackifier having an OH value of 100 or more and having a phenol skeleton.
• the elongation rate can be improved without lowering the resin strength.
• the OH value is 100 or more, it is possible to obtain a cured product having good compatibility with the component (A) and having a high toughness coefficient.
• a resin that is solid at 25° C. is preferable from the viewpoint of maintaining resin strength, and a terpene phenol resin is preferable from the viewpoint of further improving the elongation rate and the toughness coefficient.
• the OH value of the component (C) is preferably 100-500, more preferably 100-300, and most preferably 100-250. If the OH value is 100 or more, the compatibility with the component (A) is excellent and the toughness coefficient can be improved.
• the softening point of the component (C) is preferably 90-200°C, more preferably 100-180°C, and most preferably 110-160°C. If it is 90°C or higher, the resin strength does not decrease even in a high temperature environment, and if it is 200°C or lower, it is difficult to crystallize when mixed with other components, so the storage stability as a curable resin composition is affected. does not affect
• the content of component (C) is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, and more preferably 5 to 30 parts by mass with respect to the total of 100 parts by mass of components (A) and (B). Most preferred. When it is 1 part by mass or more, the elongation rate and toughness coefficient can be improved, and when it is 50 parts by mass or less, resin strength and adhesive strength are not lowered.
• component (C) examples include YS Polyster K125, YS Polyster G125, YS Polyster N125, YS Polyster S145 (manufactured by Yasuhara Chemical Co., Ltd.), Tamanol 803L, Tamanol 901 (manufactured by Arakawa Chemical Industries, Ltd.), and the like. mentioned.
• the component (D) that can be used in the present invention is an inorganic filler. By containing the component (D), it is possible to further improve the resin strength and toughness modulus while realizing a high elongation rate.
• Component (D) is preferably powder, and specific examples of component (D) include glass, silica, alumina, mica, ceramics, silicone rubber powder, calcium carbonate, calcium oxide, aluminum nitride, carbon powder, Minerals such as kaolin clay, wollastonite, and aluminum are included.
• the shape of component (D) is not particularly limited, but may be spherical, acicular, or the like. These may be used alone or in combination of two or more.
• one or more is preferably selected from the group consisting of silica, calcium carbonate and wollastonite from the viewpoint of improving toughness modulus without lowering flexibility and resin strength.
• the average particle size of the component (D) is preferably 0.1 to 200 ⁇ m.
• the average fiber diameter is preferably 1-20 ⁇ m, more preferably 3-15 ⁇ m.
• the average fiber length is preferably 10-200 ⁇ m, more preferably 30-100 ⁇ m.
• the aspect ratio is preferably 3 or more, more preferably 4 or more.
• the content of the component (D) is preferably 0.1 to 100 parts by mass, more preferably 1 to 70 parts by mass, and 5 to 50 parts by mass with respect to the total of 100 parts by mass of the components (A) and (B). part is most preferred. If it is 0.1 parts by mass or more, the resin strength and toughness coefficient can be improved, and if it is 100 parts by mass or less, the elongation rate will not decrease.
• component (E) that can be used in the present invention is a curing agent.
• Component (E) is not particularly limited as long as it can cure component (A) and component (B) and may be liquid or solid at 25°C. is preferred, and powder is more preferred.
• Specific examples of component (E) include dicyandiamide, hydrazide compounds, urea compounds, imidazole compounds, boron trifluoride-amine complexes, reaction products obtained by reacting amine compounds with epoxy compounds, isocyanate compounds, or urea compounds ( adduct type latent curing agent), and the like.
• dicyandiamide a compound selected from the group consisting of dicyandiamide, urea compounds and imidazole compounds from the viewpoint of the balance between elongation and resin strength.
• dicyandiamide a compound selected from the viewpoint of the balance between elongation and resin strength.
• Each of these may be used alone, or two or more of them may be used in combination, but it is preferable to mix two or more of them from the viewpoint of improving fracture toughness.
• a combination of dicyandiamide, a urea compound and a urea compound is more preferred, and a combination of three of dicyandiamide, a urea compound and an imidazole compound is most preferred.
• urea compound examples include phenyl-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1, 1-dimethylurea, 2,4-bis(3,3-dimethylureido)toluene, 1,1′-4(methyl-m-phenylene)bis(3,3-dimethylurea), 4,4′-methylenebis( phenyldimethylurea) and the like.
• imidazole compound examples include 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, 4-methyl-2-phenyl-5-hydroxymethylimidazole and the like. is mentioned.
• dicyandiamide Commercial products of the dicyandiamide include jER Cure DICY7, 15, 20, 7A (manufactured by Mitsubishi Chemical Corporation), Omicure DDA10, DDA50, DDA100, DDA5, CG-325, DICY-F, DICY-M (CVC Thermoset Specialties ), CG-1200, CG-1400 (manufactured by Air Products Japan Co., Ltd.) and the like.
• urea compounds examples include DCMU99 (manufactured by Hodogaya Chemical Co., Ltd.), Omicure24, Omicure52, and Omicure94 (manufactured by CVC Thermoset Specialties).
• imidazole compounds examples include Cursol SIZ, 2MZ-H, C11Z, C17Z, 2PZ, 2PZ-PW, 2P4MZ, 2PZCNS-PW, 2MZ-A, 2MZA-PW, 2E4MZ-A, 2MA-OK, 2MAOK- PW, 2PHZ-PW, 2P4MHZ-PW (manufactured by Shikoku Kasei Co., Ltd.) and the like.
• the melting point of the component (E) is preferably 150 to 300°C, more preferably 160 to 250°C, and most preferably 170 to 230°C. If it is 150° C. or higher, there is no risk of lowering the storage stability of the curable resin composition, and if it is 300° C. or lower, it does not affect the curability, and even if a plurality of curing agents are combined, the resin strength increases. does not cause a decline.
• the blending amount of the component (E) is preferably 1 to 50 parts by mass, more preferably 3 to 20 parts by mass, and most preferably 100 parts by mass of the total amount of the components (A) and (B). is 5 to 10 parts by mass.
• the amount is 1 to 50 parts by mass, a cured product having excellent elongation, resin strength, and fracture toughness can be obtained without deteriorating storage stability.
• the ratio of dicyandiamide:urea compound and/or imidazole compound is 15:1 to 2:1 from the viewpoint of improving the toughness coefficient. is preferred, and more preferably in a ratio of 12:1 to 3:1.
• additives such as organic fillers, pigments, dyes, silane coupling agents, leveling agents, rheology control agents, and storage stabilizers within the range that does not impair the properties of the present invention.
• the organic filler may be an organic powder composed of rubber, elastomer, plastic, polymer (or copolymer), or the like. Moreover, the organic filler which has multilayer structures, such as a core shell type, may be used.
• the amount of the organic filler to be blended is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass of the total amount of components (A) and (B).
• silane coupling agent examples include 3-acryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldipropyloxy Silane, 3-glycidoxypropyldimethylmonomethoxysilane, 3-glycidoxypropyldimethylmonoethoxysilane, 3-glycidoxypropyldimethylmonopropyloxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane , 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and other glycidyl group-containing silane coupling agents, vinyltris( ⁇ -methoxyethoxy)silane, Vinyl group-containing silane coupling agents such as vinyl
• (Meth) acrylic group-containing silane coupling agents N- ⁇ -(aminoethyl)- ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, etc.
• Examples include amino group-containing silane coupling agents, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -chloropropyltrimethoxysilane, and the like.
• a glycidyl group-containing silane coupling agent is more preferable from the viewpoint of excellent adhesive strength. These may be used alone or in combination of two or more.
• the amount of the silane coupling agent to be blended is preferably 0.1 to 20 parts by mass per 100 parts by mass of the total amount of components (A) and (B) of the present invention. If it is 0.1 to 20 parts by mass, there is no risk of impairing the properties of the present invention.
• boric acid ester As the storage stabilizer, boric acid ester, phosphoric acid, alkyl phosphate, and p-toluenesulfonic acid can be used.
• Borate esters include, but are not limited to, tributyl borate, trimethoxyboroxine, ethyl borate, and the like.
• alkyl phosphates examples include trimethyl phosphate and tributyl phosphate, but are not limited to these.
• Storage stabilizers may be used singly or in combination. Considering storage stability, it is preferably one or more selected from the group consisting of phosphoric acid, tributyl borate, trimethoxyboroxine, and methyl p-toluenesulfonate.
• a known sealant or adhesive method As a method for applying the curable resin composition of the present invention to an adherend, a known sealant or adhesive method is used. For example, methods such as dispensing using an automatic coating machine, spraying, inkjet, screen printing, gravure printing, dipping, and spin coating can be used.
• the curable resin composition of the present invention can be cured under any heating conditions. Therefore, in one embodiment of the present invention, a cured product obtained by curing a curable resin composition by heating is provided.
• the heating temperature is not particularly limited, for example, a temperature of 100°C to 300°C is preferable, and a temperature of 120°C to 200°C is more preferable.
• the curing time is not particularly limited, but when the temperature is 100° C. to 300° C., it is preferably 3 minutes to 3 hours, more preferably 5 minutes to 2 hours.
• a cured product obtained from the curable resin composition of the present invention has an excellent toughness modulus.
• the toughness coefficient is an index of resistance to fracture when mechanical stress is applied, and the index of the toughness coefficient in the present invention indicates the tenacity of the cured product to fracture.
• evaluation can be made by measuring elongation and resin strength, which will be described later. The higher the toughness modulus, the more energy is required until the cured product is destroyed, so even if various stresses are applied, the cured product is less likely to be destroyed.
• the toughness coefficient is preferably 10 MPa or more. Although the upper limit is not particularly limited, it is 30 MPa or less. In one embodiment, the toughness modulus of the cured product at 25°C when cured at 170°C for 60 minutes is 10 MPa or more.
• the epoxy resin composition of the present invention can be used for various purposes. Specific examples include the bonding, sealing, and sealing of automobile bodies, switch parts, headlamps, internal engine parts, electrical parts, drive engines, brake oil tanks, front hoods, fenders, body panels such as doors, and windows. Molds, coatings, etc.; In the field of electronic materials, flat panel displays (liquid crystal displays, organic EL displays, light-emitting diode displays, field emission displays), video discs, CDs, DVDs, MDs, pickup lenses, hard discs, etc. are adhered and sealed.
• flat panel displays liquid crystal displays, organic EL displays, light-emitting diode displays, field emission displays
• the curable resin composition of the present invention has high adhesive strength and is excellent in elongation and resin strength, and is therefore suitable for use in structural adhesion where adhesive strength and impact resistance are required.
• Shear bond strength (tensile shear bond strength)] A 25 mm wide ⁇ 100 mm long ⁇ 1.6 mm thick SUS304 test piece is coated with the curable resin adhesives of Examples and Comparative Examples. Thereafter, a similar test piece was pasted together so that the overlapping surface was 25 mm ⁇ 10 mm, fixed with a clip, and cured in a hot air drying oven at 170° C. for 60 minutes to obtain a test piece.
• the shear bond strength (unit: MPa) is measured according to JISK6850 with a universal tensile tester (pulling speed: 10 mm/min) at 25° C., and evaluated according to the following evaluation criteria. Acceptance: 15 MPa or more Although the upper limit is not particularly limited, it is 50 MPa or less.
• the curable resin composition was squeegeeed onto a polytetrafluoroethylene plate to a thickness of 1.5 mm and cured in a hot air drying oven at 170° C. for 60 minutes to obtain a sheet-like cured product.
• a No. 2 dumbbell was used to punch out the cured product to obtain a test piece. Both ends of the test piece are fixed to chucks of a universal testing machine (Autograph/manufactured by Shimadzu Corporation), and the test piece is pulled in the tensile direction at a tensile speed of 50 mm/min to break it.
• the horizontal axis represents displacement (%) until breakage
• the vertical axis represents stress (MPa)
• a vertical line is drawn from the breaking point to the X-axis
• the area surrounded by this vertical line, the X-axis, and the SS curve is defined as the toughness coefficient.
• Acceptance 10 MPa or more
• the upper limit is not particularly limited, it is 30 MPa or less.
• Examples 1 to 7 are excellent in elongation, resin strength, shear adhesive strength, and toughness coefficient.
• Comparative Example 1 which did not contain the component (B), had excellent resin strength and shear adhesive strength, but had extremely low elongation and toughness modulus. Satisfactory results were not obtained in Comparative Example 2 using the component (C) having a low OH value.
• Comparative Example 3 using the component (C) having no OH, the components could not be compatible with each other during the production of the curable resin composition, resulting in separation, and the measurement of physical properties was abandoned.
• Comparative Examples 4 and 5 using the component (C) having no OH the toughness coefficient was also low.
• Comparative Example 6 which did not contain the component (C), had a low toughness coefficient. From the above, by combining the components (A) to (E), a cured product having excellent elongation, resin strength, shear adhesive strength, and toughness coefficient can be obtained, and the problems of the present invention can be solved. .
• the curable resin composition of the present invention has excellent elongation, resin strength, shear adhesive strength, and toughness coefficient, so it can be applied to various fields where high durability, reliability, and flexibility are required. It is very useful especially for structural bonding applications.

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• 2022
  • 2022-05-20 CN CN202280030957.3A patent/CN117242134A/zh active Pending
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