Classifications

• • 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
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
• • 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
• • 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
  • C08G59/223—Di-epoxy compounds together with monoepoxy compounds
• • 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
  • C08G59/4064—Curing agents not provided for by the groups C08G59/42 - C08G59/66 sulfur containing compounds
• • 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
  • C08G59/5006—Amines aliphatic
• • 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
  • C08G59/66—Mercaptans
• • 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
  • C08G59/68—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 catalysts used
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/16—Solid spheres
  • C08K7/18—Solid spheres inorganic
• • 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
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • 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
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2190/00—Compositions for sealing or packing joints
• • 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
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
  • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
  • C09K2200/0647—Polyepoxides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents

Definitions

• the present invention relates to an epoxy resin composition having excellent adhesiveness to different materials and a cured product thereof.
• epoxy resin is used in a wide range of fields because it exhibits good adhesive strength and is excellent in chemical resistance and durability, and is also suitably used for bonding different materials.
• Japanese Patent Application Laid-Open No. 2019-156965 contains (A) a thiol-based curing agent, (B) a polyfunctional epoxy resin, and (C) a monofunctional epoxy resin.
• Epoxy resin compositions containing agents and having a specific relationship between the number (amount) of thiol groups and the number (amount) of epoxy groups contained in these components have been proposed.
• the conventional adhesive (epoxy resin) used for adhesion between different materials does not have sufficient adhesiveness to different materials, and further improvement in the adhesiveness is required. Further, the conventional adhesive (epoxy resin) has problems such as high curing temperature, high viscosity and poor workability. Further, when the viscosity of the conventional adhesive (epoxy resin) is lowered in order to improve workability, the curing shrinkage is large, and at the time of curing, the member to be bonded may be distorted.
• the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an epoxy resin composition having excellent adhesiveness to different materials. Another object of the present invention is to provide an epoxy resin composition having excellent adhesiveness to different materials, low temperature curability and low viscosity for exhibiting good workability, and low curing shrinkage. To provide. Still another object of the present invention is to provide a cured product obtained by curing the epoxy resin composition.
• the present inventor has found that the epoxy resin composition described in detail below has excellent adhesiveness to different materials, and has completed the present invention.
• the gist of the present invention will be described below.
• X to Y means the range including the numerical values (X and Y) described before and after that as the lower limit value and the upper limit value, and means "X or more and Y or less”.
• concentration and% shall represent the mass concentration and the mass%, respectively, unless otherwise specified, and the ratio shall be the mass ratio unless otherwise specified.
• operations and measurements of physical properties are performed under the conditions of room temperature (20 to 25 ° C.) / relative humidity of 40 to 55% RH.
• a and / or B means to include each of A and B and a combination thereof.
• epoxy resin composition contains the following components (A) to (E): (A) A compound that is liquid at 25 ° C., has two or more epoxy groups in one molecule, and has an epoxy equivalent of less than 210 g / eq. (B) (B-1) Liquid at 25 ° C., in one molecule. A compound having 2 or more epoxy groups and an epoxy equivalent of 210 g / eq or more and / or a compound having (B-2) solid at 25 ° C. and having 2 or more epoxy groups in one molecule (C) thiol curing Agent (D) Latent curing agent (E) Reactive diluent.
• the epoxy resin composition according to one aspect of the present invention has excellent adhesiveness to different materials. Further, the epoxy resin composition according to one aspect of the present invention has excellent adhesiveness to different materials, low temperature curability and low viscosity for exhibiting good workability, and further has low curing shrinkage. Therefore, it is very useful.
• the epoxy resin composition according to the present invention contains the component (A) and the component (B) having a higher molecular weight (higher epoxy equivalent) than the component (A). Therefore, it is considered that an excellent effect of improving the adhesiveness to different materials can be obtained. On the other hand, when the epoxy resin composition does not contain the compound corresponding to the component (B), the adhesiveness to different materials is lowered (Comparative Example 1 described later).
• the component (A) contained in the epoxy resin according to the present invention is a compound which is liquid at 25 ° C., has two or more epoxy groups in one molecule, and has an epoxy equivalent of less than 210 g / eq.
• liquid at 25 ° C means a state having fluidity at 25 ° C.
• liquid at 25 ° C.” means one that satisfies at least one of the following (i) and (ii); (I) The viscosity measured by a cone plate type rotational viscometer at 25 ° C. is 100 Pa ⁇ s or less; (Ii) The softening point or melting point (or the softening point if it has both a softening point and a melting point) is less than 35 ° C.
• the softening point is obtained by a method based on JIS K 7234: 1986 (ring ball method).
• the melting point is determined by differential scanning calorimetry (DSC).
• the epoxy equivalent is a value measured in accordance with JIS K 7236: 2001. If the epoxy equivalent cannot be determined by the method, the molecular weight of the target epoxy resin may be calculated by dividing by the number of epoxy groups contained in one molecule of the epoxy resin.
• the epoxy equivalent of the component (A) is preferably 50 g / eq or more and less than 210 g / eq, and more than 100 g / eq and less than 210 g / eq, from the viewpoint of exhibiting low-temperature curability and lowering the curing shrinkage. More preferably, it is 130 g / eq or more and 180 g / eq or less.
• the viscosity of the component (A) is preferably 0.01 Pa ⁇ s or more and less than 100 Pa ⁇ s at 25 ° C., and is 0.1 Pa ⁇ s to 70 Pa ⁇ s. -S is more preferable, 0.1 to 50 Pa ⁇ s is even more preferable, 0.3 to 10 Pa ⁇ s is even more preferable, and 0.5 to 5 Pa ⁇ s is most preferable.
• the softening point or melting point (in the case of having both the softening point and the melting point, the softening point) of the component (A) is preferably 10 ° C. or higher and lower than 35 ° C., and more preferably 15 ° C. or higher and 30 ° C. or lower. preferable.
• the number of epoxy groups contained in one molecule is not particularly limited as long as it is 2 or more, but 2 to 6 (2 to 6 functional epoxy resin) is preferable, and 2 to 6 are preferable. Three (2 to trifunctional epoxy resin) is more preferable, and two (bifunctional epoxy resin) is particularly preferable.
• the compound of the component (A) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, bisphenol AF type epoxy resin, hydrogenated bisphenol type epoxy resin and the like.
• examples thereof include, but are not limited to, bisphenol type epoxy resin; phenol novolac type epoxy resin; glycidylamine type epoxy resin; dimer acid-modified epoxy resin; alicyclic epoxy resin. These may be used alone or in combination of two or more.
• the component (A) is preferably a bisphenol type epoxy resin from the viewpoint of being able to lower the curing shrinkage.
• the component (A) contains at least one selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol AF type epoxy resin, and more preferably bisphenol A type epoxy. It is particularly preferable to include both the resin and the bisphenol F type epoxy resin.
• the compound (epoxy resin) as the component (A) either a synthetic product or a commercially available product may be used.
• jER registered trademark
• 825, 827, 828, 828EL, 828XA, 828US, 806, 806H, 807, 152, 871, 872, YL980, YL983U, YX8000, YX8034 Mitsubishi Chemical
• EPICLON (registered trademark) 840, 840S, 850, 850S, 850CRP, 850-LC, 830, 835, EXA-830LVP, EXA-830LVP, EXA-835LV, N-730A (manufactured by DIC Corporation), Denacol (registered trademark) EP-4100, EP-4100G, EP-4100E, EP-4300E, EP-4530, EP-4901, EP-491E (manufactured by ADEKA CORPORATION), EX-810, EX-811, EX-850 , EX-821, EXA-920, EX-201, EX-212 (manufactured by Nagase ChemteX Corporation) and the like, but are not limited thereto.
• the compound (epoxy resin) as the component (A) may be used alone or in combination of two or more. When two or more kinds are used in combination, the content of the component (A) refers to the total amount.
• the component (B) contained in the epoxy resin according to the present invention includes the following component (B-1) and / or component (B-2):
• (B-1) Component A compound that is liquid at 25 ° C., has two or more epoxy groups in one molecule, and has an epoxy equivalent of 210 g / eq or more.
• (B-2) Component Solid at 25 ° C. A compound having two or more epoxy groups in one molecule.
• component (B) By combining the component (B) with the component (A) described above, it is possible to improve the adhesiveness to different materials while maintaining a low curing shrinkage.
• the compound is "liquid at 25 ° C.” follows the definition described in the description of the component (A) above.
• the epoxy equivalent of the compound is a value measured by the measuring method described in the above description of the component (A).
• solid (solid) at 25 ° C.” means a state having no fluidity at 25 ° C.
• solid at 25 ° C.” means one that satisfies at least one of the following (i') and (ii');
• the viscosity measured using a cone plate type rotational viscometer exceeds 100 Pa ⁇ s;
• the softening point or the melting point (or the softening point when having both the softening point and the melting point) is 35 ° C. or higher.
• the method for measuring the softening point and the melting point follows the method described in the description of the component (A) above.
• the epoxy equivalent of the component (B-1) is preferably 210 to 1000 g / eq, more preferably 230 to 700 g / eq, even more preferably 230 to 500 g / eq, and 230 to 300 g / eq. Most preferably.
• the epoxy equivalent of the component (B-1) is 210 g / eq or more, further 230 g / eq or more, it is possible to improve the adhesive strength to different materials while maintaining the curing shrinkage low.
• the epoxy equivalent of the component (B-1) is 1000 g / eq or less, an epoxy resin composition having a low viscosity and excellent workability can be obtained.
• the viscosity of the component (B-1) is preferably 0.01 Pa ⁇ s or more and less than 100 Pa ⁇ s at 25 ° C., preferably 0.1 Pa ⁇ s. It is more preferably about 70 Pa ⁇ s, even more preferably 0.1 to 50 Pa ⁇ s, even more preferably 0.3 to 10 Pa ⁇ s, and most preferably 0.5 to 5 Pa ⁇ s. ..
• the softening point or melting point (in the case of having both a softening point and a melting point, the softening point) of the component (B-1) is preferably 10 ° C. or higher and lower than 35 ° C., and more than 25 ° C. and lower than 35 ° C. It is more preferable to have it.
• the epoxy equivalent of the component (B-2) is not particularly limited, but is preferably 100 to 3000 g / eq, more preferably 130 to 2000 g / eq, and even more preferably 150 to 1000 g / eq, 230. Most preferably, it is ⁇ 800 g / eq.
• the epoxy equivalent of the component (B-2) is 100 g / eq or more, further 230 g / eq or more, it is possible to improve the adhesive strength to different materials while maintaining the curing shrinkage low. Further, if the epoxy equivalent of the component (B-2) is 3000 g / eq or less, and further 800 g / eq or less, an epoxy resin composition having a low viscosity and excellent workability can be obtained.
• the softening point or melting point (softening point when having both a softening point and a melting point) of the component (B-2) is preferably 40 to 200 ° C., more preferably 50 to 150 ° C., and 55 to 55 to The temperature is even more preferably 130 ° C, and most preferably 60 to 100 ° C.
• an epoxy resin composition having good compatibility with the component (A) and having a low viscosity can be obtained.
• the number of epoxy groups contained in one molecule is not particularly limited as long as it is 2 or more, but 2 to 6 (2 to 6) ( It is preferably 2 to 6 functional epoxy resins), more preferably 2 to 3 (2 to 3 functional epoxy resins), and particularly preferably 2 (bifunctional epoxy resins).
• the number of epoxy groups in the above range it is possible to improve the adhesive strength to different materials while keeping the curing shrinkage low.
• component (B) examples include bisphenol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, phenol novolac resin, and cresol novolak resin.
• examples thereof include, but are not limited to, biphenyl type epoxy resins. These may be used alone or in combination of two or more.
• the component (B) is preferably a bisphenol type epoxy resin and / or a biphenyl type epoxy resin from the viewpoint of being able to lower the curing shrinkage. Further, from the same viewpoint as above, the component (B) preferably contains at least one selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin and biphenyl type epoxy resin.
• the component (B) is preferably contained in (B-1). Further, from the same viewpoint, it is preferable that the component (B) contains only the component (B-1) (that is, the component (B) is the component (B-1)).
• the compound (epoxy resin) as the component (B) either a synthetic product or a commercially available product may be used.
• jER registered trademark
• 1001, 1002, 1003, 1055, 1004, 1004AF, 4005P, 4007P, YX4000H manufactured by Mitsubishi Chemical Corporation
• EPICLON registered trademark
• the compound (epoxy resin) as the component (B) may be used alone or in combination of two or more. When two or more kinds are used in combination, the content of the component (B) refers to the total amount.
• the content of the component (B) is preferably 1 to 100 parts by mass, more preferably 5 to 100 parts by mass, and further preferably 10 to 80 parts by mass with respect to 100 parts by mass of the component (A). It is preferably 15 to 70 parts by mass, more preferably 20 to 50 parts by mass, and most preferably 20 to 50 parts by mass.
• the content of the component (B) is 1 part by mass or more, further 5 parts by mass or more, the adhesiveness to different materials can be improved while keeping the curing shrinkage low. Further, when the content of the component (B) is 100 parts by mass or less, an epoxy resin composition having a low viscosity and excellent workability can be obtained.
• the component (C) contained in the epoxy resin according to the present invention is a thiol curing agent.
• the thiol curing agent as the component (C) is not particularly limited as long as it has one or more thiol groups (SH groups) in one molecule.
• the thiol curing agent is preferably a compound having 2 or more SH groups, more preferably a compound having 3 or more, and a compound having 4 or more.
• the upper limit of the number of SH groups is not particularly limited, but is 10 or less from the viewpoint of obtaining an epoxy resin composition having a low viscosity and excellent workability.
• the thiol equivalent of the component (C) is not particularly limited, but is preferably 50 to 500 g / eq (g / mol), more preferably 70 to 300 g / eq (g / mol). , 90 to 200 g / eq (g / mol) is even more preferable, and 110 to 150 g / eq (g / mol) is most preferable.
• the thiol equivalent can be determined by the iodine titration method. If the thiol equivalent cannot be determined by the method, the molecular weight of the target thiol curing agent may be calculated by dividing by the number of SH groups contained in one molecule of the thiol curing agent. ..
• the substitution position of the SH group contained in the thiol curing agent as the component (C) is not particularly limited and may be present at the end of the compound or may be present as a side chain (in the side chain). ..
• the SH group contained in the thiol curing agent as the component (C) may be any of a primary thiol group, a secondary thiol group, and a tertiary thiol group. Among them, a primary thiol group or a secondary thiol group is preferable, and a secondary thiol group is more preferable, from the viewpoint of reducing the curing shrinkage of the epoxy resin composition.
• the thiol curing agent as the component (C) is preferably a primary thiol compound or a secondary thiol compound, and is secondary.
• a thiol compound is more preferable.
• the primary thiol group means that the carbon bonded to the sulfur atom (the carbon to which the SH group is bonded) is a primary carbon atom, and similarly, a secondary thiol group and a tertiary thiol group.
• the carbon bonded to the sulfur atom (the carbon to which the SH group is bonded) is a secondary carbon atom and a tertiary carbon atom, respectively.
• component (C) examples include trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, and pentaerythritol tetrakis (3-mercaptopropionate).
• thiol curing agent as the component (C), either a synthetic product or a commercially available product may be used.
• TMMP TMMP
• TEMPIC PEMP
• EGMP-4 DPMP manufactured by SC Organic Chemistry Co., Ltd.
• Calends MT registered trademark PE1, BD1, NR1, TPMB manufactured by Showa Denko KK, etc.
• PE1, BD1, NR1, TPMB manufactured by Showa Denko KK etc.
• the thiol curing agent as the component (C) may be used alone or in combination of two or more. When two or more kinds are used in combination, the content of the component (C) refers to the total amount.
• the content of the component (C) is preferably 50 to 300 parts by mass, more preferably 130 to 250 parts by mass, and most preferably 150 to 230 parts by mass with respect to 100 parts by mass of the component (A). ..
• the content of the component (C) is 50 parts by mass or more, an epoxy resin composition having excellent low temperature curability and adhesiveness can be obtained. Further, when the content of the component (C) is 300 parts by mass or less, good adhesive strength can be maintained.
• the content of the component (C) is preferably 50 to 300 parts by mass, more preferably 70 to 200 parts by mass, and 100 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). It is even more preferably about 170 parts by mass, and most preferably 135 to 160 parts by mass.
• an epoxy resin composition having excellent low temperature curability and adhesiveness can be obtained.
• the content of the component (C) is 300 parts by mass or less, good adhesive strength can be maintained.
• the functional group equivalent ratio of the component (A) and the component (B) to the component (C) ( ⁇ functional group equivalent of the component (A) + functional group equivalent of the component (B) ⁇ / functional group equivalent of (C)) is It is preferably 0.1 to 2.0, more preferably 0.2 to 1.5, even more preferably 0.3 to 1.0, and most preferably 0.40 to 0.60. preferable.
• the functional group equivalent ratio is 0.1 to 2.0, the curability of the epoxy resin composition can be improved.
• the functional group equivalent ratio is calculated by calculating the ratio ( ⁇ (A) + (B) ⁇ / (C)) of the content (blending amount) of each component divided by the epoxy equivalent or the SH equivalent. The value obtained.
• the epoxy functional group equivalent that is, the total number of epoxy groups contained in each of these components is determined. Specifically, the value obtained by dividing the mass (g) of the epoxy resin contained in each of the component (A) and the component (B) by the epoxy equivalent of the epoxy resin is obtained.
• the thiol functional group equivalent that is, the total number of SH groups contained in the component (C) is determined. Specifically, the value obtained by dividing the mass (g) of the thiol compound contained in the component (C) by the thiol (SH) equivalent of the thiol compound is obtained.
• the above values are calculated for each epoxy resin or each thiol compound, and the weighted averages thereof are the epoxy functional group equivalents of each component.
• the equivalent amount is a thiol functional group.
• the sum of the epoxy functional group equivalents of the component (A) and the component (B) obtained as described above is divided by the thiol functional group equivalent of the component (C) to obtain ((C) component (C).
• the functional group equivalent ratio of the component A) and the component (B) can be determined.
• the component (D) contained in the epoxy resin according to the present invention is a latent curing agent.
• the latent curing agent refers to a curing agent capable of ensuring storage stability such that there is little change in viscosity or physical properties with time in a state of being dispersed in the components (A) and (B).
• the component (D) is not particularly limited as long as it is a latent curing agent as described above, but it promotes curing by the component (C), and a compound having thermosetting property is particularly preferable.
• the component (D) is a compound having an imidazole skeleton; an epoxy adduct compound (epoxy compound, tertiary amine compound, etc.) obtained by adding a tertiary amine compound or the like to an epoxy resin and stopping the reaction in the middle. It is preferable to use the reaction product with and the like); and further, it is preferable to use fine powder obtained by crushing these compounds.
• the component (D) is preferably a modified aliphatic polyamine adduct or a modified alicyclic polyamine adduct, and is a modified aliphatic polyamine adduct. Is particularly preferable.
• the amine value thereof is preferably 50 to 300, more preferably 70 to 200, and most preferably 80 to 150.
• the amine value is the mass (mg) of hydrochloric acid and equivalent potassium hydroxide (KOH) required to neutralize the primary, secondary and tertiary amines contained in 1 g of the epoxy adduct compound. Is.
• the amine value can be measured according to ASTM D2074.
• the component (D) is preferably solid at 25 ° C.
• the softening point of the component (D) is preferably 70 to 300 ° C., more preferably 90 to 200 ° C., and more preferably 100 to 130 ° C. from the viewpoint of low temperature curability and storage stability. Is the most preferable.
• the average particle size of the component (D) is preferably 0.1 to 50 ⁇ m, more preferably 1 to 30 ⁇ m, even more preferably 2 to 20 ⁇ m, and most preferably 5 to 10 ⁇ m.
• the average particle size is 0.1 to 50 ⁇ m, the dispersibility when mixed with the component (A) and the component (B) becomes good, and an epoxy resin composition exhibiting stable low temperature curability can be obtained.
• Examples of the method for measuring the average particle size include image analysis of a laser diffraction / scattering type, a microsorting control type particle size / shape distribution measuring device, an optical microscope, an electron microscope, and the like.
• the latent curing agent as the component (D), either a synthetic product or a commercially available product may be used.
• PN-23 commercially available products of the component (D) include, for example, Amicure (registered trademark) PN-23, PN-23J, PN-31, PN-31J, PN-40J, PN-H, PN-R, MY-24, MY.
• Amicure registered trademark
• PN-23J PN-23J
• PN-31 PN-31J
• PN-40J PN-H
• PN-R MY-24
• MY MY.
• the latent curing agent as the component (D) may be used alone or in combination of two or more.
• the content of the component (D) refers to the total amount.
• the content of the component (D) is preferably 0.001 to 30 parts by mass, more preferably 0.01 to 20 parts by mass, and 0.01 to 17 parts by mass with respect to 100 parts by mass of the component (C). It is even more preferably by mass, and most preferably 5 to 16 parts by mass.
• the content of the component (D) is 0.001 to 30 parts by mass, the low temperature curability can be maintained while maintaining good storage stability of the epoxy resin composition.
• the component (E) contained in the epoxy resin according to the present invention is a reactive diluent.
• the reactive diluent refers to a compound that has a function of a solvent and has a group that reacts with the components (A) to (D) by itself.
• the component (E) is not particularly limited as long as it is a reactive diluent as described above, but is a compound having one epoxy group in one molecule from the viewpoint of reducing the viscosity of the epoxy resin composition. preferable.
• the viscosity of the component (E) is preferably 1 to 1000 mPa ⁇ s, more preferably 1 to 700 mPa ⁇ s, and 1 to 500 mPa ⁇ s. It is even more preferable to have it, and most preferably 10 to 100 mPa ⁇ s.
• the epoxy equivalent of the component (E) is preferably 100 to 500 g / eq, more preferably 150 to 300 g / eq, and most preferably 170 to 250 g / eq.
• the epoxy equivalent is 100 to 500 g / eq, it is possible to obtain an epoxy resin composition having a low viscosity and excellent curing shrinkage while maintaining good curability of the epoxy resin composition.
• component (E) examples include phenylglycidyl ether, cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, C12 to C14 alcohol glycidyl ether, butane diglycidyl ether, and the like.
• Examples thereof include, but are not limited to, hexane diglycidyl ether, cyclohexanedimethyl diglycidyl ether, neodecanoic acid glycidyl ester, and glycidyl ether having polyethylene glycol or polypropylene glycol as a main skeleton. Further, these may be used alone or in combination of two or more. When two or more kinds are used in combination, the content of the component (E) refers to the total amount.
• the component (E) contains p-tert-butylphenylglycidyl ether from the viewpoint of improving the adhesive strength to different materials while maintaining the curing shrinkage low.
• the content of the component (E) is preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, and 50 to 120 parts by mass with respect to 100 parts by mass in total of (A) and (B). It is even more preferably by mass, and most preferably 60 to 100 parts by mass.
• an epoxy resin composition having a low viscosity can be obtained while maintaining good adhesive strength.
• the epoxy resin composition according to the present invention may further contain an inorganic filler as the component (F) in addition to the above components (A) to (E).
• the component (F) a known material used as an inorganic filler can be used.
• Specific examples of the component (F) include alumina powder, calcium carbonate powder, talc powder, silica powder, fumed silica powder, silver powder, nickel powder, palladium powder, carbon powder, tungsten powder, and plated powder. Not limited. These may be used alone or in combination of two or more. When two or more kinds are used in combination, the content of the component (E) refers to the total amount.
• the component (F) preferably contains silica powder or fumed silica powder, more preferably contains silica powder, and particularly preferably contains spherical silica powder.
• the average particle size of the component (F) is preferably 0.01 to 50 ⁇ m, more preferably 0.1 to 30 ⁇ m, and particularly preferably 0.1 to 5 ⁇ m.
• the average particle size is 0.01 to 50 ⁇ m, it is possible to effectively suppress the increase in the viscosity of the obtained epoxy resin composition.
• the content of the component (F) is preferably 1 to 300 parts by mass, more preferably 30 to 200 parts by mass, and 50 to 50 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). Most preferably, it is 150 parts by mass.
• the content of the component (F) is 1 to 300 parts by mass, the adhesive strength can be improved while suppressing the increase in the viscosity of the obtained epoxy resin composition.
• the epoxy resin according to the present invention is an organic filler (however, excluding the components (A) to (E)) and a pigment in addition to the above components (A) to (E), as long as the characteristics of the present invention are not impaired.
• Dyes, silane coupling agents, leveling agents, rheology control agents, storage stabilizers and other additives may be further contained as optional components.
• organic filler powder of an organic substance (however, excluding the components (A) to (E)) composed of rubber, elastomer, plastic, polymer (or copolymer) and the like can be used. Further, as the organic filler, an organic filler having a multi-layer structure such as a core-shell type can also be used. These may be used alone or in combination of two or more.
• the average particle size of the organic filler is preferably in the range of 0.05 to 50 ⁇ m.
• examples of the organic filler include a polymer of an acrylic acid ester and / or a methacrylic acid ester or a filler made of a copolymer thereof, a filler made of a polymer of a styrene compound or a filler made of a copolymer, and the like. Is preferable.
• the suitable content of the organic filler (when two or more kinds are contained, the total amount thereof) is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (A), and is preferably 5 to 30 parts by mass. It is more preferable to have it.
• silane coupling agent examples include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldipropyloxysilane, and 3-glycidoxypropyldimethyl.
• Glycidyl group-containing silane coupling agents such as silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane; vinyltris ( ⁇ -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane Vinyl group-containing silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldimethylmonomethoxysilane, 3-methacryloxypropyldimethylmonoethoxysi
• (Meta) acrylic group-containing silane coupling agent N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, etc.
• Examples thereof include amino group-containing silane coupling agents; ⁇ -mercaptopropyltrimethoxysilane; ⁇ -chloropropyltrimethoxysilane.
• a glycidyl group-containing silane coupling agent is preferable from the viewpoint of excellent adhesive strength. These may be used alone or in combination of two or more.
• the preferable range of the content of the silane coupling agent (when two or more kinds are contained, the total amount thereof) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A).
• borate ester As the storage stabilizer, borate ester, phosphoric acid, alkyl phosphoric acid ester, and p-toluenesulfonic acid can be used.
• the borate ester include, but are not limited to, tributyl borate, trimethoxyboroxin, ethyl borate and the like.
• the alkyl phosphate ester trimethyl phosphate, tributyl phosphate and the like can be used, but the present invention is not limited thereto. These may be used alone or in combination of two or more.
• the storage stabilizer is one or more selected from the group consisting of phosphoric acid, alkyl phosphate ester, borate ester, trimethoxyboroxin, and methyl p-toluenesulfonate. It is preferable, and it is more preferable that it is a phosphoric acid or a borate ester. From the viewpoint of maintaining low-temperature curability and lowering the curing shrinkage, the suitable content of the storage stabilizer (if two or more are contained, the total amount) is based on 100 parts by mass of the component (A). , 0.1 to 10 parts by mass is preferable.
• the method for producing the epoxy resin composition according to the present invention is not particularly limited, and can be produced by a conventionally known method. For example, each of the components (A) to (E), the component (F) added as needed, and the component (arbitrary component) added arbitrarily are weighed in predetermined amounts and sequentially or in any order.
• the epoxy resin composition according to the present invention can be obtained by adding the epoxy resin composition to the mixing pot at the same time and then mixing the mixture using a mixing means such as a mixer. At this time, the production conditions are not particularly limited, but the mixing temperature is preferably 10 to 50 ° C., and the mixing time is preferably 10 minutes to 3 hours.
• ⁇ Applying method> As a method for applying the epoxy resin composition according to the present invention to an adherend, a method similar to a known method for applying a sealant or an adhesive is used. For example, methods such as dispensing, spraying, inkjet printing, screen printing, gravure printing, dipping, and spin coating using an automatic coating machine can be used.
• the viscosity (25 ° C.) of the epoxy resin composition according to the present invention is preferably 10,000 mPa ⁇ s or less, more preferably 5000 mPa ⁇ s or less, and even more preferably 2000 mPa ⁇ s or less. It is preferable that it is 1500 mPa ⁇ s or less, and most preferably 600 mPa ⁇ s or less.
• the lower limit thereof is not particularly limited, but is, for example, 100 mPa ⁇ s or more, and further 200 mPa ⁇ s or more.
• the epoxy resin composition according to the present invention can be cured by heating. Therefore, another aspect of the present invention is a cured product obtained by curing the epoxy resin composition (cured product of the epoxy resin composition).
• the curing shrinkage rate is 5% or less.
• the curing shrinkage rate is a value obtained by the method described in Examples.
• the curing shrinkage rate is more preferably 4.5% or less for the purpose of suppressing distortion of the adherend.
• the lower limit of the curing shrinkage rate is not particularly limited, but is substantially 0%.
• the method for producing the cured product is not particularly limited, and a known method can be used.
• One example is a method in which the epoxy resin composition according to the present invention is applied onto an adherend and then heated to cure. At this time, the thickness of the coating film is not particularly limited, and is appropriately adjusted within a range in which the adherend can be adhered.
• the conditions for the heating temperature and the heating time (curing time) are not particularly limited as long as the epoxy resin composition can be sufficiently cured. However, as a suitable specific example of the heating conditions, for example, the heating temperature may be used.
• the temperature is preferably 50 ° C to 200 ° C, more preferably 50 ° C or higher and lower than 200 ° C, even more preferably 60 ° C to 150 ° C, and particularly preferably 70 to 100 ° C.
• the curing temperature is low.
• the curing time is also not particularly limited, but is preferably, for example, 30 seconds to 5 hours, more preferably 1 minute to 3 hours.
• the heating temperature and the heating time when the temperature is 50 ° C. or higher and lower than 200 ° C., it is preferably 1 minute to 3 hours, more preferably 2 minutes to 2 hours. ..
• the epoxy resin composition according to the present invention has excellent adhesiveness to different materials, it is suitable for adhesion and / or sealing applications between members having different linear expansion coefficients such as plastic and metal.
• the "different materials” refer to two or more materials having different materials from each other, specifically, materials having different coefficients of linear expansion from each other. That is, the epoxy resin composition according to the present invention is preferably used for adhesion and / or sealing between adherends having different coefficients of linear expansion.
• the difference in the linear expansion coefficient of the materials having different linear expansion coefficients is not particularly limited, but is preferably 0.1 ⁇ 10 -6 / K to 300 ⁇ 10 -6 / K, and is preferably 1 ⁇ 10 -6 / K. It is more preferably about 200 ⁇ 10 -6 / K, and particularly preferably 5 ⁇ 10 -6 / K to 100 ⁇ 10 -6 / K.
• the "difference in the coefficient of linear expansion of materials having different coefficients of linear expansion" is the line from the coefficient of linear expansion of the material having a larger coefficient of linear expansion to the line of the material having a smaller coefficient of linear expansion. It shall represent the value obtained by subtracting the expansion coefficient.
• the coefficient of linear expansion is determined by a method for measuring the coefficient of linear expansion of each material in accordance with JIS Z 2285: 2003 for metal materials and JIS K 7197: 2012 for plastics.
• adhesion between different materials include metal-to-metal, metal-to-plastic, metal-to-rubber, plastic-to-rubber, plastic-to-plastic, and rubber-to-rubber.
• metals and metals, metals and plastics, and plastics are preferable, and metals and plastics are more preferable.
• Examples of the metal to be adhered include iron, stainless steel, copper, nickel, zinc, aluminum, magnesium, gold, silver, and titanium.
• Examples of the plastic to be adhered include fiber reinforced plastic (FRP), glass fiber reinforced plastic (GFRP), carbon fiber reinforced plastic (CFRP), polyacrylic, polyester, polyamide, and acrylonitrile-butadiene-styrene co-weight.
• FRP fiber reinforced plastic
• GFRP glass fiber reinforced plastic
• CFRP carbon fiber reinforced plastic
• ABS Combined
• 6 nylon, 6,6-nylon, polycarbonate, polyacetal, polyethylene terephthalate, polybutylene terephthalate (PBT), polyphenylene sulfide, polyphenylene ether, polyether ether ketone, polyethylene, polypropylene and the like can be mentioned.
• Examples of the rubber to be adhered include nitrile rubber, urethane rubber, silicone rubber, EPDM and the like. More detailed specific examples of adhesion and / or encapsulation between dissimilar materials include adhesion between at least two or more adherends selected from these materials.
• each material (each adherend) listed above may be surface-treated in advance or may remain untreated.
• the epoxy resin composition according to the present invention can be used for various purposes. Specific examples of applications include, in the field of automobiles, bonding of switch parts for automobiles, head lamps, engine internal parts, electrical parts, drive engines, brake oil tanks, front hoods, fenders, doors and other body panels, windows, etc. Encapsulation, casting, coating, 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 disks, etc.
• optical fiber materials around optical switches and optical connectors, optical passive components, optical circuit components, adhesion around optical electron integrated circuits, encapsulation, coating, etc. In the field of optical equipment, cameras Adhesion, sealing, coating, etc.
• the epoxy resin composition according to the present invention has a low viscosity, it can be applied in a minute amount and is suitable for use in minute parts.
• the epoxy resin (mixture) is a bifunctional bisphenol A type epoxy resin (epoxy equivalent: about 180 g / eq) liquid at 25 ° C. and a bifunctional bisphenol F type epoxy resin (epoxy equivalent: about) liquid at 25 ° C. 160 g / eq) with a mass ratio of about 50:50.
• Product name jER (registered trademark) 834 manufactured by Mitsubishi Chemical Corporation
• (B-2) Ingredient: (B-2-1) Bifunctional bisphenol A type epoxy resin solid at 25 ° C
• Product name jER (registered trademark) 1001 (manufactured by Mitsubishi Chemical Corporation) Epoxy equivalent 450-500 g / eq Softening point 64 ° C
• B-2-2 Bifunctional biphenyl type epoxy resin solid at 25 ° C
• Product name jERYX (registered trademark) 4000H (manufactured by Mitsubishi Chemical Corporation) Epoxy equivalent 187-197 g / eq Softening point 105 ° C
• C Ingredient: Pentaerythritol tetrakis (3-mercaptobutyrate) Brand name Karenz MT (registered trademark) PE1 (manufactured by Showa Denko KK) SH equivalent 136 g / mol Number of SH groups in one molecule 4
• D Ingredient: Denatured aliphatic polyamine adduct
• the viscosity of the obtained epoxy resin composition was measured using a cone plate type viscometer at a shear rate of 10s -1 in an environment of 25 ° C. and 55% RH.
• the acceptance criteria are 2000 mPa ⁇ s or less, but in consideration of workability, 1500 mPa ⁇ s or less is preferable, and 600 mPa ⁇ s or less is more preferable.
• each epoxy resin composition is applied to a test piece of SUS304 (25 ⁇ 100 ⁇ 1.0 mm, linear expansion coefficient 18 ⁇ 10-6 / K), and the following test pieces of each plastic material are bonded onto the test piece. I fixed it with a pinch. At this time, the adhesive area of the test piece of each plastic material was set to 25 ⁇ 10 mm. It was cured in a hot air drying oven at 80 ° C. for 60 minutes to obtain a cured product. After returning the cured product to room temperature, the shear adhesive strength (unit: MPa) was measured at a tensile speed of 50 mm / min according to JIS K 6850: 1999 using a tensile tester.
• the epoxy resin composition of the example can be cured by heating at 80 ° C. for 60 minutes, and further exhibits good adhesive strength (high shear adhesive strength). .. As described above, since it can be cured at a temperature lower than 100 ° C., it was confirmed that the epoxy resin composition of the example has excellent low temperature curability.
• the epoxy resin compositions of Examples 1 to 3 were used in all the combinations of the test pieces as compared with Comparative Example 1 which did not contain the component (B). It showed good shear adhesion strength. Further, it was obtained that the epoxy resin compositions of Examples 1 to 3 had a small curing shrinkage rate. Further, the epoxy resin compositions of Examples 1 to 3 had a low viscosity, and the results showed that the viscosities of the compositions of Examples 1 and 3 were particularly low.
• the epoxy resin composition according to the present invention can exhibit good adhesiveness in different materials by containing the components (A) to (E).
• the epoxy resin composition according to the present invention has good low-temperature curability, low viscosity, and excellent curing shrinkage.
• the epoxy resin composition according to the present invention has excellent adhesiveness to different materials. Further, the epoxy resin composition according to the present invention has low-temperature curability and low viscosity for exhibiting good workability, and further has low curing shrinkage, so that it is an adhesive used for various members. It is very useful as a coating agent and a potting agent.

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• 2021
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