WO2016158828A1 - 樹脂組成物、導電性樹脂組成物、接着剤、導電性接着剤、電極形成用ペースト、半導体装置 - Google Patents
樹脂組成物、導電性樹脂組成物、接着剤、導電性接着剤、電極形成用ペースト、半導体装置 Download PDFInfo
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- 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
- C08G59/56—Amines together with other curing agents
- C08G59/60—Amines together with other curing agents with amides
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
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- 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
- C08G59/56—Amines together with other curing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
Definitions
- the present invention relates to a resin composition, a conductive resin composition, an adhesive, a conductive adhesive, an electrode forming paste, and a semiconductor device.
- the resin composition is used as a sealing material or adhesive for wiring boards, circuit boards, circuit boards obtained by multilayering these, semiconductor chips, coils, electric circuits, automobile parts, and the like.
- Such a resin composition is required to have heat resistance and a property that cures in a short time (hereinafter sometimes referred to as “short-time curing property”).
- Patent Document 1 describes an epoxy resin composition using an addition reaction product of unsubstituted imidazole and bisphenol-type diglycidyl ether as a curing agent. Such an epoxy resin composition can be cured in a short time to form a cured resin layer having excellent voidless adhesiveness.
- Patent Document 2 describes a thermosetting resin composition containing a curing agent having an acidic substituent and an unsaturated maleimide group, dicyandiamide, a copolymer resin containing a specific monomer unit, and an epoxy resin.
- a thermosetting resin composition has metal foil adhesiveness, heat resistance, and the like.
- the resin composition when used, it is required to have high adhesive strength at the time of heating in addition to heat resistance and short-time curing characteristics.
- the rate of change between the adhesive strength at normal temperature and the adhesive strength during heating (change rate of adhesive strength) is low.
- the cured product of the resin composition has flexibility. That is, it is preferable that the room temperature elastic modulus is low when the resin composition is cured.
- the object of the present invention is a resin composition, conductive resin composition, adhesive having long-term heat resistance, short-time curing characteristics, high adhesive strength during heating, low rate of change in adhesive strength and low room temperature elastic modulus It is to provide an agent, a conductive adhesive, an electrode forming paste, and a semiconductor device.
- the inventor has a compound having an OH group and any of primary to tertiary amines in the molecule, dicyandiamide and / or imidazoles, bismaleimides, and one or more epoxy groups in the molecule. It has been found that a resin composition containing a compound or a cyanate ester has long-term heat resistance and short-time curing characteristics, has high adhesive strength during heating, and has a low rate of change in adhesive strength and low room temperature elastic modulus. . The present invention has been completed based on these findings.
- the present invention is a resin composition, a conductive resin composition, an adhesive, a conductive adhesive, an electrode forming paste, and a semiconductor device that have solved the above problems by having the following configuration.
- A Compound having an OH group and any one of primary to tertiary amines in the molecule,
- B Dicyandiamide and / or imidazoles,
- C Bismaleimides,
- D One in the molecule
- a resin composition comprising a compound having one or more epoxy groups or a cyanate ester.
- the resin composition of the present invention has long-term heat resistance and short-time curing characteristics, has high adhesive strength upon heating, and has a low rate of change in adhesive strength and low room temperature elastic modulus.
- FIG. 3 is a diagram schematically showing the structure of resin compositions according to Examples 1 to 21.
- FIG. 3 is a diagram schematically showing the structure of resin compositions according to Comparative Examples 7 to 11.
- the resin composition of the present invention comprises (A) a compound having an OH group in the molecule and any of primary to tertiary amines, (B) dicyandiamide and / or imidazoles, (C) bismaleimides, (D ) A compound having one or more epoxy groups in the molecule, or a cyanate ester is included.
- Low temperature refers to a temperature lower than the temperature when the compound contained in the resin composition reacts alone (self-polymerization). For example, bismaleimide cures at 300 ° C. or higher. On the other hand, when the resin composition of this invention hardens
- Short-time curing refers to curing in a time shorter than a predetermined time (for example, 30 minutes or less).
- Adhesive strength refers to the strength with which an object having a resin composition (for example, an alumina test piece) is adhered. “Change rate of adhesive strength” is the ratio between the adhesive strength at normal temperature and the adhesive strength at heating.
- Compound having an OH group and any of primary to tertiary amines in the molecule examples include compounds having a benzoxazine skeleton, aminophenols, and the like. From the viewpoint of long-term heat resistance, a compound having a benzoxazine skeleton, such as benzoxazine, which is a high heat-resistant resin, is preferable.
- “having an OH group in the molecule” means not only the case where the molecule has an OH group itself, such as phenols, but also the case where the molecule has an OH group by ring-opening like benzoxazine. Including cases.
- Dicyandiamide (“DICY”) is an amide compound represented by H 2 N—CNH—NH—CN. Dicyandiamide functions as a curing agent for bismaleimides when the resin composition of the present invention is synthesized. Further, it functions as a catalyst in the reaction of a compound having an OH group and any of primary to tertiary amines in the molecule with bismaleimides. Dicyandiamide is a compound widely used for industrial purposes, and is excellent in adhesiveness, heat resistance and the like.
- Imidazoles are heterocyclic compounds containing a nitrogen atom at the 1,3-position of a 5-membered ring. Imidazoles function as a curing agent for bismaleimides when the resin composition of the present invention is synthesized. Further, it functions as a catalyst in the reaction of a compound having an OH group and any of primary to tertiary amines in the molecule with bismaleimides. Examples of imidazoles include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, and 2-phenyl-4methyl.
- Imidazole 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl- 2-ethyl-4-methylimidazole, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, or 2,4-diamino-6- [2′- Methylimidazolyl- (1 ′)] ethyl-s-triazine isocyanur
- a hydrous addition product dehydrate.
- Bismaleimides include, for example, N, N ′-(4,4′-diphenylmethane) bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebis Maleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane , M-phenylene bismaleimide (N, N′-1,3-phenylene bismaleimide), 1,6-bismaleimide hexane, 1,2-bismaleimide ethane (N, N′-ethylene dimaleimide), N, N ′-(1,2-phenylene) bismaleimide, N, N′-1,4-phenylenedimaleimide, N, N ′-(sulfonitrile, 4-
- the bismaleimides in the present invention include solids, but are more preferably liquid.
- Solid bismaleimides have low solubility in general organic solvents. Therefore, when solid bismaleimides are used, dilution with a large amount of organic solvent is required. However, in this case, the solvent is volatilized at the time of curing to form a void, leading to a decrease in adhesive strength and generation of cracks.
- there is a technique of dispersing solid bismaleimides in the resin composition by a roll mill or the like but in this technique, the viscosity of the resin composition becomes high.
- a resin composition containing liquid bismaleimide has a low viscosity. Therefore, workability when using the resin composition is improved.
- dimer acid-modified bismaleimide is, for example, BMI-1500 or BMI-1700 which is a liquid bismaleimide or BMI-3000 which is a solid bismaleimide (both manufactured by Designer molecules).
- BMI-1500 or BMI-1700 which is a liquid bismaleimide or BMI-3000 which is a solid bismaleimide (both manufactured by Designer molecules).
- Epoxy resins include bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, novolac type epoxy resin, alicyclic epoxy resin, naphthalene type epoxy resin, ether or poly Examples include ether-based epoxy resins, oxirane ring-containing polybutadienes, and silicone epoxy copolymer resins.
- Liquid epoxy resins include bisphenol A type epoxy resins having an average molecular weight of about 400 or less; branched polyfunctional bisphenol A type epoxy resins such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; bisphenol F About 570 or less phenol novolac type epoxy resin; vinyl (3,4-cyclohexene) dioxide, 3,4-epoxycyclohexylcarboxylic acid (3,4-epoxycyclohexyl) methyl, bis (3,4-adipate) Cycloaliphatic epoxy resins such as epoxy-6-methylcyclohexylmethyl), 2- (3,4-epoxycyclohexyl) 5,1-spiro (3,4-epoxycyclohexyl) -m-dioxane; 3,3 ′, 5,5'-tetramethyl Biphenyl type epoxy resin such as 4,4'-diglycidyloxybiphenyl; glycidy
- An epoxy resin having a silicone skeleton such as 1,3-bis (3-glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane can also be used.
- diepoxide compounds such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol glycidyl ether, neopentyl glycol diglycidyl ether; trimethylolpropane triglycidyl ether, glycerin triglycidyl ether Examples of the triepoxide compound are also included.
- Solid epoxy resins include high molecular weight, ortho-cresol novolac epoxy resin, phenol novolac epoxy resin, naphthol novolac epoxy resin, modified phenol epoxy resin, naphthalene epoxy resin, dicyclopentadiene epoxy resin, glycidyl Amine type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, biphenyl aralkyl type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, aliphatic type epoxy resin, stilbene type epoxy resin, bisphenol A novolak Type epoxy resin and the like.
- the epoxy resin may be used alone or in combination of two or more. It is also possible to use a dimer acid-modified epoxy resin.
- the dimer acid-modified epoxy resin is, for example, jER871 (manufactured by Mitsubishi Chemical Corporation). By using the dimer acid-modified epoxy resin, the room temperature elastic modulus of the resin composition can be kept low. Such a cured product of the resin composition is unlikely to crack.
- the cyanate ester is not particularly limited as long as it is a compound containing a cyanate group.
- the cyanate ester is, for example, Lecy (manufactured by Lonza Japan Co., Ltd.) which is a liquid ester. By using cyanate ester, long-term heat resistance can be improved.
- the resin composition of the present invention comprises (A) a compound having an OH group in the molecule and any one of primary to tertiary amines (hereinafter sometimes referred to as “component (A)”), (B) dicyandiamide, and / Or imidazoles (hereinafter sometimes referred to as “component (B)”), (C) bismaleimides (hereinafter sometimes referred to as “component (C)”), (D) one or more in the molecule It can be produced by mixing a compound having an epoxy group or a cyanate ester (hereinafter sometimes referred to as “component (D)”).
- component (D) The manufacturing method of a resin composition will not be specifically limited if it is a method which can obtain the composition which the above-mentioned each component mixed uniformly.
- a conductive material such as a conductive filler may be added to the resin composition.
- the conductive filler include an Ag filler, an AgSn filler, and an alloy filler thereof.
- the conductive material is preferably 19 to 65% by volume (specific gravity is about 10; equivalent to 70 to 95% by weight for Ag filler or the like), and 23 to 48% by volume (specific gravity is 10%). More preferably, it is about 75 to 90% by weight for an Ag filler or the like.
- a conductive resin composition (conductive resin composition) is used when electrical connection is required, such as a circuit board or an electric circuit.
- heat conductive materials such as Ag and an alumina
- a resin composition having thermal conductivity is used when it is required to release heat from a chip or a substrate.
- the room temperature elastic modulus (tensile elastic modulus) of the resin composition is preferably less than 4 GPa, more preferably less than 2 GPa.
- the room temperature elastic modulus is 5 GPa or more. Sometimes it becomes. However, even in such a case, the room temperature elastic modulus is preferably less than 8 GPa.
- a silica filler or silicone powder may be added to the resin composition as a filler. Adding a filler such as silicone powder leads to low elasticity.
- the resin composition according to the present invention can be used as an adhesive.
- the adhesive is used as an adhesive for bonding an electronic component to a circuit, a semiconductor element and another semiconductor element, and / or a semiconductor element and a semiconductor element mounting support member.
- the adhesive is a conductive adhesive, it can be used as an alternative to solder. Since this conductive adhesive contains a resin composition, it is less elastic than solder and is very useful from the viewpoint of stress relaxation.
- the semiconductor device has a structure in which a semiconductor element and another semiconductor element and / or a semiconductor element and a semiconductor element mounting support member are bonded.
- a semiconductor device including a cured product of the resin composition or a cured product of the adhesive according to the present invention is excellent in reliability at a high temperature of 200 ° C.
- the quaternary system is a system that includes all of the components (A) to (D) (the system according to the present invention).
- the ternary system is a system including any three components among the components (A) to (D).
- component (A) “Fa type benzoxazine” (manufactured by Shikoku Kasei Kogyo Co., Ltd.) is diluted with butyl carbitol acetate (hereinafter sometimes referred to as “BCA”) to obtain a 66% solution. did.
- BCA butyl carbitol acetate
- any of the following was used. ⁇ "EH-3636AS” (DICY100%) Made by ADEKA Corporation "EH-3842” (DICY64%, accelerator 36%) Made by ADEKA Corporation "2PHZ-PW” (2-phenyl-4,5-dihydroxymethyl Imidazole) Shikoku Kasei Kogyo Co., Ltd. “2P4MHZ-PW” (2-phenyl-4-methyl-5-hydroxymethylimidazole) Shikoku Kasei Kogyo Co., Ltd.
- ⁇ "BMI” solid. 4,4'-diphenylmethane bismaleimide
- Kay made by Kasei Chemical Co., Ltd.
- BMI-1500 liquid, dimer acid modified
- any of the followings was used.
- ⁇ “EXA-835LV” (BisA-BisF mixed epoxy) manufactured by DIC Corporation
- jER871 dimer acid-modified epoxy
- Example 1 2 parts of “Fa type benzoxazine” 66% solution (solid content: 1.33 parts), 0.3 part of “EH-3636AS”, 1 part of “BMI-1500”, 1 part of “EXA-835LV” After putting into a container and stirring manually, it disperse
- Example 2 2 parts of “Fa type benzoxazine” 66% solution (solid content: 1.33 parts), 0.1 part of “2PHZ-PW”, 1 part of “BMI”, 1 part of “jER871” are put in a container, After stirring manually, it was dispersed with a three-roll mill to prepare a resin composition b.
- Example 3 2 parts of “Fa type benzoxazine” 66% solution (solid content: 1.33 parts), 0.1 part of “2PHZ-PW”, 1.5 parts of “BMI-1500”, 1 part of “jER871” After putting into a container and stirring manually, it disperse
- Example 4 2 parts of "Fa type benzoxazine” 66% solution (solid content: 1.33 parts), 0.1 part of “2P4MHZ-PW”, 1.5 parts of “BMI-1500”, 1 part of "jER871” After putting into a container and stirring manually, it disperse
- Comparative Examples 1 to 3 are examples of the ternary system in which any one of the components (A) to (C) is removed from the quaternary system of Example 1.
- Comparative Example 4 is an example of a ternary system obtained by removing the component (D) from the quaternary system of Example 2.
- Comparative Example 5 is an example of a ternary system obtained by removing the (D) component from the quaternary system of Example 3.
- Comparative Example 6 is an example of a ternary system obtained by removing the component (D) from the quaternary system of Example 4.
- the measurement of curing characteristics was performed as follows. First, the resin composition was cured (curing conditions: temperature 200 ° C., 30 minutes) to prepare a plate-shaped cured film. Each cured film was subjected to differential scanning calorimetry (DSC) using an apparatus “DSC204 F1” manufactured by NETZSCH. The measurement conditions are 25 ° C. to 350 ° C. and a temperature increase rate of 10 ° C./min.
- the measurement results were “ ⁇ ” as those having excellent exothermic characteristics at 300 ° C. or lower and having no exothermic peak, and “X” when having exothermic peaks at 300 ° C. or lower.
- the long-term heat resistance was calculated as follows. First, similarly to the measurement of curing characteristics, the resin composition was cured to produce a plate-shaped cured film, and the weight was measured. Next, the cured film was allowed to stand for 100 hours in an oven set at 200 ° C. (an apparatus “DF411” manufactured by Yamato Kagaku Co., Ltd.), and the weight of the cured film was measured. Then, the weight loss was calculated based on the weight of the cured film before standing and the weight of the cured film after standing.
- the calculation results are “ ⁇ ” with a weight loss of less than 8% and excellent long-term heat resistance, “ ⁇ ” for 8-12%, and “x” for 12% or more.
- the resin composition was applied onto a 20 mm square alumina substrate using a # 200 mesh screen mask having 1.5 mm square ⁇ 25 openings, and 10 sheets of 10 pieces of 25 printed patterns were applied.
- a test piece on which a 2 mm ⁇ 1.6 mm size alumina chip was mounted was prepared and cured under curing conditions “temperature 200 ° C., 30 minutes”. By measuring the shear strength of this test piece using a strength tester (model number: Model 1605HTP manufactured by Aiko Engineering Co., Ltd.), the bond strength at normal temperature was obtained.
- an adhesive strength of 30 N / mm 2 or more was “ ⁇ ”, 30 to 20 N / mm 2 was “ ⁇ ”, and less than 20 N / mm 2 was “x”.
- test piece cured under the curing condition “temperature of 200 ° C., 30 minutes” was heated for 1 minute or more on a 200 ° C. hot plate, and this test piece was sheared using a strength tester (same as above). By measuring the strength, the adhesive strength at 200 ° C. (adhesive strength during heating) was determined.
- an adhesive strength of 7 N / mm 2 or more was “ ⁇ ”, 7 to 5 N / mm 2 was “ ⁇ ”, and less than 5 N / mm 2 was “x”.
- the rate of change of the adhesive strength in the resin composition was calculated based on the value of the adhesive strength at normal temperature and the value of the adhesive strength at 200 ° C.
- the calculation results are “ ⁇ ” when the rate of change is less than 85%, and “x” when 85% or more.
- the resin composition was applied on a Teflon (registered trademark) sheet so that the film thickness was about 150 ⁇ m, and cured in a sheet shape at 200 ° C. for 30 minutes. Cut into a 40 mm ⁇ 10 mm strip, the tensile modulus at room temperature was determined using DMS6100 manufactured by SII Nanotechnology.
- the tensile modulus is preferably less than 4 GPa, more preferably less than 2 GPa.
- the measurement results are “O” when the room temperature elastic modulus is less than 2 GPa, “ ⁇ ” when 2 to 5 GPa, and “X” when 5 GPa or more.
- a resin composition having an overall evaluation of “ ⁇ ” or “ ⁇ ” is a resin composition according to the present invention.
- the resin compositions of Examples 1 to 4 were generally higher in adhesive strength during heating and lower in the rate of change in adhesive strength than the resin compositions of Comparative Examples 1 to 6. .
- the resin compositions of Examples 1 to 4 were substantially lower in the room temperature elastic modulus than the resin compositions of Comparative Examples 1 to 6.
- the high adhesive strength during heating in the resin compositions of Examples 1 to 4 is considered to be because the OH group of the component (A) and the epoxy group of the component (D) react to increase the crosslink density. .
- This is also inferred from the fact that the comparative example 1 including the component (A) and the component (D) also shows a high value of the adhesive strength during heating.
- Comparative Example 2 including the component (A) and the component (D) the reason why the adhesive strength during heating is low is considered to be because the component (B) that acts as a catalyst is not included.
- the component (A) is considered to be a crosslinking agent between the component (C) and the component (D). Therefore, in the resin compositions of Examples 1 to 4, it is considered that the components (A) to (D) react with each other and have a two-dimensional structure as shown in FIG. By adopting such a structure, the molecular chain can be expanded and contracted two-dimensionally and thus has high flexibility. That is, the reason why the room temperature elastic modulus of the resin compositions of Examples 1 to 4 is low is considered to be due to such a two-dimensional structure.
- the component (A) in Example and Comparative Example 12 is a 66% solution of “Fa type benzoxazine” used in Example 1 or the like, or “Pd type benzoxazine” (manufactured by Shikoku Kasei Kogyo Co., Ltd.). Was diluted with butyl carbitol acetate (hereinafter sometimes referred to as “BCA”) to obtain a 50% solution.
- BCA butyl carbitol acetate
- any of the followings was used instead of the component (A) (indicated by (A ′) in Table 2).
- “H-4” phenol resin, Tg (glass transition point) 123 ° C.) Meiwa Kasei Co., Ltd.
- “MEH-7500” phenol resin, Tg 170 ° C.) Meiwa Kasei Co., Ltd.
- “MEH-8005” phenol) Resin, Tg 105 ° C.
- H-4 and “MEH-7500” manufactured by Meiwa Kasei Co., Ltd. were diluted with butyl carbitol (BC) to give a 50% solution.
- “MEH-8005” was used as it was.
- EH-3636AS As the component (B) in the examples, at least one of “EH-3636AS”, “EH-3842”, and “2PHZ-PW” was used.
- EH-3636AS or “DDH” (Dodecandiohydrazide manufactured by Tokyo Chemical Industry Co., Ltd., shown in Table 2 as (B ′)) was used.
- BMI As the component (C), “BMI”, “BMI-1500”, or any of the following was used. ⁇ “BMI-1700” (liquid, dimer acid modified) manufactured by Designer molecules ⁇ “BMI-3000” (solid, dimer acid modified) manufactured by Designer molecules
- Example 5 2 parts of "Fa benzoxazine” 66% solution (solid content: 1.33 parts), 0.3 part of "EH-3636AS”, 1 part of "BMI-1500”, 1 part of "jER871" in a container Then, after stirring manually, the mixture was dispersed with a three-roll mill to prepare a resin composition e.
- Example 6 2 parts of 66% solution of “Fa type benzoxazine” (solid content: 1.33 parts), 0.3 part of “EH-3636AS”, 1 part of “BMI-1500”, 0.5 part of “EXA-835LV” Part, “jER871” 0.5 part was placed in a container, and after hand stirring, dispersed with a three-roll mill to prepare a resin composition f.
- Example 7 2 parts of "Fa benzoxazine” 66% solution (solid content: 1.33 parts), 0.3 parts of "EH-3636AS”, 1 part of "BMI”, 1 part of "EXA-835LV” in a container After stirring and hand stirring, the mixture was dispersed with a three roll mill to prepare a resin composition g.
- Example 8 2 parts of "Fa type benzoxazine” 66% solution (solid content: 1.33 parts), 0.1 part of "EH-3842”, 2 parts of "BMI-1500”, 1.5 parts of "jER871” After putting into a container and stirring manually, it disperse
- Example 9 2 parts of "Fa type benzoxazine” 66% solution (solid content: 1.33 parts), 0.3 parts of "EH-3636AS”, 1 part of “BMI-3000”, 1.5 parts of "jER871” After putting into a container and stirring manually, it disperse
- Example 10 2 parts of "Fa type benzoxazine” 66% solution (solid content: 1.33 parts), 0.3 parts of "EH-3636AS”, 1 part of "BMI-1500", 1 part of "jER871", "Ag 9 parts of “Filler” was placed in a container and stirred manually, and then dispersed with a three-roll mill to prepare a resin composition j.
- Example 11 2 parts of "Fa type benzoxazine” 66% solution (solid content: 1.33 parts), 0.1 part of "EH-3842", 1 part of "BMI-1500”, 1 part of "EXA-835LV” After putting into a container and stirring manually, it disperse
- Example 12 2 parts of “Pd type benzoxazine” 50% solution (solid content: 1.33 parts), 0.3 part of “EH-3636AS”, 1 part of “BMI-1500”, 1 part of “EXA-835LV” After putting into a container and stirring manually, it disperse
- Example 13 2 parts of "Fa benzoxazine” 66% solution (solid content: 1.33 parts), 0.3 parts of "EH-3636AS”, 1 part of "BMI-1700", 1 part of "jER871" in a container After stirring and hand stirring, the mixture was dispersed with a three-roll mill to prepare a resin composition m.
- Example 14 2 parts of “Fa type benzoxazine” 66% solution (solid content: 1.33 parts), 0.3 part of “EH-3636AS”, 1 part of “BMI-1500”, 1 part of “jER871”, “silane” “Coupling agent” 0.05 part was put in a container and stirred manually, and then dispersed with a three-roll mill to prepare a resin composition n.
- Example 15 2 parts of “Fa type benzoxazine” 66% solution (solid content: 1.33 parts), 0.45 part of “EH-3636AS”, 2 parts of “BMI-1500”, 0.75 part of “jER871” After putting into a container and stirring manually, it disperse
- Example 16 3 parts of “Fa type benzoxazine” 66% solution (solid content: 2 parts), 0.3 part of “EH-3636AS”, 2 parts of “BMI-1500” and 1 part of “jER871” are put in a container. After stirring manually, it was dispersed with a three-roll mill to prepare a resin composition p.
- Example 17 2 parts of “Fa type benzoxazine” 66% solution (solid content: 1.33 parts), 0.2 part of “EH-3636AS”, 0.1 part of “2PHZ-PW”, “BMI-1500” 1 Part, “jER871” 1 part was put in a container and hand-stirred, and then dispersed by a three-roll mill to prepare a resin composition q.
- Example 18 2 parts of "Fa benzoxazine” 66% solution (solid content: 1.33 parts), 0.3 parts of "EH-3636AS”, 1 part of "BMI-1500", 1 part of "Lecy” in a container Then, the mixture was stirred manually and then dispersed with a three-roll mill to prepare a resin composition r.
- the resin compositions of Examples 5 to 18 have long-term heat resistance and short-time curing characteristics, similar to the resin compositions of Examples 1 to 4. As a result, the adhesive strength during heating was high, and the rate of change in adhesive strength and the room temperature elastic modulus were low.
- the adhesive strength at the time of heating is lower than that of the example, and the strength change rate and As a result, the room temperature elastic modulus was high.
- the reason why the room temperature elastic modulus is high is that the component (A ′) does not have an N group and cannot react with the component (C). That is, since the resin compounds in Comparative Examples 7 to 11 can only have a linear structure as shown in FIG. 2, the molecular chain can expand and contract only in one direction and has low flexibility. Therefore, the resin compounds in Comparative Examples 7 to 11 are considered to have a high room temperature elastic modulus.
- Example 5 the component (C) and the component (D) in Example 7 are changed to a material having a dimer acid skeleton (Example 1 is the component (C) in Example 7).
- Example 1 is the component (C) in Example 7.
- the adhesive according to the present invention is very useful as a conductive adhesive because these effects can be obtained even when a large amount of a conductive filler is contained.
- Example 15 As is clear from Example 15 and Example 16, even when the proportions of the components (A) to (D) in Example 5 were changed, long-term heat resistance, short-time curing characteristics, heating The results showed that there was almost no effect on the adhesive strength at the time, the rate of change of the adhesive strength, the room temperature elastic modulus, and the like.
- component (A) a 66% solution of “Fa type benzoxazine” was used.
- component (B) “EH-3636AS” was used.
- component (C) “BMI” or “BMI-1500” was used.
- component (D) “jER871” was used.
- an Ag filler was used.
- Example 19 2 parts of "Fa type benzoxazine” 66% solution (solid content: 1.33 parts), 0.3 parts of "EH-3636AS”, 1 part of "BMI-1500", 1 part of "jER871", "Ag 17 parts of “Filler” was placed in a container and stirred manually, and then dispersed with a three-roll mill to prepare a resin composition s.
- Example 20 2 parts of "Fa type benzoxazine” 66% solution (solid content: 1.33 parts), 0.3 parts of "EH-3636AS”, 1 part of “BMI-1500”, 1 part of "jER871", "Ag 20 parts of “Filler” was placed in a container and stirred manually, and then dispersed with a three-roll mill to prepare a resin composition t.
- Example 21 2 parts of "Fa type benzoxazine” 66% solution (solid content: 1.33 parts), 0.3 part of "EH-3636AS”, 1 part of “BMI”, 1 part of "jER871", "Ag filler” 17 parts were put into a container, and after stirring manually, it was dispersed with a three-roll mill to prepare a resin composition u.
- the resin composition was spread on a screen mask (emulsion thickness 20 ⁇ m, # 200 mesh, pattern size 1 mm ⁇ 71 mm), screen printed on an alumina substrate, and allowed to cure at 200 ° C. for 30 minutes to obtain a test piece.
- the resistance value and film thickness of the obtained test piece were measured using a digital multimeter and a surface roughness meter, and the specific resistance value of the cured resin composition was calculated.
- the resin composition is spread on a metal mask having a thickness of 70 ⁇ m and a pattern size of 1.6 ⁇ 0.9 mm, and the resin composition is stencil-printed on an alumina substrate with a metal squeegee and allowed to stand at 200 ° C. for 30 minutes to be cured. It was. The cured film was visually observed for pattern rubbing.
- the measurement results were “ ⁇ ” when there was no rubbing, and “ ⁇ ” when only the pattern periphery was rubbed.
- a resin composition containing a compound having an epoxy group or a cyanate ester has long-term heat resistance and short-time curing characteristics, has high adhesive strength upon heating, and has a low rate of change in adhesive strength and low room temperature elastic modulus.
Abstract
Description
[1](A)分子中にOH基と、一級~三級いずれかのアミンとを有する化合物、(B)ジシアンジアミド及び/またはイミダゾール類、(C)ビスマレイミド類、(D)分子中に一つ以上のエポキシ基を有する化合物、又はシアネートエステルを含む樹脂組成物。
[2](C)及び/または(D)がダイマー酸骨格を有する化合物である上記[1]記載の樹脂組成物。
[3](A)がベンゾオキサジン骨格を有する化合物である上記[1]または[2]記載の樹脂組成物。
[4]上記[1]~[3]のいずれか一つに記載の樹脂組成物と、導電性フィラ―とを有することを特徴とする導電性樹脂組成物。
[5]上記[1]~[3]記載の樹脂組成物を用いたことを特徴とする接着剤。
[6]上記[4]記載の導電性樹脂組成物を用いたことを特徴とする導電性接着剤。
[7]上記[4]記載の導電性樹脂組成物を用いたことを特徴とする電極形成用ペースト。
[8]上記[1]~[3]のいずれか一つに記載の樹脂組成物の硬化物、上記[4]記載の導電性樹脂組成物の硬化物、上記[5]に記載の接着剤の硬化物、上記[6]に記載の導電性接着剤の硬化物、または上記[7]に記載の電極形成用ペーストの硬化物を用いたことを特徴とする半導体装置。
分子中にOH基と、一級~三級いずれかのアミンとを有する化合物は、たとえば、ベンゾオキサジン骨格を有する化合物、アミノフェノール類等である。長期の耐熱性の観点からは、高耐熱性樹脂であるベンゾオキサジンのように、ベンゾオキサジン骨格を有する化合物が好ましい。なお、本発明における「分子中にOH基を有する」とは、フェノール類のように分子中にOH基そのものを有する場合だけでなく、ベンゾオキサジンのように開環によって分子中にOH基を有する場合も含む。
ジシアンジアミド(Dicyandiamide、「DICY」)は、H2N-CNH-NH-CNで表されるアミド化合物である。ジシアンジアミドは、本発明の樹脂組成物を合成する際に、ビスマレイミド類に対しては硬化剤として機能する。また、分子中にOH基と一級~三級いずれかのアミンとを有する化合物と、ビスマレイミド類との反応においては触媒として機能する。ジシアンジアミドは工業用として広く用いられる化合物であり、接着性、耐熱性等に優れている。
イミダゾール類(Imidazole、「IMZ」)は、5員環の1、3位に窒素原子を含む複素環式化合物である。イミダゾール類は、本発明の樹脂組成物を合成する際に、ビスマレイミド類に対しては硬化剤として機能する。また、分子中にOH基と一級~三級いずれかのアミンとを有する化合物と、ビスマレイミド類との反応においては触媒として機能する。イミダゾール類は、たとえば、2-メチルイミダゾール、2-ウンデシルイミダゾール、2-ヘプタデシルイミダゾール、1,2-ジメチルイミダゾール、2-フェニルイミダゾール、2-エチル-4-メチルイミダゾール、2-フェニル-4メチルイミダゾール、1-ベンジル-2-メチルイミダゾール、1-ベンジル-2-フェニルイミダゾール、2-フェニル-4,5-ジヒドロキシメチルイミダゾール、2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾール、1-シアノエチル-2-エチル-4-メチルイミダゾール、2,4-ジアミノ-6-[2’-メチルイミダゾールイル-(1’)]-エチル-s-トリアジン、または2,4-ジアミノ-6-[2’-メチルイミダゾリル-(1’)]エチル-s-トリアジンイソシアヌル酸付加生成物脱水和物等である。
ビスマレイミド類は、たとえば、N,N’-(4,4’-ジフェニルメタン)ビスマレイミド、ビスフェノール A ジフェニルエーテルビスマレイミド、3,3'-ジメチル-5,5'-ジエチル-4,4'-ジフェニルメタンビスマレイミド、4-メチル-1,3-フェニレンビスマレイミド、1,6’-ビスマレイミド-(2,2,4-トリメチル)ヘキサン、ビス-(3-エチル-5-メチル-4-マレイミドフェニル)メタン、m-フェニレンビスマレイミド(N,N’-1,3-フェニレンビスマレイミド)、1,6-ビスマレイミドヘキサン、1,2-ビスマレイミドエタン(N,N'-エチレンジマェイミド)、N,N'-(1,2-フェニレン)ビスマレイミド、N,N'-1,4-フェニレンジマレイミド、N,N'-(スルホニルジ-p-フェニレン)ジマレイミド、N,N'-[3,3'-(1,3-フェニレンジオキシ)ジフェニル]ビスマレイミド等である。
分子中に一つ以上のエポキシ基を有する化合物としてはエポキシ樹脂がある。エポキシ樹脂としては、ビスフェノールA型エポキシ樹脂、臭素化ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビフェニル型エポキシ樹脂、ノボラック型エポキシ樹脂、脂環式エポキシ樹脂、ナフタレン型エポキシ樹脂、エーテル系又はポリエーテル系エポキシ樹脂、オキシラン環含有ポリブタジエン、シリコーンエポキシコポリマー樹脂等が挙げられる。
本発明の樹脂組成物は、(A)分子中にOH基と、一級~三級いずれかのアミンとを有する化合物(以下、「(A)成分」という場合がある)、(B)ジシアンジアミド及び/またはイミダゾール類(以下、「(B)成分」という場合がある)、(C)ビスマレイミド類(以下、「(C)成分」という場合がある)、(D)分子中に一つ以上のエポキシ基を有する化合物、又はシアネートエステル(以下、「(D)成分」という場合がある)を混合することにより製造できる。樹脂組成物の製造方法は、上述の各成分が均一に混合した組成物を得ることができる方法であれば、特に限定されない。
導電性を持たせるため、樹脂組成物に導電性フィラ―などの導電性材料を添加してもよい。導電性フィラーとしては、Agフィラー、AgSnフィラー、これらの合金フィラーが挙げられる。導電性の観点から、導電性材料は、19~65体積%(比重が10程度の、Agフィラー等では70~95重量%に相当)であることが好ましく、23~48体積%(比重が10程度の、Agフィラー等では75~90重量%に相当)であることがさらに好ましい。導電性を有する樹脂組成物(導電性樹脂組成物)は、回路基板や電気回路等、電気的接続が要求される場合に使用される。また、熱伝導性を持たせるため、樹脂組成物にAgやアルミナといった熱伝導性材料を添加してもよい。熱伝導性を有する樹脂組成物は、チップや基板からの熱を逃がすことが要求される場合に使用される。樹脂組成物の常温弾性率(引張弾性率)は4GPa未満であることが好ましく、より好ましくは2GPa未満であるが、導電性材料や熱伝導性材料を多量に添加すると、常温弾性率が5GPa以上となることもある。ただし、そのような場合であっても、常温弾性率は8GPa未満であることが好ましい。さらに、樹脂組成物には、充填材としてシリカフィラーやシリコーンパウダーを添加してもよい。シリコーンパウダーのような充填材を添加することで、低弾性化につながる。また、シランカップリング剤等、本発明の効果を損なわない範囲で必要に応じて添加剤等を含有してもよい。
本発明に係る樹脂組成物は接着剤として用いることができる。接着剤は、電子部品の回路への接着用途や、半導体素子と他の半導体素子、及び/又は、半導体素子と半導体素子搭載用支持部材とを接着するダイアタッチ剤として使用される。接着剤は、導電性接着剤であれば、はんだの代替として用いることができる。この導電性接着剤は、樹脂組成物を含むため、はんだより低弾性であり、応力緩和の観点から非常に有用である。また、半導体装置は、半導体素子と他の半導体素子、及び/又は、半導体素子と半導体素子搭載用支持部材が接着された構造を有している。本発明に係る樹脂組成物の硬化物または接着剤の硬化物を含む半導体装置は、200℃といった高温下での信頼性に優れる。
以下の実施例1~4及び比較例1~6で得られた樹脂組成物について、硬化特性、長期耐熱性、接着強度(常温及び200℃)、常温弾性率を求めた。4元系とは、(A)成分~(D)成分全てを含む系(本発明に係る系)である。3元系とは、(A)成分~(D)成分のうち、いずれか3つの成分を含む系である。
・「EH-3636AS」(DICY100%) 株式会社ADEKA製
・「EH-3842」(DICY64%、促進剤36%) 株式会社ADEKA製
・「2PHZ-PW」(2-フェニル-4,5-ジヒドロキシメチルイミダゾール) 四国化成工業株式会社製
・「2P4MHZ-PW」(2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾール) 四国化成工業株式会社製
・「BMI」(固形。4,4´-ジフェニルメタンビスマレイミド) ケイ・アイ化成株式会社製
・「BMI-1500」(液状。ダイマー酸変性) Designer molecules社製
・「EXA-835LV」(BisA-BisF混合エポキシ) DIC株式会社製
・「jER871」(ダイマー酸変性エポキシ) 三菱化学株式会社製
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3636AS」0.3部、「BMI-1500」1部、「EXA-835LV」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物aを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「2PHZ-PW」0.1部、「BMI」1部、「jER871」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物bを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「2PHZ-PW」0.1部、「BMI-1500」1.5部、「jER871」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物cを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「2P4MHZ-PW」0.1部、「BMI-1500」1.5部、「jER871」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物dを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3636AS」0.3部、「EXA-835LV」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物αを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「BMI-1500」1部、「EXA-835LV」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物βを作製した。
「EH-3636AS」0.3部、「BMI-1500」1部、「EXA-835LV」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物γを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「2PHZ-PW」0.1部、「BMI」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物δを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「2PHZ-PW」0.1部、「BMI-1500」1.5部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物εを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「2P4MHZ-PW」0.1部、「BMI-1500」1.5部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物ζを作製した。
硬化特性の測定は、以下のように行った。まず、樹脂組成物を硬化(硬化条件:温度200℃、30分)させて板状の硬化膜を作製した。そして、各硬化膜に対して、NETZSCH社製装置「DSC204 F1」を用いて、示差走査熱量測定(Differential scanning calorimetry:DSC)を行った。測定条件は、25℃~350℃、昇温速度10℃/minである。
長期耐熱性の算出は、以下のように行った。まず、硬化特性の測定と同様に、樹脂組成物を硬化させて板状の硬化膜を作製し、重量を測定した。次に、その硬化膜を200℃設定のオーブン(ヤマト科学社製装置「DF411」)内で100時間放置し、放置後の硬化膜の重量を測定した。そして、放置前の硬化膜の重量及び放置後の硬化膜の重量に基づいて重量損失を算出した。
1.5mm角×25個の開口部を持つ#200メッシュスクリーンマスクを使用して20mm角のアルミナ基板上に樹脂組成物を塗布し、25個の印刷パターンのうち10箇所に10枚の3.2mm×1.6mmサイズのアルミナチップを搭載させた試験片を作製し、硬化条件「温度200℃、30分」にて硬化させた。この試験片を、強度試験機(アイコーエンジニアリング株式会社製 型番:Model 1605HTP)を用いてせん断強度を測定することにより、常温での接着強度を求めた。
テフロン(登録商標)シート上に膜厚が約150μmになるように、樹脂組成物を塗布し、200℃×30分でシート状に硬化させた。40mm×10mmの短冊状に切り出し、エスアイアイ・ナノテクノロジー社製のDMS6100を用いて、室温での引張弾性率を求めた。引張弾性率は、4GPa未満が好ましく、より好ましくは2GPa未満である。
以下の実施例5~18及び比較例7~12で得られた樹脂組成物について、硬化特性、長期耐熱性、接着強度(常温及び200℃)、常温弾性率を求めた。
・「H-4」(フェノール樹脂。Tg(ガラス転移点)123℃) 明和化成株式会社製
・「MEH-7500」(フェノール樹脂。Tg170℃) 明和化成株式会社製
・「MEH-8005」(フェノール樹脂。Tg105℃) 明和化成株式会社製
「H-4」及び「MEH-7500」は、ブチルカルビトール(BC)で希釈し、50%溶液としたものを用いた。「MEH-8005」は、そのまま用いた。
・「BMI-1700」(液状。ダイマー酸変性) Designer molecules社製
・「BMI-3000」(固形。ダイマー酸変性) Designer molecules社製
・Agフィラ― リン片状、タップ密度4.0g/cc、比表面積0.6m2/g
・シランカップリング剤(3-グリシドキシプロピルトリメトキシシラン) KBM-403 信越化学工業株式会社製
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3636AS」0.3部、「BMI-1500」1部、「jER871」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物eを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3636AS」0.3部、「BMI-1500」1部、「EXA-835LV」0.5部、「jER871」0.5部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物fを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3636AS」0.3部、「BMI」1部、「EXA-835LV」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物gを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3842」0.1部、「BMI-1500」2部、「jER871」1.5部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物hを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3636AS」0.3部、「BMI-3000」1部、「jER871」1.5部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物iを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3636AS」0.3部、「BMI-1500」1部、「jER871」1部、「Agフィラ―」9部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物jを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3842」0.1部、「BMI-1500」1部、「EXA-835LV」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物kを作製した。
「P-d型ベンゾオキサジン」50%溶液を2部(固形分:1.33部)、「EH-3636AS」0.3部、「BMI-1500」1部、「EXA-835LV」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物lを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3636AS」0.3部、「BMI-1700」1部、「jER871」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物mを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3636AS」0.3部、「BMI-1500」1部、「jER871」1部、「シランカップリング剤」0.05部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物nを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3636AS」0.45部、「BMI-1500」2部、「jER871」0.75部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物oを作製した。
「F-a型ベンゾオキサジン」66%溶液を3部(固形分:2部)、「EH-3636AS」0.3部、「BMI-1500」2部、「jER871」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物pを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3636AS」0.2部、「2PHZ-PW」0.1部、「BMI-1500」1部、「jER871」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物qを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3636AS」0.3部、「BMI-1500」1部、「Lecy」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物rを作製した。
「H-4」50%溶液を2.66部(固形分:1.33部)、「EH-3636AS」0.3部、「BMI-1500」1部、「jER871」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物ηを作製した。
「MEH-7500」50%溶液を2.66部(固形分:1.33部)、「EH-3636AS」0.3部、「BMI-1500」1部、「jER871」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物θを作製した。
「MEH-8005」66%溶液を2部(固形分:1.33部)、「EH-3636AS」0.3部、「BMI-1500」1部、「jER871」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物ιを作製した。
「H-4」50%溶液を2部(固形分:1部)、「EH-3636AS」0.3部、「BMI-1500」1部、「EXA-835LV」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物κを作製した。
「MEH-7500」50%溶液を2部(固形分:1部)、「EH-3636AS」0.3部、「BMI-1500」1部、「EXA-835LV」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物λを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「DDH」1部、「BMI-1500」1部、「EXA-835LV」1部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物μを作製した。
以下の実施例19~21で得られた樹脂組成物について、導電性及び印刷性を求めた。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3636AS」0.3部、「BMI-1500」1部、「jER871」1部、「Agフィラ―」17部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物sを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3636AS」0.3部、「BMI-1500」1部、「jER871」1部、「Agフィラ―」20部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物tを作製した。
「F-a型ベンゾオキサジン」66%溶液を2部(固形分:1.33部)、「EH-3636AS」0.3部、「BMI」1部、「jER871」1部、「Agフィラ―」17部を容器に入れ、手攪拌した後、三本ロールミルで分散し、樹脂組成物uを作製した。
樹脂組成物をスクリーンマスク(乳剤厚20μm、♯200メッシュ、パターン寸法1mm×71mm)上に広げ、アルミナ基板上にスクリーン印刷し、200℃で30分放置して硬化させて試験片を得た。得られた試験片の抵抗値と膜厚を、デジタルマルチメーターと表面粗さ計を用いて測定し、硬化させた樹脂組成物の比抵抗値を算出した。
厚さ70μm・パターン寸法1.6×0.9mmのメタルマスク上に樹脂組成物を広げ、メタルスキージにて樹脂組成物をアルミナ基板上に孔版印刷し、200℃で30分放置して硬化させた。
硬化後の塗膜について、パターンの擦れの有無を目視にて観察した。
Claims (8)
- (A)分子中にOH基と、一級~三級いずれかのアミンとを有する化合物
(B)ジシアンジアミド及び/またはイミダゾール類
(C)ビスマレイミド類
(D)分子中に一つ以上のエポキシ基を有する化合物、又はシアネートエステル
を含むことを特徴とする樹脂組成物。 - (C)及び/または(D)がダイマー酸骨格を有する化合物であることを特徴とする請求項1記載の樹脂組成物。
- (A)がベンゾオキサジン骨格を有する化合物であることを特徴とする請求項1または2記載の樹脂組成物。
- 請求項1~3のいずれか一つに記載の樹脂組成物と、導電性フィラ―とを有することを特徴とする導電性樹脂組成物。
- 請求項1~3記載の樹脂組成物を用いたことを特徴とする接着剤。
- 請求項4記載の導電性樹脂組成物を用いたことを特徴とする導電性接着剤。
- 請求項4記載の導電性樹脂組成物を用いたことを特徴とする電極形成用ペースト。
- 請求項1~3のいずれか一つに記載の樹脂組成物の硬化物、請求項4記載の導電性樹脂組成物の硬化物、請求項5に記載の接着剤の硬化物、請求項6に記載の導電性接着剤の硬化物、または請求項7に記載の電極形成用ペーストの硬化物を用いたことを特徴とする半導体装置。
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JP7137576B2 (ja) | 2017-11-10 | 2022-09-14 | 株式会社プリンテック | 樹脂組成物の製造方法 |
JPWO2019092968A1 (ja) * | 2017-11-10 | 2021-01-28 | 株式会社プリンテック | 樹脂組成物 |
JP7210031B2 (ja) | 2017-11-27 | 2023-01-23 | ナミックス株式会社 | フィルム状半導体封止材 |
JPWO2019102719A1 (ja) * | 2017-11-27 | 2020-12-17 | ナミックス株式会社 | フィルム状半導体封止材 |
WO2019102719A1 (ja) * | 2017-11-27 | 2019-05-31 | ナミックス株式会社 | フィルム状半導体封止材 |
WO2019172227A1 (ja) * | 2018-03-05 | 2019-09-12 | タツタ電線株式会社 | 接着剤用組成物 |
JP6660513B1 (ja) * | 2018-03-28 | 2020-03-11 | 積水化学工業株式会社 | 樹脂材料及び多層プリント配線板 |
JP7087810B2 (ja) | 2018-08-09 | 2022-06-21 | 信越化学工業株式会社 | 半導体封止用熱硬化性樹脂組成物及び半導体装置 |
JP2020026450A (ja) * | 2018-08-09 | 2020-02-20 | 信越化学工業株式会社 | 半導体封止用熱硬化性樹脂組成物及び半導体装置 |
JP7124657B2 (ja) | 2018-11-14 | 2022-08-24 | 味の素株式会社 | 樹脂組成物、樹脂シート、プリント配線板及び半導体装置 |
JP2020083898A (ja) * | 2018-11-14 | 2020-06-04 | 味の素株式会社 | 樹脂組成物、樹脂シート、プリント配線板及び半導体装置 |
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JP6770509B2 (ja) | 2020-10-14 |
US20180079856A1 (en) | 2018-03-22 |
TWI698488B (zh) | 2020-07-11 |
EP3279261A1 (en) | 2018-02-07 |
EP3279261B1 (en) | 2023-11-01 |
JPWO2016158828A1 (ja) | 2018-01-25 |
TW201710382A (zh) | 2017-03-16 |
EP3279261A4 (en) | 2018-11-21 |
US10294324B2 (en) | 2019-05-21 |
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