WO2012124780A1 - エポキシ樹脂組成物およびその製造方法ならびにそれを用いた半導体装置 - Google Patents
エポキシ樹脂組成物およびその製造方法ならびにそれを用いた半導体装置 Download PDFInfo
- Publication number
- WO2012124780A1 WO2012124780A1 PCT/JP2012/056762 JP2012056762W WO2012124780A1 WO 2012124780 A1 WO2012124780 A1 WO 2012124780A1 JP 2012056762 W JP2012056762 W JP 2012056762W WO 2012124780 A1 WO2012124780 A1 WO 2012124780A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- carbon atoms
- compound
- general formula
- epoxy resin
- Prior art date
Links
- UHOVQNZJYSORNB-UHFFFAOYSA-N c1ccccc1 Chemical compound c1ccccc1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- NDKBGKGVUOZCJQ-UHFFFAOYSA-N CC(C1C2CC=CC1)C2C(O)=O Chemical compound CC(C1C2CC=CC1)C2C(O)=O NDKBGKGVUOZCJQ-UHFFFAOYSA-N 0.000 description 1
- UTEIUSUWIZICDO-UHFFFAOYSA-N CC(CC=CC1)C1C(O)=O Chemical compound CC(CC=CC1)C1C(O)=O UTEIUSUWIZICDO-UHFFFAOYSA-N 0.000 description 1
- QUKLXEPILLISOV-UHFFFAOYSA-N OC(C(C1C2C3C=CCC2C1)C3C(O)=O)=O Chemical compound OC(C(C1C2C3C=CCC2C1)C3C(O)=O)=O QUKLXEPILLISOV-UHFFFAOYSA-N 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N OC(C(C1C=CC2C1)C2C(O)=O)=O Chemical compound OC(C(C1C=CC2C1)C2C(O)=O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- UCUARXLLXUYNLH-UHFFFAOYSA-N OC(C(CC1C(C2)CC=CC1)C2C(O)=O)=O Chemical compound OC(C(CC1C(C2)CC=CC1)C2C(O)=O)=O UCUARXLLXUYNLH-UHFFFAOYSA-N 0.000 description 1
- 0 OC(C(CC1C(O)=O)C2*1C=CC2)=O Chemical compound OC(C(CC1C(O)=O)C2*1C=CC2)=O 0.000 description 1
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
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
-
- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
- H01L23/3737—Organic materials with or without a thermoconductive filler
-
- 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
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to an epoxy resin composition excellent in heat resistance, having a low coefficient of thermal expansion and excellent workability dissolved in a ketone solvent, and a semiconductor device using the same.
- solder has been changed from a conventional lead-containing solder to a lead-free type solder composed of tin, silver and the like.
- lead-free solder solder connection at a higher temperature than that of lead-containing solder is required, and a glass transition temperature higher than ever is required for the substrate material.
- a method of adding an inorganic filler is generally used to reduce the thermal expansion coefficient of an epoxy resin (see, for example, Patent Document 1).
- a phloroglucinol is added to the epoxy resin (see, for example, Patent Document 2), or a curing agent having three or more phenolic hydroxyl groups is added to the epoxy resin (for example, , Patent Document 3), a resin composition containing a cyanate ester resin added to an epoxy resin (see, for example, Patent Document 4), an epoxy resin, a polyphenolic epoxy resin curing agent, and a polyethersulfone. (For example, refer patent document 5) etc. are proposed.
- thermosetting resin composition containing a bismaleimide compound and an epoxy resin can be used to increase the adhesiveness to a semiconductor element, or can be a liquid epoxy resin, a curing agent, or a polyether type. It has been disclosed that a liquid epoxy resin composition containing a compound or a composition containing a polyimide having a special structure with an epoxy resin can increase heat resistance (see, for example, Patent Document 7). ). However, the resin compositions disclosed therein have a problem of insufficient workability and heat resistance, such as not being dissolved in a low boiling point solvent.
- thermosetting resin composition comprising a polyimide obtained by reacting a substituted guanamine compound and at least two unsaturated N-substituted maleimide groups (see Patent Document 8), epoxy A curable resin composition that is compatible with an equivalent 200-1000 polymer and an epoxy compound (see Patent Document 9), an adhesive for electronic materials composed of a polyimide having a hydroxyl group and an epoxy resin (see Patent Document 10), an amino group and phenol Heat-resistant resin composition comprising a compound having a group, a bismaleimide compound and an epoxy resin (see Patent Document 11), a polymer of a bismaleimide compound and a diamine, and a resin composition comprising a polyethersulfone resin and an epoxy resin (Patent Document) 12), a maleimide compound having a hydroxyl group having a specific structure And a heat resistant composition comprising an epoxy compound having two or more glycidyl groups (see Patent Document 13), and a heat resistant composition
- JP 2006-28294 A (Claims) JP 2010-95646 A (Claims) JP 2010-95645 A (Claims) JP 2010-90237 A (Claims) JP 2001-72833 A (Claims) JP 2003-221443 A (Claims) JP 2008-81686A (Claims) JP 2009-149742 A (Claims) JP 2008-274300 A (Claims) JP 2004-35650 A (Claims) JP 2007-169454 A (Claims) JP 2009-155354 A (Claims) JP 2009-161605 A (Claims) JP 07-268077 A (Claims)
- the present invention provides an epoxy resin composition that satisfies all of storage stability, heat resistance after curing, and low thermal expansibility, can be dissolved in a solvent such as cyclohexanone, and has low viscosity and high workability. With the goal.
- the resin composition of the present invention has the following constitution. That is, the present invention contains (a) a compound having an imide structure represented by general formula (1) and (b) a compound having at least two epoxy groups, and (a) represented by general formula (1).
- An epoxy resin composition in which a compound having an imide structure has a number average molecular weight of 1000 to 5000 is provided.
- R 1 has 50% or more of the structure represented by the general formula (2);
- R 2 is any one selected from the following formula (4) and different.
- the benzene ring in any structure selected from the following formula (4) may be a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or 1 to 4 may be substituted by one or more groups selected from an alkoxyl group having 4 carbon atoms, a fluoroalkoxyl group having 1 to 4 carbon atoms, an ester group having 2 to 5 carbon atoms, a carboxyl group, a cyano group, and a nitro group;
- G is any one selected from the following formula (5), and different ones may be mixed.
- R 4 and R 5 may be independent of each other or may be mixed together, and may be an alkyl group having 1 to 4 carbon atoms, It represents a group selected from a 1 to 4 fluoroalkyl group, an alkoxyl group having 1 to 4 carbon atoms, a fluoroalkoxyl group having 1 to 4 carbon atoms, an ester group having 2 to 5 carbon atoms, a carboxyl group, a cyano group, and a nitro group.
- X is a direct bond, —CH 2 —, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —C (C 2 F 5 ) 2 —, —O—, —SO 2 —, fluorene , —CO—, —COO—, —CONH—, —CF 2 —, and any one selected from the following formulas (3) to (5) may be present together; Represents an integer of 0 to 3, s and t represent an integer of 0 to 4 and s + t>0; w is 0 It represents an integer of 8.)
- the epoxy resin composition has an extremely high glass transition temperature, a low coefficient of thermal expansion, and an excellent processability that is soluble in ketone solvents such as methyl ethyl ketone and cyclohexanone. Can be provided.
- the epoxy resin composition of the present invention contains (a) a compound having an imide structure represented by the above general formula (1) and (b) a compound having at least two epoxy groups, and (a) the above general formula.
- the number average molecular weight of the compound having an imide structure represented by (1) is 1000 to 5000.
- R 1 has 50% or more of the structure represented by the general formula (2).
- R 2 is any one selected from the above formula (4), and different ones may be mixed.
- the benzene ring in any structure selected from the above formula (4) has a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, and a carbon number 1 or more selected from a carboxyl group, a cyano group, and a nitro group of a fluoroalkoxyl group having 1 to 4 carbon atoms, an ester group having 2 to 5 carbon atoms (the carbon number of R in the ester group represented by -COOR is 1 to 4) It may be substituted with a group.
- v represents an integer of 1 to 8; G is any one selected from the above formula (5), and different ones may be mixed.
- “different things may be mixed” means that when there is only one thing represented by the symbol in one molecule, the difference between different molecules. It means that what is represented by the symbol may be different. In the case where there can be a plurality of compounds represented by the symbol in one molecule, it means that the components represented by the symbol may be different within one molecule.
- each of R 4 and R 5 may be independent of each other or may be a mixture of different alkyl groups having 1 to 4 carbon atoms, It represents a group selected from a 1 to 4 fluoroalkyl group, an alkoxyl group having 1 to 4 carbon atoms, a fluoroalkoxyl group having 1 to 4 carbon atoms, an ester group having 2 to 5 carbon atoms, a carboxyl group, a cyano group, and a nitro group. .
- an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, and a carboxyl group are preferable.
- X is a direct bond, —CH 2 —, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —C (C 2 F 5 ) 2 —, —O—, —SO 2 —, fluorene, Any one selected from —CO—, —COO—, —CONH—, —CF 2 —, and the above formulas (3) to (5) may be mixed.
- a direct bond, -C (CF 3) 2 - , - O -, - SO 2 -, fluorene are preferred.
- p and q represent an integer of 0 to 3
- s and t represent an integer of 0 to 4
- w represents an integer of 0 to 8.
- the compound (a) having an imide structure represented by the general formula (1) used in the present invention is a diamine compound having a phenolic hydroxyl group, a carbonic acid such as tetracarboxylic dianhydride, maleic anhydride or nadic anhydride. It can be obtained by reacting a dicarboxylic anhydride having a carbon double bond.
- solubility with a low molecular weight can be improved in the reaction with diamine, and during the epoxy group curing reaction, maleic anhydride, nadic anhydride, etc. Reaction occurs with double bonds or with an amino group, and the molecular weight of the compound having an imide structure increases. Thereby, mechanical properties can be improved.
- diamine compounds having a phenolic hydroxyl group examples include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP, manufactured by AZ Electronic Materials), 9,9-bis ( 3-amino-4-hydroxyphenyl) fluorene (BAHF, manufactured by AZ Electronic Materials Co., Ltd.)), 9,9-bis (4-amino-3-hydroxyphenyl) fluorene, dihydroxybenzidine, bis (3-amino- 4-hydroxyphenyl) sulfone (ABPS, manufactured by AZ Electronic Materials), bis (3-amino-4-hydroxyphenyl) ether (ADPE), bis (3-amino-4-hydroxyphenyl) propane, hydroxyphenylene Diamine, Dihydroxydiaminobenze Bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, bis (aminophenoxy) hydroxybenzene, bis
- Diamine having 1 to 4 aromatic rings such as propane and bis (aminophenyl) fluorene, ethylenediamine, diaminopropane, diaminobutane, diaminoheptane, diaminohexane, diaminocycloheptane, diaminocyclohexane, methylenebis (aminocyclohexane), etc.
- tetracarboxylic dianhydride examples include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetra Carboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, diphenylsulfone tetracarboxylic dianhydride, hexa Fluoroisopropylidene-bis (phthalic anhydride), phenylenebisoxybis (phthalic anhydride), bis (phenyltrimellitic anhydride), hydroquinonebis (trimellitic anhydride), (isopropylidenediphenoxy) bis (Phthalic anhydride), etc., and these can be reacted
- the benzene ring of these acid anhydrides is a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or a fluoroalkoxyl having 1 to 4 carbon atoms. It may be substituted with one or more groups selected from a group, an ester group having 2 to 5 carbon atoms, a carboxyl group, a cyano group and a nitro group.
- the number average molecular weight of the compound having an imide structure represented by the general formula (1) is 1000 to 5000, preferably 1000 to 4000, and preferably 1000 to 3000. More preferably.
- the weight average molecular weight is preferably 10,000 or less.
- the weight average molecular weight is desirably 1000 or more. Therefore, a desirable weight average molecular weight range is 1000 to 10,000, and more preferably 1000 to 5000.
- a dicarboxylic anhydride having a carbon-carbon double bond such as 1,3-dione
- This reaction is generally performed in a polar solvent having a high boiling point such as N-methyl-2-pyrrolidone (NMP) or gamma-butyrolactone, but the imide structure represented by the general formula (1) of the present invention is used. Since the compound having a ketone group dissolves in a solvent having a ketone group, a diamine compound is dissolved in a solvent such as cyclohexanone, and a dicarboxylic acid anhydride having a carbon-carbon double bond such as maleic anhydride or nadic anhydride, tetracarboxylic A compound having an imide structure represented by the general formula (1) can be obtained by adding acid dianhydride and reacting while distilling off water at a temperature of 100 ° C.
- NMP N-methyl-2-pyrrolidone
- gamma-butyrolactone gamma-butyrolactone
- a base compound such as pyridine, triethylamine or isoquinoline or an acid anhydride such as acetic anhydride may be added as a catalyst for imidization.
- an acid-type or base-type ion exchange resin can also be used as an imidation catalyst.
- the solvent is distilled off with an evaporator, or poured into water or alcohol to precipitate a compound having an imide structure represented by the general formula (1). And collected by filtration, washed and dried to obtain the desired compound having an imide structure represented by the general formula (1). Further, after evaporation, a ketone solvent may be added to replace the solvent.
- a solid of the compound having an imide structure represented by the general formula (1) may be obtained by the above method, but (b) at least two or more in the solution. You may mix with the compound which has the epoxy group of.
- (B) As a compound having at least two epoxy groups used in the present invention, those of bisphenol A type (for example, “jER (registered trademark)” 828, trade name, manufactured by Mitsubishi Chemical Corporation), bisphenol F type (For example, “JER (registered trademark) 807, trade name) manufactured by Mitsubishi Chemical Corporation”, biphenyl type (for example, “jER (registered trademark)“ YX4000, trade name ”manufactured by Mitsubishi Chemical Corporation), Phenol novolac type (for example, Mitsubishi Chemical Corporation “jER (registered trademark) 152, trade name), cresol novolac type (for example, DIC Corporation, manufactured by“ Epiclon (registered trademark) ”N660, commodity Name), glycidylamine type (for example, “jER (registered trademark)” 604, trade name, manufactured by Mitsubishi Chemical Corporation), cyclopentadiene type (For example, “Epiclon (registered trademark)” HP7200, product name) manufactured by DIC Corporation,
- Examples of the compound (b) having at least two or more epoxy groups used in the present invention include bifunctional epoxy resins, trifunctional epoxy resins, and polyfunctional epoxy resins having four or more epoxy groups.
- Bifunctional epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, aliphatic glycidyl ether type epoxy resin, alicyclic glycidyl ether type epoxy resin, glycidyl aniline type epoxy resin, cyclohexane A pentadiene type epoxy resin and a naphthalene type epoxy resin are mentioned.
- Examples of the trifunctional epoxy resin include a triazine skeleton-containing epoxy resin, an aminophenol type epoxy resin, and an aminocresol type epoxy resin.
- Examples of the polyfunctional epoxy resin having four or more epoxy groups include a cresol novolac epoxy resin, a phenol novolac epoxy resin, a biphenyl epoxy resin, a naphthalene epoxy resin, and an aromatic glycidylamine epoxy resin.
- the epoxy resins represented by the general formulas (6) to (8) are preferably used in that the epoxy equivalent is small, the crosslinking density in the cured product is increased, and the low thermal expansion and high heat resistance are greatly improved.
- the epoxy resin represented by the general formula (9) is preferably used from the viewpoint of enhancing the rigidity and orientation of the cured product and greatly improving the low thermal expansion and the high heat resistance.
- R 6 to R 37 may be independent from each other or may be mixed together, and may be a hydrogen atom, halogen atom, carbon
- An alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, and a cycloalkyl group (preferably having 6 to 8 carbon atoms and preferred cycloalkyl groups appearing below) Are the same) and an aryl group (preferably having 6 to 8 carbon atoms, and the same preferred aryl groups appearing below).
- R 6 to R 37 include, but are not limited to, a methyl group, an ethyl group, and a propyl group.
- Y 1 to Y 4 may be independent from each other or may be mixed together, and may be a direct bond, methylene group, ether group, thioether group, SO 2 group, isopropylene group And a group selected from the group represented by the following general formula (10).
- preferred examples include a direct bond, a methylene group, and an SO 2 group.
- R 38 and R 39 may be independent from each other or may be mixed together, and may be a hydrogen atom, a halogen atom, a carbon number of 1 to 6 A group selected from an alkyl group, an alkoxy group, a fluoroalkyl group, a cycloalkyl group, and an aryl group. Of these, preferred are a methyl group, an ethyl group, and a propyl group.
- aminophenol type epoxy compound represented by the general formula (6) examples include p-aminophenol, m-aminophenol, p-aminocresol, trifluoromethylhydroxyaniline, hydroxyphenylaniline, methoxyhydroxyaniline, Triglycidyl compounds such as butylhydroxyaniline and hydroxynaphthylaniline can be mentioned.
- aromatic glycidylamine type epoxy compounds represented by the general formulas (7) and (8) include tetraglycidyldiaminodiphenyl ether, tetraglycidyltetramethyldiaminodiphenyl ether, tetraglycidyltetraethyldiaminodiphenylether, tetraglycidylbis ( Aminophenoxyphenyl) propane, tetraglycidylbis (aminophenoxyphenyl) sulfone, tetraglycidylbis (trifluoromethyl) diaminobiphenyl, tetraglycidylbenzidine, tetraglycidyltolidine, tetraglycidyl-p-phenylenediamine, tetraglycidyl-m-phenylenediamine , Tetraglycidyldiaminotoluene, tetraglycidyldiamin
- Alpha .'- bis (4-aminophenyl) -1,4-diisopropylbenzene and epichlorohydrin 1 like 4 addition reaction product.
- Commercially available products include ELM434 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), “Araldite (registered trademark)” MY720, “Araldite” MY721, “Araldite” MY722, “Araldite” MY9512, “Araldite” MY9612, “Araldite” MY9634, “Araldite” MY9663 (above, trade name, manufactured by Vantico Co., Ltd.), “jER (registered trademark)” 604 (manufactured by Mitsubishi Chemical Corporation), TGDAS (above, trade name, Konishi Chemical Industry ( Etc.).
- These epoxy compounds have good storage stability, a large density of epoxy groups in the compound, a high crosslinking density after curing, and excellent heat resistance and thermal expansion after curing. .
- the naphthalene type epoxy compound represented by the above general formula (9) can be obtained from a tetraglycidylated product through a tetravalent naphthol intermediate which is a condensate of dihydroxynaphthalene and formaldehyde.
- a tetravalent naphthol intermediate which is a condensate of dihydroxynaphthalene and formaldehyde.
- Specific examples thereof include “Epicron (registered trademark)” HP4700, “Epicron” HP4710, “Epicron” HP4770 (trade name, manufactured by DIC Corporation), and the like.
- the naphthalene skeleton in the compound has increased rigidity and strong orientation, and is excellent in heat resistance and thermal expansion after curing.
- the equivalent of the epoxy group in the compound having at least two epoxy groups is (a) the equivalent of the hydroxyl group of the compound having an imide group represented by the general formula (1) and the general formula (2).
- the groups represented by R 4 and R 5 it is preferable to add the same equivalent as the total equivalent of the functional groups (hydroxyl group, carboxyl group, cyano group) that react with the epoxy group.
- the equivalent of epoxy refers to the mass of a resin containing one equivalent of an epoxy group, and can be obtained by dividing the molecular weight obtained from the structural formula by the number of epoxy groups contained in the structure, as well as JIS-K7236 ( 2001)-It can also be determined by the potentiometric titration method described in ISO3001.
- the functional group that reacts with the hydroxyl group of the compound having an imide group represented by the general formula (1) and the epoxy group represented by R 4 and R 5 in the general formula (2) is 1: 1 with the epoxy group. Therefore, the relationship between the equivalent of the functional group that reacts with the epoxy group and the equivalent of the epoxy group is preferably 0.7 to 1.2: 1, and preferably 0.9 to 1.1: 1. Is more preferable.
- the compound having at least two epoxy groups functions as a curing agent for the compound (a) having an imide group represented by the general formula (1).
- the curing agent refers to an agent that has an effect of curing alone
- the curing accelerator refers to an agent that has an effect of promoting the reaction when used together with the curing agent.
- novolak resins As other curing agents and curing accelerators, it is preferable to use novolak resins, phenol resins, aliphatic polyamines, alicyclic polyamines, and aromatic polyamines.
- Aliphatic polyamines include diethyltriamine, triethylenetetramine, xylenediamine, etc., alicyclic polyamines such as isophorone diamine, 1,3-bisaminomethylcyclohexane, norbornene diamine, etc. Examples include diaminodiphenylmethane and diaminodiphenylsulfone.
- curing agents are preferably added in the same amount as the equivalent of the epoxy group in the compound (b) having at least two or more epoxy groups.
- the hydroxyl group (OH) of other curing agents and curing accelerators reacts with epoxy groups 1: 1, and the amino group (NH 2 ) of other curing agents and curing accelerators reacts 1: 2 with epoxy groups. Therefore, the relationship between the equivalent of the reactive group of the other curing agent and the equivalent of the epoxy group is preferably 0.7 to 1.2: 1, more preferably 0.9 to 1.1: 1. . If the relationship between the equivalents of reactive groups of other curing agents and the equivalents of epoxy groups is 0.7 to 1.2: 1, there is little reaction between epoxy groups, and the glass transition temperature and chemical resistance are reduced. In addition, since other unreacted other curing agents and curing accelerators are reduced, an increase in water absorption and a decrease in chemical resistance are less likely to occur.
- curing agents or curing accelerators that can be used in the epoxy resin composition of the present invention
- acid anhydrides, dicyandiamide and derivatives thereof, imidazoles and derivatives thereof, condensates of amine derivatives and formaldehyde urea formaldehyde, (Melamine formaldehyde), organometallic complexes, polythiols, onium salts and the like can be mentioned, and two or more of these may be used.
- acid anhydrides include succinic anhydride, itaconic anhydride, phthalic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, hexahydrophthal Acid anhydride, methyltetrahydrophthalic anhydride, “ADEKA HARDNER (registered trademark)” EH-3326, “ADEKA HARDNER” EH-703, “ADEKA HARDNER” EH-705A (above, trade name, Asahi Denka Kogyo Co., Ltd.) ), “Epicron” B-570, “Epicron” B-650 (trade name, manufactured by Dainippon Ink and Chemicals), “Licacid (registered trademark)” MH-700 (trade name, Shin Nippon Rika) Etc.).
- Dicyandiamide and its derivatives include DICY7, DICY15, and DICY50 (above, trade names, manufactured by Mitsubishi Chemical Corporation), “Amicure (registered trademark)” AH-154, “Amicure” AH-162 (above, trade names, Ajinomoto) Fine Techno Co., Ltd.).
- Examples of imidazoles and their derivatives include imidazole, 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxy.
- Imidazole imidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, IS-1000, IS-1000D, IM-1000, SP-1000, IA-100A, IA-100P, IA-100F ( Less than Trade name, Nikko Materials Co.'s, Ltd.) imidazole silane of the like.
- condensation product of amine derivative and formaldehyde examples include 4-chloro-phenyl-N, N-dimethylurea and 3,4-dichlorophenyl-N, N-dimethylurea (DCMU).
- organometallic complexes examples include triphenylphosphine and triphenylphosphonium triphenylborate
- polythiols examples include aliphatic polythioethers, aliphatic polythioesters, aromatic ring-containing polythioethers, and the like.
- onium salts include onium salts such as sulfonium and iodonium, and onium salt-type diphenyliodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, Syracure UVI-6992, Syracure UVI-6974 (above, trade names, Dow Chemical Japan Co., Ltd.), Adekaoptomer SP150, Adekaoptomer SP170 (above, trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), Sun-Aid SI-60L, SI-80L, SI-100L, SI-150L (The above is a trade name, manufactured by Sanshin Chemical Industry Co., Ltd.).
- onium salts such as sulfonium and iodonium
- onium salt-type diphenyliodonium hexafluorophosphate triphenylsulfonium hexafluorophosphate
- microcapsule-type latent curing agents and amine adducts examples include molding latent curing agents and the like.
- the microcapsule type latent curing agent is a curing agent having a core (core material) / shell (capsule film) structure, and various imidazole compounds and triphenylphosphine are used as the core.
- Organic polymers and inorganics are used as the shell. Compounds and the like.
- the amine adduct type latent curing agent is a pulverized product obtained by reacting an imidazole compound, a tertiary amino group-containing compound or a hydrazide compound with an epoxy compound, an isocyanate compound, or the like to obtain a high molecular weight, and has a solubility at room temperature. Is low and shows potential.
- “Amicure” PN-23, “Amicure” PN-40, “Amicure” MY-24, “Amicure” MY-H above, trade name, manufactured by Ajinomoto Fine Techno Co., Ltd.
- the content of these other curing agents and curing accelerators is preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the compound (b) having at least two or more epoxy groups. More preferably, it is a part.
- the content of other curing agents and curing accelerators is preferably 0.1 to 60 parts by weight or more, (b) the compound having at least two epoxy groups is effectively cured to 60 parts by weight or less. The reaction start at room temperature can be suppressed.
- an oxetane compound other than the compound having at least two epoxy groups can be contained.
- the thermal stability is increased, so that the heat resistance after curing can be improved.
- monofunctional oxetane compounds include “Ethanacol (registered trademark)” EHO, “Ethanacol” OXMA (trade name, manufactured by Ube Industries, Ltd.), OXT-101, OXT- 211, OXT-212, OXT-610 (above, trade name, manufactured by Toa Gosei Co., Ltd.) and 3-ethyl-3- (cyclohexyloxy) methyloxetane.
- bifunctional oxetane compound examples include “ethanacol”. OXBP, “Ethanacol” OXTP, “Ethanacol” OXIPA (above, trade name, manufactured by Ube Industries, Ltd.), OXT-121, OXT-221 (above, trade name, manufactured by Toa Gosei Co., Ltd.), trifunctional oxetane Compounds include oxetaneated phenol resin, oxetanyl silicate, phenol novolac oxetane Thing, and the like. Two or more of these may be contained.
- the content of these oxetane compounds is preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the compound (b) having at least two epoxy groups.
- the content of the oxetane compound is 0.1 parts by weight or more, the heat resistance of the epoxy resin composition is increased, and when the content is 60 parts by weight or less, layer separation of the cured product can be prevented.
- the epoxy resin composition of the present invention is preferably dissolved in (c) cyclohexanone at a concentration of 30% by weight or more. As a result, it is easily compatible with many epoxy resins and can be easily dried thereafter, resulting in less shrinkage during curing.
- Propyl ketone, methyl amyl ketone, methyl cyclohexanone, ethyl cyclohexanone, methyl dipropyl ketone, methyl propyl ketone, mesityl oxide, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and the like can also be used as the reaction solvent.
- ether solvents 1,4-dioxane, tetrahydrofuran, glycidol, diglyme glycol ether solvents methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, etc.
- the epoxy resin composition of the present invention may contain 0.1 to 1% by weight of a solvent having a ketone group other than cyclohexanone or cyclohexanone for the purpose of adjusting the viscosity or improving the coating property.
- a solvent having a ketone group other than cyclohexanone or cyclohexanone for the purpose of adjusting the viscosity or improving the coating property.
- the epoxy resin composition of the present invention comprises (d) at least one inorganic fine particle selected from the group consisting of boron nitride, silica, titania, zirconia, silicon nitride, alumina, ceria, talc and calcium carbonate, silica-titania composite particles.
- inorganic fine particles selected from the group consisting of boron nitride, silica, titania, zirconia, silicon nitride, alumina, ceria, talc and calcium carbonate, silica-titania composite particles.
- thermal conductivity can be imparted or the thermal linear expansion coefficient of the cured film can be reduced.
- boron nitride, silica, titania, alumina, calcium carbonate, and silica-titania composite particles are preferable.
- the surface of the inorganic fine particles is treated with various coupling agents such as silane, titanium and aluminum, fatty acids, phosphate esters, etc., or rosin treatment Those subjected to acidic treatment and basic treatment are also preferably used.
- a silane coupling agent which is a silane coupling agent, is preferable in order to increase the affinity with the epoxy compound, and in particular, a silane coupling agent having an epoxy group is preferably used from the viewpoint of increasing toughness.
- Preferred examples of the silane coupling agent include ⁇ -glycidoxytrimethoxysilane, ⁇ -glycidoxytriethoxysilane, ⁇ -glycidoxytripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-amino And propyltripropoxysilane. Two or more of these may be used.
- the content of these (d) inorganic fine particles is preferably 5 to 5000 parts by weight with respect to 100 parts by weight of the compound (b) having at least two epoxy groups.
- the content of the inorganic fine particles is 5 parts by weight or more, the thermal expansion coefficient can be reduced, and when the content is 5000 parts by weight or less, the adhesiveness and mechanical properties of the epoxy resin composition can be maintained. More preferably, it is 30 to 500 parts by weight with respect to 100 parts by weight as a total of the compound having an imide group as the component (a) and the epoxy compound as the component (b).
- the average particle diameter of the inorganic fine particles is preferably 5 nm to 30 ⁇ m, more preferably 10 nm to 10 ⁇ m.
- the average particle diameter in the present invention is determined by using a transmission electron microscope (H-7100FA type, manufactured by Hitachi, Ltd.), with a cross section of a coating film having a thickness of 20 ⁇ m prepared by using an ultrathin section method. , Observed at an accelerating voltage of 100 kV at an observation magnification of 200,000 times, selected 50 arbitrary particles from the obtained image, measured the particle size of each single particle, and obtained the number average value thereof It is.
- the particle diameter is 5 nm or more, an appropriate viscosity can be imparted, and at the same time, stable particle dispersibility can be obtained.
- the particle diameter is set to 30 ⁇ m or less, low viscosity can be improved and sedimentation of inorganic fine particles can be prevented. it can.
- the epoxy resin composition of the present invention can contain (e) at least one organic fine particle selected from the group consisting of polyimide, polyamide, polyamideimide, polystyrene, polyacrylonitrile, polyphenylene ether, polyester and polycarbonate.
- organic fine particles By containing these organic fine particles, toughness, heat resistance, and low hygroscopicity can be imparted.
- the content of these organic fine particles is preferably 5 to 1000 parts by weight with respect to 100 parts by weight of the compound (b) having at least two or more epoxy groups. When the amount is 5 parts by weight or more, toughness, heat resistance, and mechanical properties are improved, and when the amount is 1000 parts by weight or less, the mechanical properties can be maintained, and the solution viscosity does not increase excessively.
- the average particle size of the organic fine particles is preferably 5 nm to 10 ⁇ m, more preferably 5 nm to 5 ⁇ m.
- the method for measuring the average particle size of the organic fine particles is the same as the method for measuring the average particle size of the inorganic fine particles.
- phenoxy resin polyurethane, polypropylene, acrylonitrile-butadiene copolymer (NBR), styrene-butadiene copolymer, (SBR), acrylonitrile-butadiene-methacrylic acid copolymer, acrylonitrile-butadiene-acrylic acid copolymer, etc. It may contain.
- the epoxy resin composition of the present invention contains a nonionic, cationic, anionic surfactant, a wetting agent such as a polyvalent carboxylic acid, an amphoteric substance, a resin having a highly sterically hindered substituent, and the like. May be.
- a stabilizer e.g., a stabilizer, a dispersing agent, an anti-settling agent, a plasticizer, antioxidant, etc. as needed.
- the epoxy resin composition of the present invention is, for example, one or more tetracarboxylic acid anhydrides selected from diamines having a structure represented by the following general formula (2) ′ of 50 mol% or more and the following formula (4) ′: And one or more compounds selected from the following formula (5) ′ are mixed in a solvent having a ketone group (c) ′ under conditions of 50 to 80 ° C. for 0.5 to 2 hours, and (a) the above general formula It can be obtained by obtaining a compound having an imide structure represented by (1) and further mixing (b) a compound having at least two epoxy groups.
- R 4 and R 5 may be independent of each other or may be mixed together, and may be an alkyl group having 1 to 4 carbon atoms or carbon atoms.
- X represents a direct bond, —CH 2 —, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —C (C 2 F 5 ) 2 —, —O—, —SO 2 —, Any one selected from fluorene, —CO—, —COO—, —CONH—, —CF 2 —, and the following formula (3) may be mixed: p and q are 0 to 3
- organic / inorganic fine particles, a curing agent, a curing accelerator and the like can be mixed in the same manner.
- organic / inorganic fine particles there may be mentioned a method of dispersing using a method such as ultrasonic dispersion, ultrasonic dispersion, ball mill, roll mill, kneader, clear mix, homogenizer, media disperser and the like.
- a method of dispersing using a method such as ultrasonic dispersion, ultrasonic dispersion, ball mill, roll mill, kneader, clear mix, homogenizer, media disperser and the like.
- it is preferable to carry out at 0 degreeC or more and it is more preferable to carry out at 10 degreeC or more. By carrying out at 0 degreeC or more and 80 degrees C or less, it becomes an appropriate viscosity and can fully stir.
- the compound having an imide structure represented by the general formula (1) can be obtained by reacting in a ketone solvent (for example, cyclohexanone), so that (b) at least 2 is added to the solution after this reaction.
- a ketone solvent for example, cyclohexanone
- a compound having two or more epoxy groups may be mixed.
- the epoxy resin composition of the present invention is suitably used as an adhesive (underfill agent) for joining a semiconductor element and a substrate.
- the film obtained by curing the thermosetting resin composition of the present invention is used for applications such as a protective film for semiconductor elements, an interlayer insulating film for multilayer wiring for high-density mounting, and a wiring protective insulating film for circuit boards. Used. Thus, a semiconductor device can be obtained.
- Hydroxyl equivalent (g / eq) ((Mwb ⁇ Mb + Mwa + Ma + Mwe ⁇ 2) ⁇ (Mb + Ma + 2-1) ⁇ 18) / (OHb + OHa + OHe)
- Mwb represents the molecular weight of the diamine component
- Mwa represents the molecular weight of the acid component
- Mwe represents the molecular weight of the end-capping agent
- OHb represents the number of hydroxyl groups in the diamine component
- OHa represents the number of hydroxyl groups in the acid component
- OHe represents the number of hydroxyl groups in the end-capping agent.
- Mb represents the molar ratio of the diamine component when the molar ratio of the end capping agent is 2
- Ma similarly represents the molar ratio of the acid component when the molar ratio of the end capping agent is 2.
- Mb represents the molar ratio of the diamine component when the molar ratio of the end capping agent is 2
- Ma similarly represents the molar ratio of the acid component when the molar ratio of the end capping agent is 2.
- the cured film on the obtained silicon wafer was immersed in 47 wt% hydrofluoric acid for 7 minutes at room temperature, then washed with tap water, and carefully peeled from the silicon wafer so as not to be broken.
- NMP was added to the epoxy resin composition to a solid content concentration of 70% by weight, a solution was prepared, and then applied by spin coating, followed by a hot plate at 120 ° C. (Dainippon Screen) Baking was performed for 3 minutes with SKW-636 manufactured by Manufacture Co., Ltd. to prepare a pre-baked film having a thickness of 10 ⁇ m ⁇ 1 ⁇ m. This film was placed in an inert oven (INH-21CD manufactured by Koyo Thermo System Co., Ltd.), raised to a curing temperature of 170 ° C. over 30 minutes, and heat-treated at 170 ° C. for 120 minutes. Thereafter, the oven was gradually cooled to 50 ° C.
- inert oven IH-21CD manufactured by Koyo Thermo System Co., Ltd.
- the cured film on the obtained silicon wafer was immersed in 47% hydrofluoric acid at room temperature for 7 minutes, washed with tap water, and carefully peeled from the silicon wafer so as not to be broken.
- the cured film obtained by the above method was cut out to 3 mm ⁇ 17 mm, and using a thermomechanical analyzer SS-6100 (manufactured by Seiko Instruments Inc.), a tensile mode, a temperature range of 25 to 150 ° C., a rate of temperature increase
- the elongation of the cured film was measured under the conditions of 5 ° C./min, initial load 0.5 g, and chuck interval 15 mm. From the obtained measurement results, an average coefficient of thermal expansion at 25 to 150 ° C. was calculated using the following formula.
- L 25 is the sample length at 25 ° C.
- L 150 is the sample length at 150 ° C.
- Average coefficient of thermal linear expansion (1 / L 25 ) [(L 150 ⁇ L 25 ) / (150 ⁇ 25)]
- Viscosity measurement NMP was added to the epoxy resin composition so as to have a solid content of 70% by weight, a solution was prepared, 1 ml was weighed, and measured at 25 ° C. using an E-type viscometer manufactured by Tokimec. did. When the viscosity exceeds 1000 mPa ⁇ s, workability is lowered.
- Synthesis Example 1 Synthesis of Compound A having an imide structure (Examples 1, 10 to 13) (See Table 1 for the structure of each compound) 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as 6FAP) as a diamine component in a 500 mL three-necked flask equipped with a nitrogen introduction tube, a stirring rod, and a thermometer under a dry nitrogen stream 36.6 g (100 mmol) manufactured by AZ Materials Co., Ltd. was dissolved in 100 g of cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.).
- 6FAP 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
- Synthesis Example 2 Synthesis of Compound B having an imide structure (Example 2)
- 36.6 g (100 mmol) of 6FAP as a diamine component was dissolved in 120 g of cyclohexanone under a dry nitrogen stream.
- PMDA 16.4g (75 mmol) was added here as an acid component, and it stirred at 60 degreeC for 1 hour.
- 4.9 g (50 mmol) of MA as an end-capping agent was added together with 15 g of cyclohexanone, and after stirring for 1 hour at 60 ° C., the temperature was changed to 160 ° C. for 6 hours, The reaction was performed while adding cyclohexanone. Thereafter, the mixture was cooled, and cyclohexanone was added so that the content of Compound B having an imide structure in the solution was 30% by weight.
- Synthesis Example 3 Synthesis of Compound C having an imide structure (Example 3)
- 36.6 g (100 mmol) of 6FAP as a diamine component was dissolved in 120 g of cyclohexanone under a dry nitrogen stream.
- BPDA 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride
- Synthesis Example 4 Synthesis of Compound D having an imide structure (Example 4) Bis (3-amino-4-hydroxyphenyl) sulfone (ABPS, manufactured by AZ Materials Co., Ltd.) as a diamine component in a 500 mL three-necked flask equipped with a nitrogen introduction tube, a stirring rod, and a thermometer under a dry nitrogen stream 28.0 g (100 mmol) was dissolved in 160 g of cyclohexanone.
- ABPS (3-amino-4-hydroxyphenyl) sulfone
- Synthesis Example 5 Synthesis of Compound E having an imide structure (Example 5) Bis (3-amino-4-hydroxyphenyl) ether (ADPE, manufactured by AZ Materials Co., Ltd.) as a diamine component in a 500 mL three-necked flask equipped with a nitrogen inlet tube, a stirring rod, and a thermometer under a dry nitrogen stream 23.2 g (100 mmol) was dissolved in 150 g of cyclohexanone. To this, 22.2 g (50 mmol) of 6FDA as an acid component and 9.8 g (100 mmol) of MA as an end-capping agent were added and stirred at 60 ° C. for 1 hour.
- ADPE (3-amino-4-hydroxyphenyl) ether
- the temperature was set to 160 ° C., and the reaction was carried out for 6 hours while distilling out the coming water and adding cyclohexanone appropriately. Thereafter, the mixture was cooled and cyclohexanone was added so that the content of the compound E having an imide structure in the solution was 30% by weight.
- Synthesis Example 6 Synthesis of Compound F having an imide structure (Example 6)
- 36.6 g (100 mmol) of 6FAP as a diamine component was dissolved in 160 g of cyclohexanone under a dry nitrogen stream.
- PMDA 10.9g (50 mmol) was added here as an acid component
- NA 16.4g (100 mmol) was added as terminal blocker, and it stirred at 60 degreeC for 1 hour. Thereafter, the temperature was set to 160 ° C., and the reaction was carried out for 6 hours while distilling out the coming water and adding cyclohexanone appropriately. Thereafter, the mixture was cooled, and cyclohexanone was added so that the content of the compound F having an imide structure in the solution was 30% by weight.
- Synthesis Example 7 Synthesis of Compound G having an imide structure (Example 7) A 9,9-bis (3-amino-4-hydroxyphenyl) fluorene (hereinafter referred to as BAHF (FL)) is used as a diamine component in a 500 mL three-necked flask equipped with a nitrogen introduction tube, a stirring rod, and a thermometer under a dry nitrogen stream. 38.0 g (100 mmol) of JFE Chemical Co., Ltd. was dissolved in 160 g of cyclohexanone. PMDA 10.9g (50 mmol) was added here as an acid component, and MA 9.8g (100 mmol) was added as terminal blocker, and it stirred at 60 degreeC for 1 hour.
- BAHF 9,9-bis (3-amino-4-hydroxyphenyl) fluorene
- the temperature was set to 160 ° C., and the reaction was carried out for 6 hours while distilling out the coming water and adding cyclohexanone appropriately. Thereafter, the mixture was cooled, and cyclohexanone was added so that the content of the compound G having an imide structure in the solution was 30% by weight.
- Synthesis Example 8 Synthesis of Compound H having an imide structure (Example 8) BAHF (FL) 38.0 g (100 mmol) was dissolved in 160 g of cyclohexanone as a diamine component in a 500 mL three-necked flask equipped with a nitrogen introduction tube, a stirring rod, and a thermometer under a dry nitrogen stream.
- BSAA (isopropylidenediphenoxy) bis (phthalic anhydride)
- MA is used as a terminal blocking agent.
- Synthesis Example 9 Synthesis of Compound I having an imide structure (Example 9) 10.0 g (50 mmol) of 4,4-diaminodiphenyl ether (DAE, manufactured by Tokyo Chemical Industry Co., Ltd.) as a diamine component in a 500 mL three-necked flask equipped with a nitrogen introduction tube, a stirring rod, and a thermometer under a dry nitrogen stream ), 76.0 g (200 mmol) of BAHF (FL) was dissolved in 160 g of cyclohexanone.
- DAE 4,4-diaminodiphenyl ether
- Synthesis Example 10 Synthesis of Compound J having an imide structure (Comparative Example 1)
- 36.6 g (100 mmol) of 6FAP as a diamine component was dissolved in 100 g of cyclohexanone under a dry nitrogen stream.
- 19.6 g (200 mmol) of MA as an end-capping agent was added together with 35 g of cyclohexanone, stirred at 60 ° C. for 1 hour, and then at a temperature of 160 ° C. for 6 hours.
- the reaction was performed while adding cyclohexanone. Thereafter, the solution was cooled, and cyclohexanone was added so that the content of the compound J having an imide structure in the solution was 30% by weight.
- Synthesis Example 11 Synthesis of Compound K having an imide structure (Comparative Example 2) In a 500 mL three-necked flask equipped with a nitrogen inlet tube, a stir bar, and a thermometer, 36.6 g (100 mmol) of 6FAP as a diamine component and 19.6 g (90 mmol) of PMDA as an acid component and 130 g of cyclohexanone as a diamine component. And mixed at 60 ° C. for 1 hour. 1.96 g (20 mmol) of MA was added here as a terminal blocking agent, and after stirring at 60 ° C. for 1 hour, the temperature became 160 ° C. and after a while, a precipitate was deposited.
- N-methylpyrrolidone manufactured by Mitsubishi Chemical Corporation
- cyclohexanone was added appropriately and stirred for 4 hours while removing the solvent and water at 180 ° C. Thereafter, the mixture was cooled, and cyclohexanone was added so that the content of the compound K having an imide group in the solution was 20% by weight.
- Synthesis Example 12 Synthesis of Compound L having an imide structure (Comparative Example 3)
- 31.0 g (100 mmol) of bis (3,4-dicarboxyphenyl) ether dianhydride (ODPA, Manac Co., Ltd.) as an acid component and a diamine component 32.9 g (90 mmol) of 6FAP was mixed in 150 g of cyclohexanone and stirred at a temperature of 60 ° C.
- Synthesis Example 13 Synthesis of Compound M having an imide structure (Comparative Example 4)
- a 500 mL three-necked flask equipped with a nitrogen inlet tube, a stir bar, and a thermometer 3,3′-diaminodiphenyl sulfone (3,3′-DDS, manufactured by Tokyo Chemical Industry Co., Ltd.) as a diamine component in a dry nitrogen stream 24.8 g (100 mmol) was dissolved in 100 g of cyclohexanone.
- Synthesis Example 14 Synthesis of Compound N having an imide structure (Comparative Examples 7 and 8, JP2009-161605 Synthesis Example 2)
- a 2 L glass four-necked flask equipped with a stirrer, a cooling condenser, a thermometer, and a dropping funnel 98.06 g (1.0 mol) of MA, 600 g of N-methylpyrrolidone, and 200 g of toluene were charged and completely dissolved.
- 247 g (0.5 mol) of 2,2′-methylenebis ⁇ 4-methyl-6- (3,5-dimethyl-4-aminobenzyl) phenol ⁇ was added while paying attention to the reaction temperature. Aging was carried out at 30 ° C. for 30 minutes.
- Example 1 50 g of the solution of Compound A having an imide structure obtained in Synthesis Example 1, bisphenol A type epoxy compound “jER” 828 (trade name: hereinafter referred to as jER828, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185 g / eq) 10.9 g was mixed with stirring at 25 ° C. for 60 minutes using a planetary stirring deaerator (Mazerustar (Kurabo Co., Ltd.)) to obtain an epoxy resin composition 1. The resulting epoxy resin composition 1 was evaluated for cyclohexanone solubility, glass transition temperature, coefficient of thermal expansion, and viscosity by the above methods.
- Example 2 An epoxy resin composition 2 was obtained and evaluated in the same manner as in Example 1, except that 50 g of the compound B having an imide structure was used instead of 50 g of the compound A having an imide structure. .
- Example 3 An epoxy resin composition 3 was obtained and evaluated in the same manner as in Example 1, except that 53 g of the compound C having an imide structure was used instead of 30 g of the compound A having an imide structure. .
- Example 4 An epoxy resin composition 4 was obtained and evaluated in the same manner as in Example 1, except that 52 g of the compound D having an imide structure was used instead of 50 g of the compound A having an imide structure. .
- Example 5 An epoxy resin composition 5 was obtained and evaluated in the same manner as in Example 1 except that 48 g of the compound E having an imide structure was used instead of 50 g of the compound A having an imide structure. .
- Example 6 An epoxy resin composition 6 was obtained in the same manner as in Example 1 except that 56 g of the compound F having an imide structure was used instead of 50 g of the compound A having an imide structure, and evaluated in the same manner as in Example 1. .
- Example 7 An epoxy resin composition 7 was obtained in the same manner as in Example 1 except that 52.6 g of the compound G having an imide structure was used instead of 50 g of the compound A having an imide structure. evaluated.
- Example 8 The epoxy resin composition 8 was obtained in the same manner as in Example 1 except that 66 g of the compound H solution having an imide structure was used instead of 50 g of the compound A solution having an imide structure, and evaluated in the same manner as in Example 1. did.
- Example 9 An epoxy resin composition 9 was obtained in the same manner as in Example 1 except that 91.4 g of the compound I having an imide structure was used instead of 50 g of the compound A having an imide structure. evaluated.
- Comparative Example 1 An epoxy resin composition 10 was obtained in the same manner as in Example 1 except that 49 g of the compound J having an imide structure was used instead of 50 g of the compound A having an imide structure, and evaluated in the same manner as in Example 1. .
- Comparative Example 2 An epoxy resin composition 11 was obtained in the same manner as in Example 1 except that 76 g of the compound K solution having an imide structure was used instead of 50 g of the compound A solution having an imide structure, and evaluated in the same manner as in Example 1. However, layer separation of epoxy and polyimide occurred during the curing reaction.
- Comparative Example 3 An epoxy resin composition 12 was obtained in the same manner as in Example 1 except that 64.5 g of the solution of compound L having an imide structure was used instead of 50 g of the solution of compound A having an imide structure. evaluated.
- Example 1 was used except that 50 g of a compound M having an imide structure (bismaleimide compound solution) was used instead of 50 g of the compound A having an imide structure, and 1 g of N-methylimidazole was added as a curing agent.
- the epoxy resin composition 13 was obtained and evaluated in the same manner as in Example 1.
- Comparative Example 5 Instead of 50 g of the compound A solution having an imide structure, polyethersulfone resin (manufactured by Sumitomo Chemical Co., Ltd., trade name, Sumika Excel 5003P, weight average molecular weight 67250, terminal phenolic hydroxyl group content 46 mol%, glass transition temperature) 230 ° C.) 15 g, 4,4′-diaminodiphenylsulfone (hereinafter referred to as 4,4′-DDS, manufactured by Wako Pure Chemical Industries, Ltd.) 10 g was used except that a solution of 35 g of N-methylpyrrolidone was used. In the same manner as in Example 1, an epoxy resin composition 14 was obtained and evaluated in the same manner as in Example 1.
- polyethersulfone resin manufactured by Sumitomo Chemical Co., Ltd., trade name, Sumika Excel 5003P, weight average molecular weight 67250, terminal phenolic hydroxyl group content 46 mol%, glass transition temperature) 230
- Comparative Example 6 Although it replaced with 50 g of solutions of the compound A which has an imide structure instead of using the solution which melt
- Example 10 Epoxy resin in the same manner as in Example 1 except that cresol novolac type epoxy compound “Epiclon” N660 (trade name, hereinafter referred to as N660, manufactured by DIC Corporation, epoxy equivalent 207 g / eq) was used instead of jER828. A composition 15 was obtained and evaluated in the same manner as in Example 1.
- cresol novolac type epoxy compound “Epiclon” N660 trade name, hereinafter referred to as N660, manufactured by DIC Corporation, epoxy equivalent 207 g / eq
- Example 11 The same procedure as in Example 1 was performed except that 5.4 g of p-aminophenol type epoxy compound “jER” 630 (trade name, jER630, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 96 g / eq) was used instead of Epicoat 828. Thus, an epoxy resin composition 16 was obtained and evaluated in the same manner as in Example 1.
- Example 12 In place of jER828, 7.7 g of tetraglycidyl diaminodiphenylsulfone (trade name, TGDAS, manufactured by Konishi Chemical Industry Co., Ltd., epoxy equivalent: 138 g / eq) and bisphenol F type epoxy compound “jER” 807 (trade name, hereinafter referred to as jER807) An epoxy resin composition 17 was obtained in the same manner as in Example 1 except that 5.0 g of epoxy equivalent, 171 g / eq) manufactured by Mitsubishi Chemical Corporation and 1.8 g of 4,4′-DDS were used. And evaluated in the same manner.
- TGDAS tetraglycidyl diaminodiphenylsulfone
- jER807 bisphenol F type epoxy compound
- Example 13 Instead of jER828, naphthalene type epoxy compound “Epiclon” HP4710 (trade name, manufactured by DIC Corporation, epoxy equivalent 171 g / eq) 17 g and jER807 2.5 g, 4,4′-DDS 3.6 g were used.
- the epoxy resin composition 18 was obtained and evaluated in the same manner as in Example 1.
- Comparative Example 7 An epoxy resin was prepared in the same manner as in Example 1 except that 50 g of a hydroxyl group-containing maleimide N was used instead of 50 g of the compound A having an imide structure, and a cresol novolac epoxy compound N660 was used instead of “jER” 828. A resin composition 19 was obtained and evaluated in the same manner as in Example 1.
- Comparative Example 8 The epoxy resin composition 20 was obtained in the same manner as in Example 1 except that 50 g of the hydroxyl group-containing maleimide N solution was used instead of 50 g of the compound A solution having an imide structure, and evaluated in the same manner as in Example 1.
- Tables 1 and 2 show the compositions and evaluation results of Examples and Comparative Examples.
- the epoxy resin composition has an extremely high glass transition temperature, a low coefficient of thermal expansion, and an excellent processability that is soluble in ketone solvents such as methyl ethyl ketone and cyclohexanone. Can be provided.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Epoxy Resins (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
(1-1)末端封止剤を用いた場合
各実施例および比較例で使用したジアミン成分、酸成分、末端封止剤それぞれの分子量、水酸基の数、モル比を用いて以下の計算式で求めた。なお各成分のモル比については末端封止剤のモル比を2として計算した。
水酸基当量(g/eq)=((Mwb×Mb+Mwa+Ma+Mwe×2)-(Mb+Ma+2-1)×18)/(OHb+OHa+OHe)
ここでMwbはジアミン成分の分子量を、Mwaは酸成分の分子量を、Mweは末端封止剤の分子量を表す。またOHbはジアミン成分の水酸基の数を、OHaは酸成分の水酸基の数を、OHeは末端封止剤の水酸基の数を表す。またMbは末端封止剤のモル比を2としたときのジアミン成分のモル比を、Maは同じく末端封止剤のモル比を2としたときの酸成分のモル比を表す。
以下の計算式で求めた。
水酸基当量(g/eq)=Mwb/OHb
以下の計算式で求めた。
水酸基当量(g/eq)=Mwa/OHa
各実施例および比較例で使用したジアミン成分、酸成分、末端封止剤それぞれのモル比を用いて以下の計算式で求めた。なお各成分のモル比については末端封止剤のモル比を2として計算した。
一般式(1)におけるvの平均値=(Mb/(Mb-Ma))-1
ゲルパーミエーションクロマトグラフィー(日本ウォーターズ(株)製 Waters 2690)を用い、ポリスチレン換算で数平均分子量を求めた。カラムは東ソー(株)製 TOSOH TXK-GEL α-2500、およびα-4000を用い、移動層にはNMPを用いた。
エポキシ樹脂組成物をシクロヘキサノンに固形分30重量%で混合し、肉眼で溶解するかどうかを観察した。完全に溶解している場合は○、完全に溶解していない場合は×とした。
エポキシ樹脂組成物にNMPを固形分濃度70重量%になるように加えて溶液を作製した後、スピンコート法でシリコンウエハ上に塗布し、次いで120℃のホットプレート(大日本スクリーン製造(株)製SKW-636)で3分間ベークし、厚さ10μm±1μmのプリベーク膜を作製した。この膜をイナートオーブン(光洋サーモシステム(株)製INH-21CD)に投入し、170℃の硬化温度まで80分間かけて上昇させ、170℃で120分間加熱処理を行った。その後、オーブン内が50℃以下になるまで徐冷し、キュア膜を得た。次に得られたシリコンウエハ上のキュア膜を47重量%フッ化水素酸に室温で7分間浸した後、水道水で洗浄し、破れないように慎重にシリコンウエハから剥離した。
エポキシ樹脂組成物にNMPを固形分濃度70重量%になるように加えて溶液を作製した後、スピンコート法で塗布し、次いで120℃のホットプレート(大日本スクリーン製造(株)製SKW-636)で3分間ベークし、厚さ10μm±1μmのプリベーク膜を作製した。この膜をイナートオーブン(光洋サーモシステム(株)製INH-21CD)に投入し、170℃の硬化温度まで30分間かけて上昇させ、170℃で120分間加熱処理を行った。その後、オーブン内が50℃以下になるまで徐冷し、キュア膜を得た。次に得られたシリコンウエハ上のキュア膜を47%フッ化水素酸に室温で7分間浸した後、水道水で洗浄し、破れないように慎重にシリコンウエハから剥離した。
平均熱線膨張係数=(1/L25)[(L150-L25)/(150-25)]
エポキシ樹脂組成物にNMPを固形分濃度70重量%になるように加えて溶液を作製して1mlをはかり取り、トキメック社製E型粘度計を用いて、25℃で測定した。粘度は1000mPa・sを超えると作業性が低下する。
窒素導入管、攪拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、ジアミン成分として2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン(以下6FAPとする、AZマテリアルズ(株)製)36.6g(100ミリモル)をシクロヘキサノン(和光純薬工業(株)製)100gに溶解させた。ここに酸成分として無水ピロメリット酸二無水物(以下PMDAとする、ダイセル工業(株)製)10.9g(50ミリモル)を加え、60℃で1時間攪拌した。その後、末端封止剤として無水マレイン酸(以下MAとする、和光純薬工業(株)製)9.8g(100ミリモル)をシクロヘキサノン35gとともに加え、60℃で1時間攪拌後、温度を160℃にして6時間、出てくる水を留去しながら、適宜、シクロヘキサノンを追加しながら反応させた。
その後冷却し、溶液のイミド構造を有する化合物Aの含量が30重量%になるようにシクロヘキサノンを追加した。
窒素導入管、攪拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、ジアミン成分として6FAP 36.6g(100ミリモル)をシクロヘキサノン 120gに溶解させた。ここに酸成分としてPMDA 16.4g(75ミリモル)を加え、60℃で1時間攪拌した。その後、末端封止剤としてMA 4.9g(50ミリモル)をシクロヘキサノン15gとともに加え、60℃で1時間攪拌後、温度を160℃にして6時間、出てくる水を留去しながら、適宜、シクロヘキサノンを追加しながら反応させた。
その後冷却し、溶液のイミド構造を有する化合物Bの含量が30重量%になるようにシクロヘキサノンを追加した。
窒素導入管、攪拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、ジアミン成分として6FAP 36.6g(100ミリモル)をシクロヘキサノン 120gに溶解させた。ここに酸成分として2,3,3‘,4’-ビフェニルテトラカルボン酸二無水物(BPDA、LINCHUAN CHEMICAL(株)製))14.7g(55ミリモル)を加え、60℃で1時間攪拌した。その後、末端封止剤としてMA 8.8g(90ミリモル)をシクロヘキサノン15gとともに加え、60℃で1時間攪拌後、温度を160℃にして6時間、出てくる水を留去しながら、適宜、シクロヘキサノンを追加しながら反応させた。
その後冷却し、溶液のイミド構造を有する化合物Cの含量が30重量%になるようにシクロヘキサノンを追加した。
窒素導入管、攪拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、ジアミン成分としてビス(3-アミノ-4-ヒドロキシフェニル)スルホン(ABPS、AZマテリアルズ(株)製) 28.0g(100ミリモル)をシクロヘキサノン160gに溶解させた。ここに酸成分としてヘキサフルオロプロピリデンビス(フタル酸無水物)(以下6FDAとする、ダイキン工業(株)製)22.2g(50ミリモル)、末端封止剤として無水ナジック酸(以下NAとする、東京化成工業(株)製)16.4g(100ミリモル)を加え、60℃で1時間攪拌した。その後、温度を160 ℃にして6時間、出てくる水を留去しながら、適宜、シクロヘキサノンを追加しながら反応させた。
その後冷却し、溶液のイミド構造を有する化合物Dの含量が30重量%になるようにシクロヘキサノンを追加した。
窒素導入管、攪拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、ジアミン成分としてビス(3-アミノ-4-ヒドロキシフェニル)エーテル(ADPE、AZマテリアルズ(株)製) 23.2g(100ミリモル)をシクロヘキサノン 150gに溶解させた。ここに酸成分として6FDA 22.2g(50ミリモル)、末端封止剤としてMA 9.8g(100ミリモル)を加え、60℃で1時間攪拌した。その後、温度を160℃にして6時間、出てくる水を留去しながら、適宜、シクロヘキサノンを追加しながら反応させた。
その後冷却し、溶液のイミド構造を有する化合物Eの含量が30重量%になるようにシクロヘキサノンを追加した。
窒素導入管、攪拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、ジアミン成分として6FAP 36.6g(100ミリモル)をシクロヘキサノン160gに溶解させた。ここに酸成分としてPMDA 10.9g(50ミリモル) 、末端封止剤としてNA 16.4g(100ミリモル)を加え、60℃で1時間攪拌した。その後、温度を160℃にして6時間、出てくる水を留去しながら、適宜、シクロヘキサノンを追加しながら反応させた。
その後冷却し、溶液のイミド構造を有する化合物Fの含量が30重量%になるようにシクロヘキサノンを追加した。
窒素導入管、攪拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、ジアミン成分として9,9-ビス(3-アミノ-4-ヒドロキシフェニル)フルオレン(以下BAHF(FL)とする、JFEケミカル(株)製)、38.0g(100ミリモル)をシクロヘキサノン160gに溶解させた。ここに酸成分としてPMDA 10.9g(50ミリモル)、末端封止剤としてMA 9.8g(100ミリモル)を加え、60℃で1時間攪拌した。その後、温度を160℃にして6時間、出てくる水を留去しながら、適宜、シクロヘキサノンを追加しながら反応させた。
その後冷却し、溶液のイミド構造を有する化合物Gの含量が30重量%になるようにシクロヘキサノンを追加した。
窒素導入管、攪拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、ジアミン成分として、BAHF(FL)38.0g(100ミリモル)をシクロヘキサノン160gに溶解させた。ここに酸成分として(イソプロピリデンジフェノキシ)ビス(フタール酸無水物)(以下BSAAとする、SABICイノベーティブプラスチックスジャパン(株)製)26.0g(50ミリモル)、末端封止剤としてMA 9.8g(100ミリモル)を加え、60℃で1時間攪拌した。その後、温度を160℃にして6時間、出てくる水を留去しながら、適宜、シクロヘキサノンを追加しながら反応させた。
その後冷却し、溶液のイミド構造を有する化合物Hの含量が30重量%になるようにシクロヘキサノンを追加した。
窒素導入管、攪拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、ジアミン成分として4,4-ジアミノジフェニルエーテル(DAE、東京化成工業(株)製) 10.0g(50ミリモル)、BAHF(FL)76.0g(200ミリモル)をシクロヘキサノン160gに溶解させた。ここに酸成分としてBSAA 104.1g(200ミリモル)、末端封止剤としてMA 9.8g(100ミリモル)を加え、60℃で1時間攪拌した。その後、温度を160℃にして6時間、出てくる水を留去しながら、適宜、シクロヘキサノンを追加しながら反応させた。
その後冷却し、溶液のイミド構造を有する化合物Iの含量が30重量%になるようにシクロヘキサノンを追加した。
窒素導入管、攪拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、ジアミン成分として6FAP 36.6g(100ミリモル)をシクロヘキサノン 100gに溶解させた。ここに末端封止剤としてMA 19.6g(200ミリモル)をシクロヘキサノン35gとともに加え、60℃で1時間攪拌後、温度を160℃にして6時間、出てくる水を留去しながら、適宜、シクロヘキサノンを追加しながら反応させた。
その後冷却し、溶液のイミド構造を有する化合物Jの含量が30重量%になるようにシクロヘキサノンを追加した。
窒素導入管、攪拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、ジアミン成分として6FAP 36.6g(100ミリモル)、酸成分としてPMDA 19.6g(90ミリモル)をシクロヘキサノン 130g中で混合し、60℃で1時間攪拌した。ここに末端封止剤としてMA 1.96g(20ミリモル)を加え、60℃で1時間攪拌後、温度を160℃になりしばらくすると、沈殿が析出してきた。そのため、N-メチルピロリドン(三菱化学(株)製)121gを加えて、180℃で溶媒と水を除去しながら、適宜、シクロヘキサノンを加え4時間攪拌した。
その後冷却し、溶液のイミド基を有する化合物Kの含量が20重量%になるようにシクロヘキサノンを追加した。
冷却管及び撹拌装置付きの1Lセパラブルフラスコに、酸成分としてビス(3,4-ジカルボキシフェニル)エーテル二無水物(ODPA、マナック(株)製)31.0g(100ミリモル)、ジアミン成分として6FAP 32.9g(90ミリモル)をシクロヘキサノン 150g中に混合し、温度60℃で1時間撹拌し、その後末端封止剤として3-アミノフェノール(AMP、東京化成工業(株)製)2.2g(20ミリモル)をシクロヘキサノン10gとともに加え、温度を160℃に上昇し、出てくる水をシクロヘキサノンとともに除去しながら、適宜、シクロヘキサノンを加えて、6時間攪拌してポリイミド溶液を得た。
その後冷却し、溶液のイミド基を有する化合物Lの含量が30重量%になるようにシクロヘキサノンを追加した。
窒素導入管、攪拌棒、温度計を取り付けた500mLの3つ口フラスコに乾燥窒素気流下、ジアミン成分として3,3’-ジアミノジフェニルスルホン(3,3’-DDS、東京化成工業(株)製) 24.8g(100ミリモル)をシクロヘキサノン 100gに溶解させた。ここに末端封止剤としてMA 19.6g(200ミリモル)を加え、60℃で1時間攪拌後、温度を160℃にして6時間、出てくる水を留去しながら、適宜、シクロヘキサノンを追加しながら反応させた。
その後冷却し、溶液のイミド基を有する化合物Mの含量が30重量%になるようにシクロヘキサノンを追加した。
攪拌機、冷却コンデンサー、温度計、滴下ロートを備えた、2Lのガラス製四つ口フラスコにMA98.06g(1.0モル)、N-メチルピロリドン 600g、トルエン200gを仕込み、完全に溶解させた。その中に2,2’―メチレンビス{4-メチル-6-(3,5-ジメチル-4-アミノベンジル)フェノール}247g(0.5モル)を反応温度に注意しながら、添加し、さらに40℃で30分間熟成した。その後、130℃に昇温、130~135℃で4時間脱水還流を行い、閉環反応させた。反応終了後、冷却し3Lのメタノール中に投入し、析出物をろ過した。さらにこの結晶を冷水1Lでよく洗い、乾燥した。乾燥後の重量は325gであった。この化合物30gをN-メチルピロリドン70gに溶解した。
合成例1で得られたイミド構造を有する化合物Aの溶液50g、ビスフェノールA型エポキシ化合物 “jER”828(商品名 以下jER828とする、三菱化学(株)製、エポキシ当量 185g/eq)10.9gを遊星式撹拌脱泡機(マゼルスター(クラボウ(株)製))を用いて25℃で60分間撹拌して混合させ、エポキシ樹脂組成物1を得た。得られたエポキシ樹脂組成物1のシクロヘキサノン溶解性、ガラス転移温度、熱膨張率、粘度を前記方法により評価した。
イミド構造を有する化合物Aの溶液50gに代えてイミド構造を有する化合物Bの溶液50gを用いた以外は実施例1と同様にして、エポキシ樹脂組成物2を得、実施例1と同様に評価した。
イミド構造を有する化合物Aの溶液30gに代えてイミド構造を有する化合物Cの溶液53gを用いた以外は実施例1と同様にして、エポキシ樹脂組成物3を得、実施例1と同様に評価した。
イミド構造を有する化合物Aの溶液50gに代えてイミド構造を有する化合物Dの溶液52gを用いた以外は実施例1と同様にして、エポキシ樹脂組成物4を得、実施例1と同様に評価した。
イミド構造を有する化合物Aの溶液50gに代えてイミド構造を有する化合物Eの溶液48gを用いた以外は実施例1と同様にして、エポキシ樹脂組成物5を得、実施例1と同様に評価した。
イミド構造を有する化合物Aの溶液50gに代えてイミド構造を有する化合物Fの溶液56gを用いた以外は実施例1と同様にして、エポキシ樹脂組成物6を得、実施例1と同様に評価した。
イミド構造を有する化合物Aの溶液50gに代えてイミド構造を有する化合物Gの溶液52.6gを用いた以外は実施例1と同様にして、エポキシ樹脂組成物7を得、実施例1と同様に評価した。
イミド構造を有する化合物Aの溶液50gに代えてイミド構造を有する化合物Hの溶液66gを用いた以外は実施例1と同様にして、エポキシ組樹脂成物8を得、実施例1と同様に評価した。
イミド構造を有する化合物Aの溶液50gに代えてイミド構造を有する化合物Iの溶液91.4gを用いた以外は実施例1と同様にして、エポキシ樹脂組成物9を得、実施例1と同様に評価した。
イミド構造を有する化合物Aの溶液50gに代えてイミド構造を有する化合物Jの溶液49gを用いた以外は実施例1と同様にして、エポキシ樹脂組成物10を得、実施例1と同様に評価した。
イミド構造を有する化合物Aの溶液50gに代えてイミド構造を有する化合物Kの溶液76gを用いた以外は実施例1と同様にして、エポキシ樹脂組成物11を得、実施例1と同様に評価したが、硬化反応を進めている間に、エポキシとポリイミドとの層分離が発生した。
イミド構造を有する化合物Aの溶液50gに代えてイミド構造を有する化合物Lの溶液64.5gを用いた以外は実施例1と同様にして、エポキシ樹脂組成物12を得、実施例1と同様に評価した。
イミド構造を有する化合物Aの溶液50gに代えてイミド構造を有する化合物Mの溶液(ビスマレイミド化合物溶液)50gを用い、硬化剤としてN-メチルイミダゾール1gを加えた以外は実施例1と同様にして、エポキシ樹脂組成物13を得、実施例1と同様に評価した。
イミド構造を有する化合物Aの溶液50gに代えて、ポリエーテルスルホン樹脂(住友化学(株)製、商品名、スミカエクセル5003P、重量平均分子量67250、末端フェノール性水酸基含有率46モル%、ガラス転移温度230℃)15g、4,4’-ジアミノジフェニルスルホン(以下4,4’-DDSとする、和光純薬工業(株)製)10gをN-メチルピロリドン35gに溶解した溶液を用いた以外は実施例1と同様にして、エポキシ樹脂組成物14を得、実施例1と同様に評価した。
イミド構造を有する化合物Aの溶液50gに代えて、6FAP15gをシクロヘキサノン 35gに溶解した溶液を用いた以外は実施例1と同様にしたが、混合中にゲル化が進み、評価することができなかった。
jER828に代えて、クレゾールノボラック型エポキシ化合物 “エピクロン”N660(商品名、以下N660とする、DIC(株)製、エポキシ当量 207g/eq)を用いた以外は実施例1と同様にして、エポキシ樹脂組成物15を得、実施例1と同様に評価した。
エピコート828に代えて、p-アミノフェノール型エポキシ化合物“jER”630(商品名、jER630、三菱化学(株)製、エポキシ当量 96g/eq)5.4gを用いた以外は実施例1と同様にして、エポキシ樹脂組成物16を得、実施例1と同様に評価した。
jER828に代えて、テトラグリシジルジアミノジフェニルスルホン(商品名、TGDAS、小西化学工業(株)製、エポキシ当量 138g/eq)7.7gと、ビスフェノールF型エポキシ化合物 “jER”807(商品名、以下jER807 三菱化学(株)製、エポキシ当量 171g/eq) 5.0g、4,4’-DDS 1.8gを用いた以外は実施例1と同様にして、エポキシ樹脂組成物17を得、実施例1と同様に評価した。
jER828に代えて、ナフタレン型エポキシ化合物”エピクロン“ HP4710(商品名、DIC(株)製、エポキシ当量 171g/eq)17gとjER807 2.5g、4,4’-DDS 3.6gを用いた以外は実施例1と同様にして、エポキシ樹脂組成物18を得、実施例1と同様に評価した。
イミド構造を有する化合物Aの溶液50gに代えてヒドロキシル基含有マレイミドNの溶液50gを用い、 “jER”828に代えてクレゾールノボラック型エポキシ化合物N660を用いた以外は実施例1と同様にして、エポキシ樹脂組成物19を得、実施例1と同様に評価した。
イミド構造を有する化合物Aの溶液50gに代えてヒドロキシル基含有マレイミドNの溶液50gを用いた以外は実施例1と同様にして、エポキシ樹脂組成物20を得、実施例1と同様に評価した。
Claims (5)
- (a)一般式(1)で表されるイミド構造を有する化合物および(b)少なくとも2つのエポキシ基を有する化合物を含有し、(a)一般式(1)で表されるイミド構造を有する化合物の数平均分子量が1000~5000であるエポキシ樹脂組成物。
- 前記(b)少なくとも2つのエポキシ基を有する化合物が、下記一般式(6)~(9)から選ばれた1以上の化合物である請求項1記載のエポキシ樹脂組成物。
- シクロヘキサノンに30重量%以上の濃度で溶解する請求項1または2記載のエポキシ樹脂組成物。
- 下記一般式(2)’で表される構造を示すものを50モル%以上有するジアミン、下式(4)’から選ばれる1以上のテトラカルボン酸無水物および下式(5)’から選ばれる1以上の化合物を(c)’ケトン基を有した溶剤中で50~80℃の条件下0.5~2時間混合して(a)一般式(1)で表されるイミド構造を有する化合物を得て、さらに(b)少なくとも2つのエポキシ基を有する化合物を混合するエポキシ樹脂組成物の製造方法。
- 請求項1~3のいずれかに記載のエポキシ樹脂組成物を含む半導体装置。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/004,841 US9123689B2 (en) | 2011-03-16 | 2012-03-15 | Epoxy resin composition, method for producing same, and semiconductor device using same |
JP2013504774A JP5811172B2 (ja) | 2011-03-16 | 2012-03-15 | エポキシ樹脂組成物およびその製造方法ならびにそれを用いた半導体装置 |
CN201280008508.5A CN103370354B (zh) | 2011-03-16 | 2012-03-15 | 环氧树脂组合物及其制造方法以及使用其的半导体装置 |
KR1020137023998A KR101868190B1 (ko) | 2011-03-16 | 2012-03-15 | 에폭시 수지 조성물 및 그의 제조 방법 및 그것을 사용한 반도체 장치 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-057711 | 2011-03-16 | ||
JP2011057711 | 2011-03-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012124780A1 true WO2012124780A1 (ja) | 2012-09-20 |
Family
ID=46830844
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/056762 WO2012124780A1 (ja) | 2011-03-16 | 2012-03-15 | エポキシ樹脂組成物およびその製造方法ならびにそれを用いた半導体装置 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9123689B2 (ja) |
JP (1) | JP5811172B2 (ja) |
KR (1) | KR101868190B1 (ja) |
CN (1) | CN103370354B (ja) |
TW (1) | TWI542639B (ja) |
WO (1) | WO2012124780A1 (ja) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016101538A1 (zh) * | 2014-12-26 | 2016-06-30 | 广东生益科技股份有限公司 | 一种环氧树脂组合物以及使用它的预浸料和层压板 |
JPWO2014196515A1 (ja) * | 2013-06-03 | 2017-02-23 | 株式会社ダイセル | 硬化性エポキシ樹脂組成物 |
US9873789B2 (en) | 2014-12-26 | 2018-01-23 | Shengyi Technology Co., Ltd. | Halogen-free epoxy resin composition, prepreg and laminate using same |
JP2018070668A (ja) * | 2016-10-24 | 2018-05-10 | 信越化学工業株式会社 | 液状エポキシ樹脂組成物 |
CN109721947A (zh) * | 2017-10-27 | 2019-05-07 | 财团法人工业技术研究院 | 环氧树脂组合物 |
US10544255B2 (en) | 2015-12-28 | 2020-01-28 | Shengyi Technology Co., Ltd. | Epoxy resin composition, prepreg and laminate prepared therefrom |
JP2020070359A (ja) * | 2018-10-31 | 2020-05-07 | ユニチカ株式会社 | 低誘電率ポリイミド |
JP2020517778A (ja) * | 2017-04-18 | 2020-06-18 | ハンツマン・アドバンスド・マテリアルズ・アメリカズ・エルエルシー | 硬化性樹脂系 |
US10696844B2 (en) | 2014-02-25 | 2020-06-30 | Shengyi Technology Co., Ltd. | Halogen-free flame retardant type resin composition |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104829844B (zh) * | 2015-05-12 | 2017-06-06 | 东华大学 | 一种碳纤维电缆芯用mhfpi型耐高温环氧基体树脂及其制备方法 |
CN114437509A (zh) * | 2020-10-30 | 2022-05-06 | 臻鼎科技股份有限公司 | 导电树脂组合物及应用导电树脂组合物的导电层及电路板 |
CN114656750B (zh) * | 2021-12-31 | 2023-05-26 | 华侨大学 | 户外用环氧树脂基抗紫外老化绝缘材料、制备方法和应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009203252A (ja) * | 2008-02-26 | 2009-09-10 | Ist Corp | バルクモールディングコンパウンド及びその成形品 |
JP2010132793A (ja) * | 2008-12-05 | 2010-06-17 | Toray Ind Inc | 熱硬化性樹脂組成物、それを用いたアンダーフィル剤および半導体装置 |
JP2011046928A (ja) * | 2009-07-30 | 2011-03-10 | Toray Ind Inc | 組成物およびそれからなる組成物シート |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4389504A (en) * | 1981-10-02 | 1983-06-21 | The United States Of America As Represented By The United States National Aeronautics And Space Administration Office Of General Counsel-Code Gp | Elastomer toughened polyimide adhesives |
JPH07268077A (ja) | 1994-04-01 | 1995-10-17 | Sumitomo Bakelite Co Ltd | 熱硬化性樹脂組成物 |
JP2001072833A (ja) | 1998-10-07 | 2001-03-21 | Sumitomo Chem Co Ltd | ビルドアップ工法用の樹脂組成物、ビルドアップ工法用の絶縁材料、およびビルドアッププリント配線板 |
KR100377861B1 (ko) * | 2000-07-07 | 2003-03-29 | 한학수 | 전자소자 또는 칩용 절연성 박막 또는 박막형 패키지를 위한 조성물 |
US6777525B2 (en) * | 2001-07-03 | 2004-08-17 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Heat, moisture, and chemical resistant polyimide compositions and methods for making and using them |
JP2003155325A (ja) * | 2001-11-21 | 2003-05-27 | Toto Kagaku Kogyo Kk | 耐熱性樹脂組成物 |
JP4587631B2 (ja) * | 2002-01-30 | 2010-11-24 | Dic株式会社 | 熱硬化性樹脂組成物 |
JP4174248B2 (ja) * | 2002-07-01 | 2008-10-29 | 群栄化学工業株式会社 | ポリイミド樹脂、これを含有する樹脂組成物、電子部品用被覆材料及び電子部品用接着剤 |
JP2009041019A (ja) | 2003-01-07 | 2009-02-26 | Sekisui Chem Co Ltd | 硬化性樹脂組成物、接着性エポキシ樹脂ペースト、接着性エポキシ樹脂シート、導電接続ペースト、導電接続シート及び電子部品接合体 |
JP2006028294A (ja) | 2004-07-14 | 2006-02-02 | Hitachi Chem Co Ltd | 無溶剤1液型の穴埋め用熱硬化性エポキシ樹脂組成物 |
JP4986256B2 (ja) * | 2005-12-21 | 2012-07-25 | 味の素株式会社 | 変性ポリイミド樹脂を含有するプリプレグ |
JP2009155354A (ja) | 2006-03-30 | 2009-07-16 | Ajinomoto Co Inc | 絶縁層用樹脂組成物 |
US7691475B2 (en) * | 2006-07-21 | 2010-04-06 | 3M Innovative Properties Company | Anisotropic conductive adhesives |
CN100412111C (zh) * | 2006-09-05 | 2008-08-20 | 东华大学 | 一种含酚羟基聚酰亚胺粉末的制备方法 |
JP2008081686A (ja) | 2006-09-28 | 2008-04-10 | Sumitomo Bakelite Co Ltd | 液状エポキシ樹脂組成物およびそれを用いた半導体装置 |
JP4968044B2 (ja) * | 2007-12-19 | 2012-07-04 | 日立化成工業株式会社 | ポリイミド化合物の製造方法、熱硬化性樹脂組成物並びにこれを用いたプリプレグ及び積層板 |
JP5214235B2 (ja) | 2007-12-28 | 2013-06-19 | 群栄化学工業株式会社 | フェノール性水酸基を有する新規ビスマレイミド類及びこれを必須成分とする熱硬化性樹脂組成物、及びその硬化物 |
JP2010090237A (ja) | 2008-10-07 | 2010-04-22 | Ajinomoto Co Inc | エポキシ樹脂組成物 |
JP2010095646A (ja) | 2008-10-17 | 2010-04-30 | Hitachi Chem Co Ltd | 低熱膨張率エポキシ樹脂組成物 |
JP2010095645A (ja) | 2008-10-17 | 2010-04-30 | Hitachi Chem Co Ltd | 低熱膨張率エポキシ樹脂組成物 |
EP2452964A4 (en) * | 2009-07-10 | 2014-06-11 | Toray Industries | LAYER COMPOSITION, ADHESIVE, PCB AND SEMICONDUCTOR DEVICE THEREFORE MADE AND MANUFACTURING METHOD THEREFOR |
-
2012
- 2012-03-15 WO PCT/JP2012/056762 patent/WO2012124780A1/ja active Application Filing
- 2012-03-15 CN CN201280008508.5A patent/CN103370354B/zh not_active Expired - Fee Related
- 2012-03-15 JP JP2013504774A patent/JP5811172B2/ja active Active
- 2012-03-15 US US14/004,841 patent/US9123689B2/en not_active Expired - Fee Related
- 2012-03-15 KR KR1020137023998A patent/KR101868190B1/ko active IP Right Grant
- 2012-03-16 TW TW101108997A patent/TWI542639B/zh not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009203252A (ja) * | 2008-02-26 | 2009-09-10 | Ist Corp | バルクモールディングコンパウンド及びその成形品 |
JP2010132793A (ja) * | 2008-12-05 | 2010-06-17 | Toray Ind Inc | 熱硬化性樹脂組成物、それを用いたアンダーフィル剤および半導体装置 |
JP2011046928A (ja) * | 2009-07-30 | 2011-03-10 | Toray Ind Inc | 組成物およびそれからなる組成物シート |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2014196515A1 (ja) * | 2013-06-03 | 2017-02-23 | 株式会社ダイセル | 硬化性エポキシ樹脂組成物 |
US10696844B2 (en) | 2014-02-25 | 2020-06-30 | Shengyi Technology Co., Ltd. | Halogen-free flame retardant type resin composition |
WO2016101538A1 (zh) * | 2014-12-26 | 2016-06-30 | 广东生益科技股份有限公司 | 一种环氧树脂组合物以及使用它的预浸料和层压板 |
US9873789B2 (en) | 2014-12-26 | 2018-01-23 | Shengyi Technology Co., Ltd. | Halogen-free epoxy resin composition, prepreg and laminate using same |
US10208156B2 (en) | 2014-12-26 | 2019-02-19 | Shengyi Technology Co., Ltd. | Epoxy resin composition, prepreg and laminate using same |
US10544255B2 (en) | 2015-12-28 | 2020-01-28 | Shengyi Technology Co., Ltd. | Epoxy resin composition, prepreg and laminate prepared therefrom |
JP2018070668A (ja) * | 2016-10-24 | 2018-05-10 | 信越化学工業株式会社 | 液状エポキシ樹脂組成物 |
JP2020517778A (ja) * | 2017-04-18 | 2020-06-18 | ハンツマン・アドバンスド・マテリアルズ・アメリカズ・エルエルシー | 硬化性樹脂系 |
JP7107966B2 (ja) | 2017-04-18 | 2022-07-27 | ハンツマン・アドバンスド・マテリアルズ・アメリカズ・エルエルシー | 硬化性樹脂系 |
CN109721947A (zh) * | 2017-10-27 | 2019-05-07 | 财团法人工业技术研究院 | 环氧树脂组合物 |
JP2020070359A (ja) * | 2018-10-31 | 2020-05-07 | ユニチカ株式会社 | 低誘電率ポリイミド |
JP7267567B2 (ja) | 2018-10-31 | 2023-05-02 | ユニチカ株式会社 | 低誘電率ポリイミド |
Also Published As
Publication number | Publication date |
---|---|
JP5811172B2 (ja) | 2015-11-11 |
KR20140020905A (ko) | 2014-02-19 |
CN103370354A (zh) | 2013-10-23 |
TWI542639B (zh) | 2016-07-21 |
KR101868190B1 (ko) | 2018-06-15 |
TW201242999A (en) | 2012-11-01 |
JPWO2012124780A1 (ja) | 2014-07-24 |
US9123689B2 (en) | 2015-09-01 |
CN103370354B (zh) | 2016-01-20 |
US20140005318A1 (en) | 2014-01-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5811172B2 (ja) | エポキシ樹脂組成物およびその製造方法ならびにそれを用いた半導体装置 | |
JP5471423B2 (ja) | アンダーフィル剤およびそれを用いた半導体装置 | |
JP6528404B2 (ja) | 半導体用樹脂組成物および半導体用樹脂フィルムならびにこれらを用いた半導体装置 | |
TWI606109B (zh) | 接著劑組成物、接著劑片及使用它們的硬化物及半導體裝置 | |
JP2010132793A (ja) | 熱硬化性樹脂組成物、それを用いたアンダーフィル剤および半導体装置 | |
TWI417311B (zh) | 熱硬化性樹脂組成物及其用途 | |
JP5521853B2 (ja) | アンダーフィル剤およびそれを用いた半導体装置 | |
JP6947032B2 (ja) | 樹脂組成物、それを用いたシート、積層体、パワー半導体装置、プラズマ処理装置および半導体の製造方法 | |
JP2019035087A (ja) | エポキシ樹脂、エポキシ樹脂組成物及び硬化物 | |
US20160194542A1 (en) | Polyimide resin composition, and heat-conductive adhesive film produced using same | |
TW201033250A (en) | Siloxane-containing polyimide resin | |
TW200911522A (en) | Composite material | |
TWI424004B (zh) | Polyimide silicone resin and thermosetting composition containing the same | |
JP2013143440A (ja) | 金属ベース基板 | |
JP2008277768A (ja) | 絶縁性熱伝導シート | |
TWI797117B (zh) | 醯亞胺寡聚物、硬化劑、接著劑、及醯亞胺寡聚物之製造方法 | |
JP7144182B2 (ja) | 硬化性樹脂組成物、硬化物、接着剤、及び、接着フィルム | |
JP6146999B2 (ja) | エポキシ樹脂、エポキシ樹脂組成物及び硬化物 | |
JP6420171B2 (ja) | ポリアミドイミド樹脂および当該ポリアミドイミド樹脂の製造方法、ならびに熱硬化性樹脂組成物および当該熱硬化性樹脂組成物の硬化物 | |
WO2022138160A1 (ja) | 樹脂組成物、シート状組成物、シート硬化物、積層体、積層部材、ウエハ保持体および半導体製造装置 | |
KR20200013649A (ko) | 경화성 수지 조성물, 경화물, 접착제, 접착 필름, 커버레이 필름, 및, 프린트 배선판 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201280008508.5 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12757993 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2013504774 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20137023998 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14004841 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12757993 Country of ref document: EP Kind code of ref document: A1 |