WO2014021386A1 - エポキシ樹脂組成物、エポキシ樹脂、及び硬化物 - Google Patents
エポキシ樹脂組成物、エポキシ樹脂、及び硬化物 Download PDFInfo
- Publication number
- WO2014021386A1 WO2014021386A1 PCT/JP2013/070774 JP2013070774W WO2014021386A1 WO 2014021386 A1 WO2014021386 A1 WO 2014021386A1 JP 2013070774 W JP2013070774 W JP 2013070774W WO 2014021386 A1 WO2014021386 A1 WO 2014021386A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- epoxy resin
- formula
- resin composition
- carbon atoms
- Prior art date
Links
- 0 *C(COc1ccc(C(*)(*)c(cc2)ccc2OCC(*)OCC2OC2)cc1)O* Chemical compound *C(COc1ccc(C(*)(*)c(cc2)ccc2OCC(*)OCC2OC2)cc1)O* 0.000 description 1
Images
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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
-
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/76—Post-treatment crosslinking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73203—Bump and layer connectors
- H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
Definitions
- the present invention relates to an epoxy resin composition, an epoxy resin, and a cured product.
- Patent Document 1 discloses a method for producing an epoxy resin having a polyether group in which the repeating unit composed of an alkyleneoxy group is less than 3.
- Patent Document 2 discloses a method for producing an epoxy resin having a polyether group having a repeating unit composed of an alkyleneoxy group of less than 6.
- the epoxy resin used as these materials has excellent adhesiveness while having low viscosity, and the cured product has excellent flexibility. Furthermore, from the viewpoint of corrosion resistance and electrical reliability, a low content of halogen-based impurities (so-called low halogen) is also desired.
- the conventional epoxy resin cannot sufficiently meet such a demand, and there is still room for development.
- the cured epoxy resin disclosed in Patent Document 1 cannot provide sufficient flexibility.
- the cured product of the epoxy resin disclosed in Patent Document 2 cannot obtain sufficient flexibility and has poor adhesion.
- this epoxy resin is inferior in reactivity since the content ratio of both terminal epoxy groups is small.
- the viscosity is high and the compatibility with other epoxy resins and the like is poor.
- the present invention has been made in view of the above circumstances, and provides an epoxy resin composition and an epoxy resin capable of obtaining a cured product excellent in flexibility, adhesiveness, and low water absorption while having low viscosity.
- the purpose is to do.
- An epoxy resin represented by the following formula (1) An epoxy resin represented by the following formula (2); An epoxy resin composition comprising: (In the formula, m, n, m ′ and n ′ are each independently an integer of 1 to 30, and R 1 and R 2 are each independently a divalent group having 1 to 12 carbon atoms.
- R 1 and R 2 represents a divalent aromatic group having 6 to 30 carbon atoms
- G 1 represents: Represents a glycidyl group
- G 2 represents a hydrogen atom or a glycidyl group.
- the epoxy resin composition according to [1], comprising: [3] R 2 in the formula (1) is any selected from the group consisting of a phenylene group, a naphthylene group, a biphenylene group, and a divalent aromatic group having a structure represented by the following formula (3a).
- R 3 and R 4 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, and an alkyl group having 1 to 12 carbon atoms.
- X represents an alkylene group having 1 to 10 carbon atoms, —O—, —CO—, —COO—, —S—, —SO—, —SO 2 —, and —S—S—.
- R 2 in the formula (2) is any selected from the group consisting of a phenylene group, a naphthylene group, a biphenylene group, and a divalent aromatic group having a structure represented by the following formula (3b).
- R 3 and R 4 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, and an alkyl group having 1 to 12 carbon atoms.
- X represents an alkylene group having 1 to 10 carbon atoms, —O—, —CO—, —COO—, —S—, —SO—, —SO 2 —, and —S—S—.
- R 5 and R 6 each independently represent a hydrogen atom or a methyl group
- G 3 represents a hydrogen atom or a glycidyl group.
- M and n each independently represent 1 (It is an integer above and satisfies the relationship represented by 3 ⁇ (m + n) ⁇ 12.)
- R 7 and R 8 each independently represent a hydrogen atom or a methyl group
- G 4 represents a hydrogen atom or a glycidyl group.
- M, n, m ′, and n ′ represent And each independently an integer of 1 or more, and satisfies the relationship represented by 6 ⁇ (m + n + m ′ + n ′) ⁇ 20.
- m and n in the formula (1) are each independently an integer of 1 to 11, and 3 ⁇ (m + n) ⁇ 12 Satisfy the relationship represented,
- m and n are each independently an integer of 1 to 30, and R 1 and R 2 are each independently an aliphatic group having 1 to 12 carbon atoms or a divalent aromatic group.
- R 1 and R 2 represents a divalent aromatic group having 6 to 30 carbon atoms
- G 1 represents a glycidyl group
- G 2 represents a hydrogen atom or a glycidyl group.
- R 2 in the formula (1) is any selected from the group consisting of a phenylene group, a naphthylene group, a biphenylene group, and a divalent aromatic group having a structure represented by the following formula (3a). 7] or the epoxy resin according to [8].
- R 3 and R 4 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, and an alkyl group having 1 to 12 carbon atoms.
- X represents an alkylene group having 1 to 10 carbon atoms, —O—, —CO—, —COO—, —S—, —SO—, —SO 2 —, and —S—S—.
- the epoxy resin according to any one of [7] to [9], wherein the total chlorine content is 1000 ppm by mass or less.
- m and n are each independently an integer of 1 to 30, and R 1 and R 2 are each independently an aliphatic group having 1 to 12 carbon atoms or a divalent group.
- E ′ / (273 + T 1 /3) ⁇ 8.5 (a) (In Formula (a), T 1 is the temperature of the peak top of the obtained loss tangent, and E ′ (MPa) is the storage elastic modulus measured at 30 ° C.) E ′ (T 1 ⁇ 20)> 10 ⁇ E ′ (T 1 +20) (b) (In Formula (b), E ′ (T 1 ⁇ 20) is a storage elastic modulus measured at (T 1 ⁇ 20) ° C., and E ′ (T 1 +20) is measured at (T 1 +20) ° C.
- an epoxy resin and an epoxy resin composition capable of obtaining a cured product excellent in flexibility, adhesiveness, and low water absorption while having low viscosity.
- FIG. 2 is an NMR chart of the epoxy resin composition A produced in Example 1.
- FIG. 2 is a MALDI-MS chart of epoxy resin composition A produced in Example 1.
- FIG. It is a schematic sectional drawing of the semiconductor device with which the semiconductor chip produced in the present Example was mounted.
- the present embodiment a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
- This embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following contents.
- the present invention can be appropriately modified and implemented within the scope of the gist.
- the epoxy resin composition containing the epoxy resin represented by following formula (1) and the epoxy resin represented by following formula (2) is mentioned.
- m, n, m ′ and n ′ are each independently an integer of 1 to 30, and R 1 and R 2 are each independently a divalent fat having 1 to 12 carbon atoms. Or a divalent aromatic group having 6 to 40 carbon atoms, at least one of R 1 and R 2 represents a divalent aromatic group having 6 to 30 carbon atoms, and G 1 is glycidyl And G 2 represents a hydrogen atom or a glycidyl group.
- R 1 may be linear or branched. Furthermore, R 1 may contain an unsaturated bond group.
- the carbon number of R 1 is preferably 1 to 6 from the viewpoint of the balance between flexibility and heat resistance, and more preferably 1 to 3 from the viewpoint of ease of production.
- Specific examples of R 1 include, for example, n-butylene group, sec-butylene group, isobutylene group, tert-butylene group, n-pentylene group, 1-methylbutylene group, 2-methylbutylene group, 3-methylbutylene group. 1-ethylpropylene group, 1,1-dimethylpropylene group, 1,2-dimethylpropylene group, 2,2-dimethylpropylene group and the like.
- preferable specific examples include methylene group, ethylene group, n-propylene group, isopropylene group and the like.
- R 1 in formula (1) may be the same or different.
- R 2 is preferably an aromatic group, and when R 1 is an aromatic group, R 2 is an aliphatic group.
- R 2 is preferably a divalent aromatic group having 6 to 20 carbon atoms from the viewpoint of viscosity, and more preferably a divalent aromatic group having 6 to 15 carbon atoms from the viewpoint of ease of production. .
- R 2 in the formula (1) include, for example, phenylene group, naphthylene group, biphenylene group; phenylene group, naphthylene group, biphenylene group; bisphenol A, bisphenol F, bisphenol AD, tetrabromobisphenol A, biphenyl, tetra Selected from the group consisting of methyl biphenyl, tetrabromobiphenyl, diphenyl ether, benzophenone, phenyl benzoate, diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, diphenyl disulfide, naphthalene, anthracene, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, methyl resorcin, and catechol Any selected from the group consisting of divalent aromatics derived from any of the above.
- R 2 in the formula (1) is any one selected from the group consisting of a phenylene group, a naphthylene group, and a divalent aromatic group having a structure represented by the following formula (3a) from the viewpoint of heat resistance. It is preferable.
- R 3 and R 4 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, and an alkyl group having 1 to 12 carbon atoms.
- X represents an alkylene group having 1 to 10 carbon atoms, —O—, —CO—, —COO—, —S—, —SO—, —SO 2 —, and —S—S—. Represents any one selected from the group consisting of
- R 3 and R 4 are each independently preferably a hydrogen atom, a chlorine atom, a hydroxyl group, a methyl group, an ethyl group, or a tert-butyl group from the viewpoint of availability.
- divalent aromatic group having the structure represented by the formula (3a) include, for example, bisphenol A, bisphenol F, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, and bisphenol.
- G bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, oxybiphenyl, dihydroxybenzophenone, 4-hydroxybenzoic acid-4-hydroxybenzene ester, bis (4-hydroxyphenyl) sulfide, 4,4 And divalent aromatic groups derived from any one selected from the group consisting of '-sulfinylbisphenol and bis (4-hydroxyphenyl) disulfide.
- R ⁇ 1 > of Formula (2) As R ⁇ 1 > of Formula (2), what was mentioned above as a specific example of R ⁇ 1 > of Formula (1) is mentioned, for example.
- R 1 of formula (2) may be the same as R 1 of formula (1), it may be different.
- R 1 in the formula (2) include, for example, an ethylene group, an n-propylene group, and an isopropylene group.
- R 1 in the formula (2) may be the same or different.
- R ⁇ 2 > of Formula (2) As R ⁇ 2 > of Formula (2), what was mentioned above as a specific example of R ⁇ 2 > of Formula (1) is mentioned, for example.
- R 2 of formula (2) may be the same as R 2 of formula (1), it may be different.
- R 2 in the formula (2) may be the same or different.
- R 2 when R 1 is an aliphatic group, R 2 is preferably an aromatic group, and when R 1 is an aromatic group, R 2 may be an aliphatic group.
- R 2 in the formula (2) is preferably a divalent aromatic group having 6 to 20 carbon atoms from the viewpoint of viscosity, and is a divalent aromatic group having 6 to 15 carbon atoms from the viewpoint of ease of production. More preferably.
- At least one of R 2 in the formula (2) is a group consisting of a phenylene group, a naphthylene group, a biphenylene group, and a divalent aromatic group having a structure represented by the following formula (3b) from the viewpoint of heat resistance. It is preferable that any one is selected.
- R 3 and R 4 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, and an alkyl group having 1 to 12 carbon atoms.
- X represents an alkylene group having 1 to 10 carbon atoms, —O—, —CO—, —COO—, —S—, —SO—, —SO 2 —, and —S—S—. Represents any one selected from the group consisting of
- R 3 and R 4 are each independently preferably a hydrogen atom, a chlorine atom, a hydroxyl group, a methyl group, an ethyl group, or a tert-butyl group from the viewpoint of availability.
- Formula (1) is preferably the following formula (4) from the viewpoint of impact resistance.
- the formula (2) is preferably the following formula (5) from the viewpoint of impact resistance.
- R 5 and R 6 each independently represent a hydrogen atom or a methyl group
- G 3 represents a hydrogen atom or a glycidyl group.
- M and n each independently represent 1 (It is an integer above and satisfies the relationship represented by 3 ⁇ (m + n) ⁇ 12.)
- R 7 and R 8 each independently represent a hydrogen atom or a methyl group
- G 4 represents a hydrogen atom or a glycidyl group.
- M, n, m ′, and n ′ represent And each independently an integer of 1 or more, and satisfies the relationship represented by 6 ⁇ (m + n + m ′ + n ′) ⁇ 20.
- G 4 in formula (5) is more preferably a glycidyl group from the viewpoint of water absorption and reaction rate.
- the epoxy resin composition of the present embodiment preferably includes 100 parts by mass of the epoxy resin represented by the formula (1) and 0.1 to 10 parts by mass of the epoxy resin represented by the formula (2).
- the content of the epoxy resin represented by the formula (2) with respect to 100 parts by mass of the epoxy resin represented by the formula (1) is 0.1 parts by mass or more, the cured product of the epoxy resin composition has a long period of time. There is a tendency that sufficient adhesion reliability is obtained.
- the epoxy resin composition can have a low viscosity, While handling property etc. at the time of setting it as an adhesive agent etc.
- the content of the epoxy resin represented by the formula (2) with respect to 100 parts by mass of the epoxy resin represented by the formula (1) is preferably 0.1 to 10 parts by mass, and 0.5 to 9 parts by mass. More preferably.
- a second aspect of the present embodiment is an epoxy resin represented by the following formula (1), wherein m and n in the formula (1) are each independently an integer of 1 to 11, And the ratio of the component which satisfy
- the epoxy resin which is 70 mol% or less is mentioned.
- m and n are each independently an integer of 1 to 30, and R 1 and R 2 are each independently an aliphatic group having 1 to 12 carbon atoms or a divalent aromatic group. And at least one of R 1 and R 2 represents a divalent aromatic group having 6 to 30 carbon atoms, G 1 represents a glycidyl group, and G 2 represents a hydrogen atom or a glycidyl group. .
- M and n in the formula (1) are each independently an integer of 1 to 11, and preferably satisfy the relationship of 3 ⁇ (m + n) ⁇ 12.
- (m + n) is 3 or more, the flexibility is further improved.
- (m + n) is 12 or less, the viscosity can be further lowered, so that the handling property is further improved.
- the proportion of the component satisfying the relationship of m and n in the formula (1) 6 ⁇ (m + n) ⁇ 12 (hereinafter sometimes referred to as “a component”) is 30 mol%. More than 70 mol%.
- a component the proportion of the component satisfying the relationship of m and n in the formula (1) 6 ⁇ (m + n) ⁇ 12
- the proportion of component a in the epoxy resin of this embodiment is 30 mol% or more, sufficient flexibility is obtained and the water absorption is low. Further, when the proportion of the component a is 70 mol% or less, the water absorption and the viscosity become low, and the handling property is excellent.
- the proportion of component a is preferably 40 mol% or more and 60 mol% or less from the viewpoint of the balance between flexibility and viscosity.
- M, n, (m + n), and the like described here can be obtained by the method described in Examples described later.
- the proportion of the component (hereinafter sometimes referred to as “b component”) in which G 2 in the formula (1) is a glycidyl group is 10 mol% or more and 100 mol% or less. preferable.
- the ratio of component b is 10 mol% or more, curability is further improved.
- R 1 in the formula (1) may be linear or branched. Furthermore, R 1 may contain an unsaturated bond.
- the carbon number of R 1 is preferably 1 to 6 from the viewpoint of the balance between flexibility and heat resistance, and more preferably 1 to 4 from the viewpoint of ease of production.
- Preferable specific examples of R 1 include, for example, ethylene group, n-propylene group, isopropylene group and the like.
- R 1 in formula (1) may be the same or different.
- R 2 is preferably an aromatic group, and when R 1 is an aromatic group, R 2 is an aliphatic group.
- R 2 is preferably a divalent aromatic group having 6 to 20 carbon atoms from the viewpoint of viscosity, and more preferably a divalent aromatic group having 6 to 15 carbon atoms from the viewpoint of ease of production. .
- R 2 in the formula (1) include, for example, phenylene group, naphthylene group, biphenylene group; bisphenol A, bisphenol F, bisphenol AD, tetrabromobisphenol A, biphenyl, tetramethylbiphenyl, tetrabromobiphenyl, diphenyl ether, Divalent derived from any one selected from the group consisting of benzophenone, phenylbenzoate, diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, diphenyl disulfide, naphthalene, anthracene, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, methylresorcin, and catechol An aromatic group etc. are mentioned.
- R 2 in the formula (1) is selected from the group consisting of a phenylene group, a naphthylene group, a biphenylene group, and a divalent aromatic group having a structure represented by the following formula (3a) from the viewpoint of heat resistance.
- R 3 and R 4 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, or an alkyl group having 1 to 12 carbon atoms; It represents any one selected from the group consisting of an alkylene group of the formula 1 to 10, —O—, —CO—, —COO—, —S—, —SO—, —SO 2 —, and —S—S—. )
- R 3 and R 4 are each independently selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom, a hydroxyl group, a methyl group, an ethyl group, and a tert-butyl group from the viewpoint of availability. It is preferable that R 3 and R 4 may be the same or different. Both R 3 and R 4 are preferably any of a hydrogen atom, a chlorine atom, a bromine atom, a hydroxyl group, a methyl group, an ethyl group, and a tert-butyl group.
- divalent aromatic group having the structure represented by the formula (3a) include, for example, bisphenol A, bisphenol F, bisphenol AD, tetrabromobisphenol A, diphenyl ether, benzophenone, phenylbenzoate, diphenyl sulfide, and diphenyl.
- R 2 in the formula (2) include, for example, phenylene group, naphthylene group, biphenylene group; bisphenol A, bisphenol F, bisphenol AD, tetrabromobisphenol A, biphenyl, tetramethylbiphenyl, tetrabromobiphenyl, diphenyl ether, Divalent derived from any one selected from the group consisting of benzophenone, phenylbenzoate, diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, diphenyl disulfide, naphthalene, anthracene, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, methylresorcin, and catechol An aromatic group etc. are mentioned.
- the total chlorine amount of the epoxy resin of the present embodiment is not particularly limited, but the smaller the total chlorine amount, the better the reactivity, adhesiveness, mechanical strength, corrosion resistance, electrical reliability, and the like. From such a viewpoint, the total chlorine content of the epoxy resin of the present embodiment is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and further preferably 250 mass ppm or less. In the present embodiment, the lower limit value of the total chlorine amount is not particularly limited, but may be 1 ppm by mass or more from the balance of the obtained effect and economy. The total chlorine amount can be determined by the method described in the examples described later.
- the epoxy resin of the present embodiment can also be an epoxy resin composition further containing an epoxy resin represented by the following formula (2).
- m, n, m ′ and n ′ are each independently an integer of 1 to 30, and R 1 and R 2 are each independently a divalent group having 1 to 12 carbon atoms. Represents an aliphatic group or a divalent aromatic group, at least one of R 1 and R 2 represents a divalent aromatic group having 6 to 30 carbon atoms, G 1 represents a glycidyl group, and 2 represents a hydrogen atom or a glycidyl group.)
- epoxy resin represented by the formula (2) the same epoxy resin as described in the first embodiment can be used.
- the compounding ratio of the epoxy resin of this embodiment and the epoxy resin represented by the formula (2) is not particularly limited, 100 parts by mass of the epoxy resin of the present embodiment and the epoxy resin 0 represented by the formula (2) 1 to 10 parts by mass.
- the content of the epoxy resin represented by the formula (2) with respect to 100 parts by mass of the epoxy resin of the present embodiment is 0.1 parts by mass or more, the cured product of the epoxy resin composition has a long-term adhesion reliability. Tends to be sufficiently obtained.
- the content of the epoxy resin represented by the formula (2) with respect to 100 parts by mass of the epoxy resin of this embodiment is 10 parts by mass or less, the epoxy resin composition can have a low viscosity, and an adhesive or the like is obtained.
- the content of the epoxy resin represented by the formula (2) with respect to 100 parts by mass of the epoxy resin represented by the formula (1) is preferably 0.1 to 10 parts by mass, and 0.3 to 9 parts by mass. More preferably.
- the epoxy resin composition used in the epoxy resin composition of the first embodiment described above and the epoxy resin of the second embodiment are epoxy resins having at least a structure represented by the formula (1).
- an example of the manufacturing method of the epoxy resin which has a structure represented by Formula (1) is demonstrated.
- This epoxy resin can be obtained by a reaction to obtain an epoxy resin represented by the formula (1).
- an epoxy resin represented by the formula (1) for example, a compound in which an alkylene oxide is added to an aromatic compound having two phenolic hydroxyl groups at a ratio of 3 to 12 times moles with respect to 2 moles of the phenolic hydroxyl groups (hereinafter simply referred to as “a compound”). And an “oxyalkylene adduct”) and epihalohydrin in the presence of an alkaline compound.
- epihalohydrin examples include epichlorohydrin and epibromohydrin.
- the amount of epihalohydrin added is usually 1 to 10 equivalents, preferably 2 to 8 equivalents, per 1 equivalent of the alcoholic hydroxyl group of the oxyalkylene adduct.
- alkaline compound examples include sodium hydroxide, potassium hydroxide, barium hydroxide, potassium carbonate and the like. These may be used individually by 1 type and may use 2 or more types together.
- the state of the alkaline compound is not particularly limited, and may be, for example, a solid, liquid, or aqueous solution.
- the addition amount of the alkaline compound is usually 1 to 10 equivalents, preferably 1.5 to 7.5 equivalents, more preferably 2 to 5 equivalents per equivalent of phenolic hydroxyl group or alcoholic hydroxyl group. .
- phase transfer catalyst from the viewpoint of promoting the reaction.
- alkaline compound and the phase transfer catalyst in combination.
- phase transfer catalyst examples include tetramethylammonium chloride, tetramethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyl Quaternary ammonium salts such as trimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, phenyltrimethylammonium chloride; quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide and benzyltrimethylammonium hydroxide 15-crown-5 Crown ethers such as 18-crown-6, dibenzo-18-crow
- phase transfer catalyst examples include cryptands such as 1] -cryptand, [2.2.2] cryptand, [2.2.2] -decyl cryptand, [2.2.2] -benzocryptand. These may be used individually by 1 type and may use 2 or more types together.
- the state of the phase transfer catalyst is not particularly limited, and may be, for example, solid, liquid, aqueous solution, alcohol solution or the like.
- the amount of the phase transfer catalyst added is usually 0.25 to 10 moles, preferably 0.5 to 5 moles per mole of phenolic hydroxyl group or alcoholic hydroxyl group.
- the reaction temperature is usually 20 to 100 ° C., preferably 30 to 80 ° C.
- the reaction temperature is 20 ° C. or higher, the progress of the reaction is accelerated, so that the glycidyl group of epihalohydrin tends to be efficiently introduced into the oxyalkylene adduct.
- the reaction temperature is set to 100 ° C. or lower, the polymerization reaction between epihalohydrins can be efficiently suppressed, so that the glycidyl group of epihalohydrin tends to be efficiently introduced.
- the reaction time is usually 1 to 12 hours, preferably 1.5 to 8 hours, and more preferably 2 to 6 hours.
- the produced salt, the remaining alkaline compound, the phase transfer catalyst, etc. are removed from the reaction solution by washing with water or the like. Subsequently, the remaining epihalohydrin is removed by heating under normal pressure or reduced pressure, and the epoxy resin is recovered.
- the epoxy resin recovered above is dissolved in a solvent such as toluene or methyl isobutyl ketone, and then an alkaline compound (solid or liquid, solution, etc. You can add it).
- an alkaline compound solid or liquid, solution, etc. You can add it.
- the ring closure reaction of epihalohydrin proceeds, and the amount of hydrolyzable chlorine can be further reduced.
- the addition amount of the alkaline compound is usually 0.5 to 5 equivalents, preferably 1 to 3 equivalents, per 1 equivalent of hydrolyzable chlorine.
- the reaction temperature of the ring closure reaction is preferably 60 to 120 ° C., and the reaction time is preferably 0.5 to 3 hours.
- the epoxy resin is excellent in compatibility, it can be suitably used as an epoxy resin composition to which other components are added.
- the epoxy resin having the structure represented by the formula (2) can be obtained, for example, by appropriately controlling the production conditions in the method exemplified as the production method of the formula (1). Furthermore, the yield of the epoxy resin which is a structure represented by Formula (2) can also be improved by increasing the quantity of epihalohydrin with respect to alcoholic hydroxyl group in the case of manufacture. In particular, the yield of the epoxy resin represented by the formula (2) tends to be further improved by further adding epihalohydrin during the reaction.
- An epoxy resin composition containing the epoxy resin composition of the first embodiment and / or the epoxy resin of the second embodiment; and a curing agent can be realized.
- This epoxy resin composition may further contain other epoxy resins, curing accelerators and the like as necessary.
- the curing agent examples include an amine curing agent, an amide curing agent, an acid anhydride curing agent, a phenol curing agent, a latent curing agent, and a catalytic curing agent, but are not limited thereto. is not.
- Examples of amine-based curing agents include aliphatic amines and aromatic amines.
- Examples of aliphatic amines include diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane. Bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane and the like.
- aromatic amine examples include diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis (4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate, and the like.
- amide-based curing agent examples include dicyandiamide and a guanidine compound that is a derivative thereof, or an amine-based curing agent added with an acid anhydride.
- Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, And methyl hexahydrophthalic anhydride.
- phenolic curing agent examples include phenol novolak resin, cresol novolak resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl modified phenol resin, biphenyl modified phenol aralkyl resin, dicyclopentadiene modified phenol resin, aminotriazine modified
- phenol resin naphthol novolak resin, naphthol-phenol co-condensation novolak resin, naphthol-cresol co-condensation novolak resin, and allyl acrylic phenol resin.
- latent curing agents examples include imidazoles, dicyandiamide and its derivatives, imidazole-based latent curing agents and those encapsulating amine adducts.
- Commercially available products such as “PN23”, “PN40”, “PN-H” such as Amicure series (manufactured by Ajinomoto Fine Techno Co.), “HX-3088”, “HX-3941”, “ Novacure series (manufactured by Asahi Kasei E-Materials Co., Ltd.) such as “HX-3742”.
- catalyst type curing agent examples include a cationic thermosetting catalyst and a BF 3 -amine complex. These curing agents may be used alone or in combination of two or more.
- amine-based curing agents are preferred when importance is attached to flexibility and adhesiveness. Moreover, when importance is attached to heat resistance and low water absorption, a phenolic curing agent is preferable.
- the content of the curing agent in the epoxy resin composition is preferably 1 to 100 parts by mass and more preferably 2 to 90 parts by mass with respect to 100 parts by mass of the total amount of epoxy resin.
- the content of the curing agent in the epoxy resin composition is 0 with respect to 1 equivalent of the glycidyl group of the epoxy resin for the amine curing agent, the amide curing agent, the acid anhydride curing agent, and the phenol curing agent. It is preferably 7 to 1.5 equivalents.
- the amount is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin.
- the amount is preferably 0.5 to 6.0 parts by mass with respect to 100 parts by mass of the epoxy resin. Within this range, the curing reaction proceeds efficiently, and better cured properties tend to be expressed.
- epoxy resins other than the above-described epoxy resins may be used in combination.
- resin structures that can be used in combination with other resins include, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, tetrabromobisphenol A type epoxy resins, biphenyl type epoxy resins, and tetramethyl.
- Biphenyl type epoxy resin tetrabromobiphenyl type epoxy resin, diphenyl ether type epoxy resin, benzophenone type epoxy resin, phenyl benzoate type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl sulfoxide type epoxy resin, diphenyl sulfone type epoxy resin, diphenyl disulfide type epoxy resin Resin, naphthalene type epoxy resin, anthracene type epoxy resin, hydroquinone type epoxy resin, methylhydroquinone type epoxy resin, Bifunctional epoxy resins such as butyl hydroquinone type epoxy resin, resorcin type epoxy resin, methyl resorcin type epoxy resin, catechol type epoxy resin, N, N-diglycidyl aniline type epoxy resin; N, N-diglycidyl aminobenzene type Trifunctional epoxy resins such as epoxy resin, o- (N, N-diglycidylamino) toluene type epoxy resin, triazin
- the content of the other epoxy resin is preferably 95% by mass or less, more preferably 80% by mass or less, based on all epoxy resin components in the epoxy resin composition of the present embodiment.
- the epoxy resin composition of the present embodiment may further contain a curing accelerator.
- the curing accelerator include imidazole-based curing accelerators such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,5 -Tertiary amine curing accelerators such as diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] undec-7-ene, and phosphorus curing such as triphenylphosphine Accelerators, organic acid metal salts, Lewis acids, amine complex salts and the like. These can further accelerate the curing reaction when used in combination with the above-described curing agent.
- An appropriate type of curing accelerator can be selected according to the type of curing agent described above.
- the content of the curing accelerator in the epoxy resin composition of the present embodiment is not particularly limited as long as the effect of the present embodiment is obtained. Usually, it is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the total amount of epoxy resin. By setting the content of the curing accelerator in the above range, the curing reaction is sufficiently promoted and more excellent cured properties tend to be obtained.
- the epoxy resin composition of the present embodiment may further contain an inorganic filler as necessary.
- an inorganic filler include, for example, fused silica, crystalline silica, alumina, talc, silicon nitride, aluminum nitride and the like.
- the content of the inorganic filler in the epoxy resin composition of the present embodiment is not particularly limited as long as the effect of the present embodiment is obtained. Usually, it is preferable that it is 90 mass% or less of the epoxy resin composition of this embodiment. By making content of an inorganic filler into the said range, it exists in the tendency for the viscosity of an epoxy resin composition to be low enough, and to be excellent in handleability.
- the epoxy resin composition of the present embodiment may further contain other compounding agents such as a flame retardant, a liquid stress agent, a silane coupling agent, a diluent, a leveling agent, a release agent, and a pigment as necessary. Good. Any suitable one can be selected as long as the effects of the present embodiment can be obtained.
- Examples of flame retardants include brominated flame retardants, phosphorus flame retardants, nitrogen flame retardants, and inorganic flame retardants.
- Examples of brominated flame retardants include tetrabromophenol.
- Phosphorus flame retardants include 9,10-dihydro-9-oxa-10-phosphananthrene-10-oxide and its epoxy derivatives, triphenylphosphine and its derivatives, phosphate esters, condensed phosphate esters, phosphazene compounds, etc. Is mentioned.
- Examples of the nitrogen-based flame retardant include guanidine-based flame retardant, triazine structure-containing phenol, melamine polyphosphate, isocyanuric acid and the like.
- Examples of the inorganic flame retardant include magnesium hydroxide and aluminum hydroxide, and magnesium hydroxide is preferable from the viewpoint of heat resistance.
- the content of the flame retardant is not particularly limited, but is preferably 5 to 200% by mass, and more preferably 10 to 100% by mass with respect to the total amount of the epoxy resin.
- liquid low stress agent examples include polyalkylene glycols and amine modified products thereof, organic rubbers such as polybutadiene and acrylonitrile, silicone rubbers such as dimethylsiloxane, and silicone oils. These may be used individually by 1 type and may use 2 or more types together.
- the content of the liquid low stress agent is not particularly limited, but is preferably 5 to 40% by mass and more preferably 10 to 20% by mass with respect to the epoxy resin.
- silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl- ⁇ -aminopropyl Trimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltri Methoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane
- the diluent examples include a polyfunctional acrylate compound containing an acrylic group and a glycidyl type reactive diluent containing a monofunctional glycidyl group. These may be used individually by 1 type and may use 2 or more types together.
- the content of the diluent is not particularly limited, but is preferably 1 to 40% by mass and more preferably 5 to 30% by mass with respect to the epoxy resin.
- leveling agent examples include a silicon leveling agent and an acrylic leveling agent.
- the cured product of this embodiment can be obtained by thermally curing the above epoxy resin composition by a conventionally known method or the like. That is, examples of the cured product of this embodiment include a cured product obtained by curing the above-described epoxy resin composition.
- a curing agent, and further a curing accelerator, an inorganic filler, a compounding agent, and the like, as necessary are made uniform using an extruder, a kneader, a roll, and the like. It is also possible to make an epoxy resin composition by thoroughly mixing. Thereafter, the epoxy resin composition is molded by casting or using a transfer molding machine, an injection molding machine or the like, and further heated at about 80 to 200 ° C. for about 2 to 10 hours to obtain a cured product. it can.
- the epoxy resin composition of the present embodiment is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, and a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. And impregnated with heat to obtain a prepreg.
- a cured product can also be obtained by subjecting the obtained prepreg to hot press molding or the like.
- a cured product obtained from an epoxy resin represented by the following formula (1) (In the formula (1), m and n are each independently an integer of 1 to 30, and R 1 and R 2 are each independently an aliphatic group having 1 to 12 carbon atoms or a divalent group. Represents an aromatic group, at least one of R 1 and R 2 represents a divalent aromatic group having 6 to 30 carbon atoms, G 1 represents a glycidyl group, and G 2 represents a hydrogen atom or a glycidyl group.
- E ′ / (273 + T 1 /3) ⁇ 8.5 (a) (In Formula (a), T 1 is the temperature of the peak top of the obtained loss tangent, and E ′ (MPa) is the storage elastic modulus measured at 30 ° C.) E ′ (T 1 ⁇ 20)> 10 ⁇ E ′ (T 1 +20) (b) (In Formula (b), E ′ (T 1 ⁇ 20) is a storage elastic modulus measured at (T 1 ⁇ 20) ° C., and E ′ (T 1 +20) is measured at (T 1 +20) ° C.
- Such a cured product not only has excellent physical properties such as a drop impact, but also has a small decrease in adhesive strength due to temperature change, and greatly contributes to reliability after mounting.
- Such a cured product can also be obtained, for example, by using the epoxy resin composition of the first embodiment described above or the epoxy resin of the second embodiment.
- the cured product further satisfies the relationship represented by the mathematical formula (c) or the relationship represented by the mathematical formula (d). Furthermore, it is more preferable that the cured product further satisfies both the relationship represented by the mathematical formula (c) and the relationship represented by the mathematical formula (d). A cured product that satisfies these conditions can further suppress a decrease in adhesive strength due to a temperature change.
- the epoxy resin composition, the epoxy resin, and the cured product obtained from the epoxy resin composition of the present embodiment can be used for various applications in which an epoxy resin is conventionally used as a material.
- an epoxy resin is conventionally used as a material.
- electronic members for example, sealing materials, adhesives, printed circuit board materials, paints, composite materials, etc.
- conductive materials such as semiconductor sealing materials such as underfill and molding, adhesives, bonding paste, bonding films (for example, interlayer insulating materials), conductive materials, anisotropic conductive films (ACF), etc.
- adhesives, insulating materials, photosensitive materials such as solder resists and coverlay films, printed wiring boards, and the like is also suitably used as a coating material, prepreg, heat conductive material, fuel cell sealing material and the like.
- the adhesive, bonding paste, and bonding film obtained from the epoxy resin composition, epoxy resin, and the like of this embodiment are useful for liquid adhesives, film adhesives, die bonding materials, and the like.
- Examples of the method for producing the film adhesive include methods described in JP-A-62-141083, JP-A-05-295329, and the like.
- a solution in which a solid epoxy resin or a liquid epoxy resin is dissolved in a solvent such as toluene is prepared.
- content of a solid epoxy resin or a liquid epoxy resin may be about 50 mass%.
- a curing agent for epoxy resin is further added to this solution to obtain a varnish.
- the epoxy resin curing agent may be used alone or in combination of two or more.
- the total content of the epoxy resin curing agent in the varnish is preferably about 30% by mass.
- the varnish is applied to, for example, a peeling polyethylene terephthalate substrate having a thickness of 50 ⁇ m, and a solvent (toluene or the like) is dried to form a coating film. In this case, it is preferable to control so that the thickness of the coating film is about 30 ⁇ m. By drying the solvent (toluene or the like) in the varnish, it is possible to obtain a bonding film that is inactive at room temperature and exhibits adhesiveness when heated.
- Examples of the conductive material include a conductive film and a conductive paste.
- Examples of the anisotropic conductive material include an anisotropic conductive film and an anisotropic conductive paste.
- the method described in JP-A-01-113480 can be employed.
- a conductive material or an anisotropic conductive material is also blended to form a coating solution.
- a conductive film or an anisotropic conductive film can be produced by applying this coating solution to a substrate and then drying it.
- the conductive particles include solder particles; nickel particles; nano-sized metal crystals; composite particles in which a metal surface is coated with another metal; copper and silver inclined particles; resin particles (for example, styrene resin, urethane resin, Examples include particles in which the surface of melamine resin, epoxy resin, acrylic resin, phenol resin, styrene-butadiene resin, etc.) is coated with a conductive thin film (eg, gold, nickel, silver, copper, solder, etc.) It is done. Normally, the conductive particles are substantially spherical fine particles having an average particle diameter of about 1 to 20 ⁇ m.
- the base material that can be used for forming a film include base materials such as polyester, polyethylene, polyimide, and polytetrafluoroethylene.
- Insulating material includes an insulating adhesive film and an insulating adhesive paste.
- an insulating adhesive film that is an insulating material can be obtained.
- an insulating adhesive paste can be obtained by blending an insulating filler in the one-pack epoxy resin composition among the aforementioned fillers.
- the sealing material examples include a solid sealing material, a liquid sealing material, and a film-shaped sealing material.
- the liquid sealing material is useful as an underfill material, a potting material, a dam material, or the like.
- a manufacturing method of the sealing material for example, methods described in JP-A Nos. 05-043661 and 2002-226675 can be employed. More specifically, a sealing material can be obtained by adding a curing agent such as methylhexahydrophthalic anhydride to the epoxy resin composition or epoxy resin of the present embodiment and mixing them uniformly. Furthermore, not only a hardening
- the epoxy resin composition or epoxy resin of the present embodiment is mixed with an alkali-soluble polymer containing a carboxyl group, an ethylenically unsaturated addition polymerizable monomer, a photopolymerization initiator, etc. Can be obtained.
- the coating material examples include a coating material for an electronic material, an overcoat material for covering a printed wiring board, and a resin composition for interlayer insulation of a printed board.
- a manufacturing method of the coating material for example, methods described in Japanese Patent Publication No. 04-006116, Japanese Patent Application Laid-Open No. 07-304931, Japanese Patent Application Laid-Open No. 08-064960, Japanese Patent Application Laid-Open No. 2003-246838, and the like are employed. You can also.
- the epoxy resin composition or epoxy resin of the present embodiment, a filler such as silica, and a curing agent for epoxy resin are dissolved in a solvent (such as methyl ethyl ketone (MEK)), and the resin and filler are dissolved.
- MEK methyl ethyl ketone
- a solution having a solid content concentration of 50% is prepared.
- Other than the above-mentioned epoxy resin for example, other epoxy resins, phenoxy resins, rubber-modified epoxy resins, etc.
- This solution is applied to a polyimide film with a thickness of 50 ⁇ m, and a copper foil is further laminated thereon and laminated at 60 to 150 ° C. By heating and curing the laminated material at 180 to 200 ° C., a laminated plate having an interlayer coated with an epoxy resin composition can be obtained.
- MIBK methyl isobutyl ketone
- xylene 1/1, volume ratio
- a method for producing a prepreg for example, methods described in JP 09-071633 A, WO 98/44017 pamphlet and the like can be employed.
- a method of impregnating a reinforcing base material with an epoxy resin composition and heating it may be mentioned.
- the varnish solvent to be impregnated include methyl ethyl ketone, acetone, ethyl cellosolve, methanol, ethanol, isopropyl alcohol and the like. It is preferable that these solvents do not remain in the prepreg.
- the type of the reinforcing substrate is not particularly limited, and examples thereof include paper, glass cloth, glass nonwoven fabric, aramid cloth, and liquid crystal polymer.
- the ratio of the resin composition to the reinforcing substrate is not particularly limited, but usually the resin content in the prepreg is preferably 20 to 80% by mass.
- a composite material can be obtained by stacking several prepregs obtained and thermoforming them.
- a method for producing a heat conductive material for example, methods described in JP-A-06-136244, JP-A-10-237410, JP-A-2000-003987 and the like can be employed. More specifically, by uniformly kneading the epoxy resin composition or epoxy resin of the present embodiment, a curing agent (for example, a phenol novolac curing agent), and a heat conductive filler (for example, graphite powder), A heat conductive resin paste can be obtained.
- a curing agent for example, a phenol novolac curing agent
- a heat conductive filler for example, graphite powder
- a method for producing a fuel cell sealing material methods described in JP-A Nos. 2002-332328 and 2004-075954 can be employed. More specifically, the epoxy resin composition or epoxy resin of this embodiment and a conductive material (for example, artificial graphite material) are mixed with a mixer or the like to obtain a mixture. A composition is obtained by uniformly mixing a curing agent for epoxy resin with the obtained mixture. A fuel cell sealing material can be obtained by compression molding this composition under conditions of a mold temperature of 170 to 190 ° C. and a molding pressure of 150 to 300 kg / cm 2 . This fuel cell sealing material has practically sufficient conductivity and is excellent in bus barrier properties and molding processability.
- a conductive material for example, artificial graphite material
- an overcoat material for a flexible wiring board methods described in International Publication No. 00/64960 pamphlet, Japanese Patent Application Laid-Open No. 2006-137838, and the like can be employed. More specifically, first, the epoxy resin composition or epoxy resin of the present embodiment, the carboxyl-modified polybutadiene that reacts with these, the rubber particles, the epoxy resin curing agent, and the curing accelerator are uniformly formed. Disperse to obtain a composition. This composition is dissolved in methyl ethyl ketone (MEK) to prepare a solution of an overcoat material for a flexible wiring board.
- MEK methyl ethyl ketone
- an aqueous solution of a dicarboxylic acid for example, succinic acid
- An overcoat material for a flexible wiring board can be obtained by applying a solution of an overcoat material to a polyimide film and drying it. At this time, it is preferable to control the film thickness to be about 25 ⁇ m after drying.
- the measurement method of each physical property was as follows.
- Total chlorine content The total chlorine content was measured according to JIS K7243-3.
- Hydrolyzable chlorine content The amount of hydrolyzable chlorine was measured according to JIS K7243-2.
- viscosity The viscosity was measured according to JIS K7117-2 (E type viscometer).
- the measurement conditions for MS were as follows.
- Epoxy resin “AER4152” (produced by Asahi Kasei Epoxy Co., Ltd., isocyanate-modified epoxy resin having an oxazolidone ring; epoxy equivalent of 340 g / eq.) And a synthetic resin described later were mixed at a mass ratio of 50/50 and heated at 140 ° C. . And the compatibility at the time of cooling to room temperature was evaluated. The compatibility was evaluated based on the following criteria. ⁇ : The whole was transparent and had a uniform phase. ⁇ : Some were marbled, but transparent as a whole, and at a level with no practical problems. X: The whole became cloudy and was a heterogeneous phase.
- the copper plate shear bond strength (a) before the heat cycle test was measured using a tensile tester AGS-H 5 kN in a constant temperature and humidity chamber at 23 ° C. and 50% RH.
- the obtained sample was subjected to 1000 cycles of a heat cycle test of ⁇ 40 ° C. (held for 15 minutes) to + 125 ° C. (held for 15 minutes).
- the copper plate shear bond strength (b) after a heat cycle test was measured.
- the bond strength retention rate (b / a) was calculated by determining the ratio of the copper plate shear bond strength (b) after the heat cycle test to the copper plate shear bond strength (a) before the heat cycle test.
- the gel time was measured according to JACT test method RS-5 and JIS K-6910-1995. Specifically, the epoxy resin composition prepared according to Table 3 was used as a sample, and the gel time was measured using a gelation tester. The sample was heated on a hot plate at 170 ° C. with stirring, and the time until no yarn was pulled between the sample and the stirring bar was defined as gel time.
- Adhesiveness to silver plating Ten samples were produced in the same manner as in the section of “Copper plate shear adhesive strength” using a silver-plated standard test piece C1100P (manufactured by Nippon Test Panel Co., Ltd.) (conforming to JIS K6850). About five of the samples, “adhesive strength a to silver plating before moisture absorption test” was measured. The adhesive strength a was the arithmetic average of the measured values of five samples. The other five samples were allowed to stand for 300 hours in a constant temperature and humidity chamber at 85 ° C. and 85 RH% to absorb moisture.
- the “adhesion strength b to the silver plating after the moisture absorption test” was measured for the sample after moisture absorption in the same manner as the measurement method of “adhesion strength a to the silver plating before the moisture absorption test”.
- the adhesive strength b was the arithmetic average of the measured values of the five samples after moisture absorption.
- the ratio of the adhesive strength b to the adhesive strength a was defined as the adhesive strength retention rate (b / a).
- a semiconductor device manufactured by a method described later is subjected to a JEDEC moisture resistance level 3 moisture absorption treatment (treatment at 30 ° C. and 60% relative humidity for 168 hours), followed by IR reflow treatment (peak temperature 260 ° C., treatment time: 60 seconds). ) Three times. And the presence or absence of peeling of the epoxy resin composition inside the semiconductor device was confirmed. The presence or absence of peeling was confirmed using an ultrasonic flaw detector (Hitachi Construction Machinery Co., Ltd., model mi-scope hyper). The reflow resistance was evaluated according to the following criteria. ⁇ : No peeling was observed. X: Peeling was observed.
- Example 1 (Glycidylation reaction) 270 g of dialcohol (1 equivalent of hydroxyl group) obtained by adding 5 mol of propylene oxide to 1 mol of bisphenol A in a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, epichlorohydride Phosphorus (463 g, 5.00 mol) and 50 mass% tetramethylammonium chloride aqueous solution (10 g) were mixed, heated under reduced pressure, and refluxed at 60 to 65 ° C. And 400 g of 50 mass% sodium hydroxide aqueous solution was dripped over 2 hours.
- FIG. 1 shows an NMR chart of the epoxy resin composition A obtained in Example 1
- FIG. 2 shows a MALDI-MS chart of the epoxy resin composition A obtained in Example 1.
- 100 parts by mass of the epoxy resin a1 having the structure represented by the formula (1) was 1.3 parts by weight. Part by mass was included.
- R 1 is an isopropylene group
- R 2 is a divalent group derived from bisphenol A
- G 1 is a glycidyl group
- 74 mol% of G 2 is a glycidyl group
- 26 mole% of G 2 is hydrogen.
- the range of m and n in the formula (1) was 6 ⁇ (m + n) ⁇ 12.
- the epoxy resin a1 the ratio of m and n is 6 ⁇ of formula (1) (m + n) component (a component) satisfying the relationship of ⁇ 12, for epoxy resin a2 was 48 mole percent, R 1 Is an isopropylene group, R 2 is a divalent group derived from bisphenol A, G 1 is a glycidyl group, and G 2 is a glycidyl group.
- R 1 Is an isopropylene group
- R 2 is a divalent group derived from bisphenol A
- G 1 is a glycidyl group
- G 2 is a glycidyl group.
- the epoxy equivalent of epoxy resin A is 371 g / eq.
- the viscosity at 25 ° C. was 952 mPa ⁇ s
- the total chlorine content was 512 ppm
- the hydrolyzable chlorine content was 56
- Example 2 For the dialcohol used in Production Example 1, "2 mol of epoxypentane is added to 1 mol of biphenol” from “dialcohol obtained by addition reaction of 5 mol of propylene oxide to 1 mol of bisphenol A”. It was changed to “dialcohol obtained by reaction”. Other conditions were the same as in Example 1, and an epoxy resin composition B was obtained. When the obtained epoxy resin composition B was analyzed, the epoxy resin b1 represented by the formula (2) was 2.5 parts per 100 parts by mass of the epoxy resin b1 having the structure represented by the formula (1). Part by mass was included.
- R 1 is a pentyl group (—CHCH (C 3 H 7 ) —)
- R 2 is a biphenyl group
- G 1 is a glycidyl group
- 0.5 mole% of G 2 is hydrogen.
- the range of m and n in the formula (1) of the epoxy resin b1 was 1 ⁇ (m + n) ⁇ 9.
- R 1 is a pentyl group
- R 2 is a biphenyl group
- G 1 is a glycidyl group
- G 2 is a glycidyl group.
- m, n, m ′ and n ′ in the formula (2) it was confirmed that 2 ⁇ (m + n + m ′ + n ′) ⁇ 13.
- the epoxy equivalent of the epoxy resin composition B is 262 g / eq.
- the viscosity at 25 ° C. was 1782 mPa ⁇ s
- the total chlorine content was 423 ppm
- the hydrolyzable chlorine content was 50 ppm.
- Example 3 270 g of the epoxy resin composition A produced in Example 1 was charged, and 1.8 g of boron trifluoride diethyl ether complex was charged as a catalyst, and then heated to 60 ° C. to obtain phenyl glycidyl ether (manufactured by Nagase ChemteX Corporation, “ EX141 ", epoxy equivalent 150 g / eq.) 36 g was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was reacted at 60 ° C.
- Example 1 except that 270 g of the obtained crude resin composition was used in place of “dialcohol obtained by addition reaction of 5 mol of propylene oxide to 1 mol of bisphenol A” in Example 1. In the same manner as in Example 1, an epoxy resin composition C was obtained.
- the epoxy resin c1 which is a structure represented by Formula (1) is 100 mass parts
- the epoxy resin c2 which is a structure represented by Formula (2) is 1.2 parts by mass were included.
- R 1 is an isopropylene group or a phenoxy isopropylene group (—CH 2 CH (CH 2 OC 6 H 6 ) —)
- R 2 is a divalent group derived from bisphenol A, wherein G 1 is a glycidyl group, 71.8 mole% of G 2 is a glycidyl group, it was confirmed 28.2% of G 2 is a hydrogen atom.
- the range of m and n in the formula (1) of the epoxy resin c1 was 3 ⁇ (m + n) ⁇ 12. And the ratio of the component (a component) in which m and n of Formula (1) satisfy
- Epoxy resin composition C has an epoxy equivalent of 385 g / eq.
- the viscosity at 25 ° C. was 1245 mPa ⁇ s, the total chlorine content was 621 ppm, and the hydrolyzable chlorine content was 57 ppm.
- Example 4 A flask equipped with a thermometer and a stirrer was charged with 120 g of resorcinol and 172 g of triethylene glycol divinyl ether and heated to 120 ° C. over 1 hour. Then, it was made to react at 120 degreeC for 6 hours, and 290g of transparent semi-solid modified polyhydric phenols were obtained. 290 g of the obtained modified polyphenols, 735 g of epichlorohydrin, and 185 g of n-butanol were charged and dissolved. Then, the mixture was heated under reduced pressure and refluxed at 60 to 65 ° C. 130.3 g of 50 mass% sodium hydroxide aqueous solution was dripped over 2 hours.
- Epoxy resin D has an epoxy equivalent of 286 g / eq.
- the viscosity at 25 ° C. was 12000 mPa ⁇ s
- the total chlorine content was 877 ppm
- the hydrolyzed chlorine content was 72 ppm.
- Example 5 In the glycidylation reaction, an epoxy resin composition E was obtained in the same manner as in Example 1 except that the reaction time after dropping the 50% by mass aqueous sodium hydroxide solution was changed to 8 hours.
- the epoxy resin e2 which is a structure represented by Formula (1) is 100 mass parts
- the epoxy resin e2 which is a structure represented by Formula (2) is 2.4 parts by mass were included.
- the epoxy resin a1, R 1 is isopropylene group
- a divalent radical R 2 is derived from bisphenol A
- G 1 is a glycidyl group
- 80 mole% of G 2 is a glycidyl group
- the range of m and n in the formula (1) of the epoxy resin e1 was 3 ⁇ (m + n) ⁇ 12. And the ratio of the component (a component) in which m and n of Formula (1) satisfy
- R 1 is an isopropylene group
- R 2 is a divalent group derived from bisphenol A
- G 1 is a glycidyl group
- G 2 is a glycidyl group.
- the epoxy equivalent of the epoxy resin composition E is 420 g / eq.
- the viscosity at 25 ° C. was 1481 mPa ⁇ s, the total chlorine content was 1273 ppm, and the hydrolyzable chlorine content was 366 ppm.
- Example 6 In the glycidylation reaction, an epoxy resin composition F was obtained in the same manner as in Example 1 except that the 50 mass% tetramethylammonium chloride aqueous solution was not added.
- the epoxy resin f1 which is a structure represented by Formula (1) is 100 mass parts
- the epoxy resin f2 represented by Formula (2) is 0.5. Part by mass was included.
- the epoxy resin f1, R 1 is isopropylene group
- a divalent radical R 2 is derived from bisphenol A
- G 1 is a glycidyl group
- 62 mole% of G 2 is a glycidyl group
- it was confirmed 38 mole% of G 2 is hydrogen.
- the range of m and n in the formula (1) of the epoxy resin f1 was 3 ⁇ (m + n) ⁇ 12. And the ratio of the component (a component) in which m and n of Formula (1) satisfy
- R 1 is an isopropylene group
- R 2 is a divalent group derived from bisphenol A
- G 1 is a glycidyl group
- G 2 is a glycidyl group.
- Epoxy resin composition F has an epoxy equivalent of 332 g / eq.
- the viscosity at 25 ° C. was 1213 mPa ⁇ s, the total chlorine content was 530 ppm, and the hydrolyzable chlorine content was 242 ppm.
- Example 7 In the glycidylation reaction, an epoxy resin composition G was obtained in the same manner as in Example 1 except that 640 g of 50% by mass aqueous potassium hydroxide was used instead of 400 g of 50% by mass aqueous sodium hydroxide.
- the epoxy resin g2 represented by the formula (2) was 5.4 with respect to 100 parts by mass of the epoxy resin g1 having the structure represented by the formula (1). Part by mass was included.
- the epoxy resin g1, R 1 is isopropylene group, a divalent radical R 2 is derived from bisphenol A, G 1 is a glycidyl group, 81 mole% of G 2 is a glycidyl group, it was confirmed 19 mole% of G 2 is hydrogen.
- the range of m and n in the formula (1) of the epoxy resin g1 was 3 ⁇ (m + n) ⁇ 12.
- R 1 is an isopropylene group
- R 2 is a divalent group derived from bisphenol A
- G 1 is a glycidyl group
- G 2 is a glycidyl group.
- m, n, m ′ and n ′ in the formula (2) it was confirmed that 6 ⁇ (m + n + m ′ + n ′) ⁇ 18.
- the epoxy equivalent of the epoxy resin composition G is 495 g / eq.
- the viscosity at 25 ° C. was 2093 mPa ⁇ s
- the total chlorine content was 2883 ppm
- the hydrolyzable chlorine content was 657 ppm.
- Example 8 In the glycidylation reaction, dialcohol was added from 3 mol of propylene oxide to 1 mol of bisphenol A from “dialcohol obtained by addition reaction of 5 mol of propylene oxide to 1 mol of bisphenol A”. Except for the point changed to “dialcohol obtained by reaction”, the same procedure as in Example 1 was carried out to obtain an epoxy resin composition H.
- the epoxy resin h1 which is a structure represented by Formula (1) is 100 mass parts
- the epoxy resin h2 represented by Formula (2) is 1.4. Part by mass was included.
- the epoxy resin h1, R 1 is isopropylene group, a divalent radical R 2 is derived from bisphenol A, G 1 is a glycidyl group, 90 mole% of G 2 is a glycidyl group, it was confirmed 10 mole% of G 2 is hydrogen.
- the range of m and n in the formula (1) of the epoxy resin h1 was 1 ⁇ (m + n) ⁇ 10.
- R 1 is an isopropylene group
- R 2 is a divalent group derived from bisphenol A
- G 1 is a glycidyl group
- G 2 is a glycidyl group.
- m, n, m ′ and n ′ in the formula (2) it was confirmed that 2 ⁇ (m + n + m ′ + n ′) ⁇ 12.
- the viscosity at 25 ° C. was 1565 mPa ⁇ s
- the total chlorine content was 499 ppm
- the hydrolyzable chlorine content was 50 ppm.
- Example 9 (Glycidylation reaction) 270 g (1 equivalent of hydroxyl group) of dialcohol obtained by adding 5 moles of propylene oxide to 1 mole of bisphenol A in a flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer, epichlorohydrin 185 g (2.00 mol) and a 50 mass% tetramethylammonium chloride aqueous solution (10 g) were mixed, heated under reduced pressure, and refluxed at 60 to 65 ° C. And 80 g of 50 mass% sodium hydroxide aqueous solution was dripped over 2 hours.
- R 1 is an isopropylene group
- R 2 is a divalent group derived from bisphenol A
- G 1 is a glycidyl group
- 87 mol% of G 2 is a glycidyl group
- 13 mole% of G 2 is hydrogen.
- the range of m and n in the formula (1) of the epoxy resin i1 was 3 ⁇ (m + n) ⁇ 12.
- R 1 is an isopropylene group
- R 2 is a divalent group derived from bisphenol A
- G 1 is a glycidyl group
- G 2 is a glycidyl group.
- m, n, m ′ and n ′ in the formula (2) it was confirmed that 6 ⁇ (m + n + m ′ + n ′) ⁇ 20.
- the epoxy equivalent of the epoxy resin composition I is 335 g / eq.
- the viscosity at 25 ° C. was 8052 mPa ⁇ s
- the total chlorine content was 612 ppm
- the hydrolyzable chlorine content was 56 ppm.
- Example 10 An epoxy resin composition J was obtained in the same manner as in Example 1 except that all the condensed epichlorohydrin was returned to the reactor without recovering the condensed epichlorohydrin during the glycidylation reaction.
- the epoxy resin j2 which is a structure represented by Formula (2) with respect to 100 mass parts of the epoxy resin j1 which is a structure represented by Formula (1) is 0.05 part by mass was contained.
- R 1 is an isopropylene group
- R 2 is a divalent group derived from bisphenol A
- G 1 is a glycidyl group
- 82 mol% of G 2 is a glycidyl group
- 18 mole% of G 2 is hydrogen.
- the range of m and n in the formula (1) of the epoxy resin j1 was 3 ⁇ (m + n) ⁇ 12.
- R 1 is an isopropylene group
- R 2 is a divalent group derived from bisphenol A
- G 1 is a glycidyl group
- G 2 is a glycidyl group.
- m, n, m ′ and n ′ in the formula (2) it was confirmed that 6 ⁇ (m + n + m ′ + n ′) ⁇ 15.
- Epoxy equivalent was 385 g / eq.
- the viscosity at 25 ° C. was 1020 mPa ⁇ s
- the total chlorine content was 486 ppm
- the hydrolyzable chlorine content was 47 ppm.
- Epoxy resin K has an epoxy equivalent of 392 g / eq.
- the viscosity at 25 ° C. was 1400000 mPa ⁇ s
- the total chlorine content was 1512 ppm
- the hydrolyzable chlorine content was 253 ppm.
- Tables 1 and 2 show the physical property measurement results of Examples 1 to 10 and Comparative Examples 1 and 2.
- Example 11 to 21, Comparative Examples 3 to 8 Each material was mixed with the epoxy resin compositions of Examples 1 to 3, 5 to 10 and Comparative Examples 1 and 2 or the epoxy resin of Example 4 under the conditions described in Tables 3 and 4 to obtain an epoxy.
- a resin composition was prepared. In Example 11, the epoxy resin composition A was used alone. To the obtained epoxy resin composition, diaminodiphenylmethane (see Tables 3 and 4) was added at a ratio of 1 equivalent of active hydrogen (> NH) to 1 equivalent of epoxy group, and conditions of 180 ° C. and 2 hours And cured with an epoxy resin. The cured epoxy resin was evaluated as shown in Tables 3-4.
- Examples 22 to 31, Comparative Examples 9 to 13 Each material was mixed on the conditions of Table 5, 6, and the epoxy resin composition was prepared. A semiconductor device was manufactured using the obtained epoxy resin composition as an epoxy resin composition for sealing.
- FIG. 3 is a schematic cross-sectional view of the semiconductor device 1 on which the semiconductor chip 3 is mounted manufactured in the example.
- the substrate 2 Siliconitomo Bakelite, “ELC4782”
- the semiconductor chip 3 Panasonic, “BGA377”
- solder bumps 4 Mitsubishi Materials, “MUL ⁇ S”; the composition of the solder bumps 4 is Sn / Ag /
- the semiconductor chip mounting substrate is flip-chip connected by Cu).
- the size of the semiconductor chip 3 was 10 mm ⁇ 10 mm ⁇ 0.2 mm, and the size of the substrate 2 was 20 mm ⁇ 20 mm ⁇ 0.4 mm.
- the substrate 2 and the semiconductor chip 3 are joined to peripherals (a shape having bumps only on the outer peripheral portion) by 176 solder bumps 4.
- the height of the solder bumps 4 is 0.08 mm and the pitch distance is 0. 0.04 mm.
- Silicon nitride (SiN) was used for the circuit protective film 5 of the semiconductor chip 3, and “AUS308” manufactured by Taiyo Ink Co., Ltd. was used for the solder resist 6 on the substrate 2.
- Plasma treatment was performed before the sealing epoxy resin composition 7 was filled in the substrate 2 on which the semiconductor chip 3 was mounted.
- AP-1000 manufactured by March Plasma Systems was used.
- the processing conditions were as follows: Gas type: Ar Gas flow rate: 50 mL / m Processing strength: 350W Processing time: 420 seconds Direct plasma mode
- the substrate 2 on which the above-described semiconductor chip 3 is mounted is heated on a hot plate at 110 ° C.
- 12 mg of the epoxy resin composition 7 for sealing is dispensed on one side of the semiconductor chip 3, and the substrate 2 and the semiconductor chip After filling the gap between 3, it was maintained in an oven at 150 ° C. for 120 minutes, and the epoxy resin composition 7 for sealing was thermally cured to obtain the semiconductor device 1.
- the obtained epoxy resin composition 7 for sealing, its cured product, and the semiconductor device 1 were evaluated. The respective results are shown in Tables 5 and 6 below.
- the epoxy resin composition and the epoxy resin of the present invention include a sealing material, an adhesive, a printed board material, a paint, a composite material, a semiconductor sealing material such as underfill and molding, a conductive adhesive such as ACF, a solder resist, It can be suitably used for a printed wiring board such as a coverlay film.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
Description
〔1〕
下記式(1)で表されるエポキシ樹脂と、
下記式(2)で表されるエポキシ樹脂と、
を含む、エポキシ樹脂組成物。
〔2〕
前記式(1)で表されるエポキシ樹脂100質量部と、
前記式(2)で表されるエポキシ樹脂0.1~10質量部と、
を含む、〔1〕に記載のエポキシ樹脂組成物。
〔3〕
前記式(1)のR2が、フェニレン基、ナフチレン基、ビフェニレン基、及び下記式(3a)で表される構造を有する2価の芳香族基からなる群より選ばれるいずれかである、〔1〕又は〔2〕に記載のエポキシ樹脂組成物。
〔4〕
前記式(2)のR2の少なくとも1つが、フェニレン基、ナフチレン基、ビフェニレン基、及び下記式(3b)で表される構造を有する2価の芳香族基からなる群より選ばれるいずれかである、〔1〕~〔3〕のいずれか一項に記載のエポキシ樹脂組成物。
〔5〕
前記式(1)が、下記式(4)であり、前記式(2)が、下記式(5)である、〔1〕~〔4〕のいずれか一項に記載のエポキシ樹脂組成物。
〔6〕
前記式(5)のG4が、グリシジル基である、〔5〕に記載のエポキシ樹脂組成物。
〔7〕
下記式(1)で表されるエポキシ樹脂であって、前記式(1)中のm及びnが、それぞれ独立して、1~11の整数であり、かつ、3≦(m+n)≦12で表される関係を満たし、
前記エポキシ樹脂中における、m及びnが、6≦(m+n)≦12で表される関係を満たす成分の割合が、30モル%以上70モル%以下である、エポキシ樹脂。
〔8〕
前記エポキシ樹脂中における、前記式(1)のG2がグリシジル基である成分の割合が、10モル%以上100モル%以下である、〔7〕に記載のエポキシ樹脂。
〔9〕
前記式(1)のR2が、フェニレン基、ナフチレン基、ビフェニレン基、及び下記式(3a)で表される構造を有する2価の芳香族基からなる群より選ばれるいずれかである、〔7〕又は〔8〕に記載のエポキシ樹脂。
〔10〕
全塩素量が、1000質量ppm以下である、〔7〕~〔9〕のいずれか一項に記載のエポキシ樹脂。
〔11〕
〔1〕~〔6〕のいずれか一項に記載のエポキシ樹脂組成物、又は〔7〕~〔10〕のいずれか一項に記載のエポキシ樹脂と、
硬化剤と、
を含有する、エポキシ樹脂組成物。
〔12〕
〔11〕に記載のエポキシ樹脂組成物を硬化させて得られる硬化物。
〔13〕
下記式(1)で表されるエポキシ樹脂から得られる硬化物であって、
前記硬化物を、動的粘弾性装置を用いて振動数1Hzの硬化物測定をする場合、下記数式(a)で表される関係と下記数式(b)で表される関係とを満たす、硬化物。
E’/(273+T1/3)<8.5 ・・・(a)
(数式(a)中、T1は、得られた損失正接のピークトップの温度であり、E’(MPa)は、30℃で測定した貯蔵弾性率である。)
E’(T1-20)>10×E’(T1+20) ・・・(b)
(数式(b)中、E’(T1-20)は、(T1-20)℃で測定した貯蔵弾性率であり、E’(T1+20)は、(T1+20)℃で測定した貯蔵弾性率である。)
〔14〕
前記硬化物が、下記数式(c)で表される関係と、下記数式(d)で表される関係とを更に満たす、〔13〕に記載の硬化物。
E’/(273+T1/3)<7 ・・・(c)
(数式(c)中、E’は、30℃で測定した貯蔵弾性率であり、T1は、得られた損失正接のピークトップの温度である。)
E’(T1-20)>20×E’(T1+20)・・・(d)
(数式(d)中、E’は、30℃で測定した貯蔵弾性率であり、T1は、得られた損失正接のピークトップの温度である。)
〔15〕
〔12〕~〔14〕のいずれか一項に記載の硬化物を含む電子部材。
上述した第1の実施形態のエポキシ樹脂組成物に用いられるエポキシ樹脂組成物や、第2の実施形態のエポキシ樹脂は、少なくとも式(1)で表される構造を有するエポキシ樹脂である。以下、式(1)で表される構造を有するエポキシ樹脂の製造方法の一例を説明する。
E’/(273+T1/3)<8.5 ・・・(a)
(数式(a)中、T1は、得られた損失正接のピークトップの温度であり、E’(MPa)は、30℃で測定した貯蔵弾性率である。)
E’(T1-20)>10×E’(T1+20) ・・・(b)
(数式(b)中、E’(T1-20)は、(T1-20)℃で測定した貯蔵弾性率であり、E’(T1+20)は、(T1+20)℃で測定した貯蔵弾性率である。)
このような硬化物は、落下衝撃等の物性に優れるだけでなく、温度変化による接着強度の低下が少なく、実装したあとの信頼性に大きく寄与する。このような硬化物は、例えば、上述した第1の実施形態のエポキシ樹脂組成物や、第2の実施形態のエポキシ樹脂を用いることでも得られうる。
「エポライト40E」:エチレングリコールジグリシジルエーテル(共栄社化学社製;エポキシ当量135g/eq.、粘度40mPa・s、グリシジル化率96モル%、全塩素量18220質量ppm)
「YED216D」:1,6-ヘキサメチレンジグリシジルエーテル(三菱化学社製;エポキシ当量120g/eq.)
「AER260」:ビスフェノールA型エポキシ樹脂(旭化成イーマテリアルズ社製;エポキシ当量188g/eq.)
「AER6011」:固形ビスフェノールA型エポキシ樹脂(旭化成イーマテリアルズ社製;エポキシ当量425g/eq.)
「YL983U」:ビスフェノールF型エポキシ樹脂(三菱化学社製;エポキシ当量170g/eq.)
「ジアミノジフェニルメタン」(和光純薬工業社製;アミン当量49.6g/eq.)
「エタキュア100」:芳香族アミン(三井化学ファイン社製;アミン当量44.5g/eq.)
「MEH8000H」:液状フェノール樹脂(明和化成社製;フェノール当量142g/eq.)
「リカシッドMHT」:4-メチルヘキサヒドロ無水フタル酸(新日本理化社製;酸無水物当量168g/eq.)
「HX3941」:マイクロカプセル型硬化剤(旭化成イーマテリアルズ社製;アミンアダクト系マイクロカプセル型硬化剤)
「AC-5V」:シリカ(龍森社製;平均粒子径5μm)
「KBM-403」:シリカ表面処理剤(信越化学工業社製;エポキシ系シランカップリング剤)
JIS K7236に準拠して、エポキシ当量を測定した。
JIS K7243-3に準拠して、全塩素量を測定した。
JIS K7243-2に準拠して、加水分解性塩素量を測定した。
高速液体クロマトグラフィー(HPLC)及び質量分析装置(MS)を用いて、エポキシ樹脂組成物やエポキシ樹脂の構造確認等を行った。例えば、式(1)のm及びnに関する(m+n)に関する比率や、式(1)の構造等も確認した。また、式(2)のm、n、m、及びn’に関する比率や、式(2)の構造等も同様にして確認した。
HPLCの測定条件は、以下のとおりであった。
・東ソー社製「LC8020model II」システム、
・カラム:ウォーターズ社製「NOVA PACK C18」、
・移動相;蒸留水/アセトニトリル(混合割合は、0分~20分の間において、蒸留水/アセトニトリル=50/50~0/100(体積比)となるよう、等速的に変化させた。)
・流量:1.5mL/分
・分検出器:280nm
MSの測定条件は、以下のとおりであった。
・ThermoElectron社製「LCQ」装置
・イオン化法:大気圧光化学イオン化法(APCI)
・スキャンレンジ:m/z=150~2000
なお、上記式(1)のm、n及び(m+n)の値等は、得られたHPLC及びGCチャート中のそれぞれのピーク面積比より求めた。
JIS K7117-2(E型粘度計)に準拠して、粘度を測定した。
高速液体クロマトグラフィー(HPLC)及び質量分析装置(MS)を用いて、式(1)中の(m+n)の数値、式(2)中の(m+n+m’+n’)の数値等を求めた。
HPLCの測定条件は、以下のとおりとした。
・測定装置:東ソー社製「LC8020model II」システム、
・カラム:ウォーターズ社製「NOVA PACK C18」、
・移動相:蒸留水/メタノール/アセトニトリル系(混合割合は、0分~20分の間において、蒸留水/アセトニトリル=50/50~0/100(体積比)となるよう、等速的に変化させた。)、
・流量:1.5mL/分
・分検出器:280nm
MSの測定条件は、以下のとおりであった。
・測定装置:ThermoElectron社製「LCQ」装置、
・イオン化:APCI+
・スキャンレンジ:m/z=150~2000
得られたHPLC及びMSチャート中のそれぞれのピーク面積比より、前記各数値及び含有率を求めた。
エポキシ樹脂「AER4152」(旭化成エポキシ社製、オキサゾリドン環を有するイソシアネート変性エポキシ樹脂;エポキシ当量340g/eq.)と、後述する合成樹脂と、を50/50の質量比で混合し、140℃加熱した。そして室温まで冷却した際の相溶性を評価した。相溶性は、以下の基準に基づき評価した。
○:全体が透明であり、均一相であった。
△:一部はマーブル状であったが、全体としては透明であり、実用上問題がないレベルであった。
×:全体が白濁し、不均一相であった。
表2に従って調製したエポキシ樹脂組成物を180℃で2時間硬化させて硬化物を得た。得られた硬化物を、ダイヤモンドカッターを用いて切断し、10mm×40mm×0.5mmの試験片を得た。この試験片を、固体粘弾性測定装置(DMA;TAインストルメントル社製「RSA-G2」)にセットし、温度範囲-50~300℃(昇温速度:2℃/分)の測定条件で測定した。tanδが最大値になったときの温度をガラス転移点(Tg)=T1とした。得られた測定結果から、30℃の貯蔵弾性率E’、(Tg-20)℃のときの貯蔵弾性率E’(Tg-20)、(Tg+20)℃のときの貯蔵弾性率E’(Tg+20)をそれぞれ求めた。
JIS K7116に準拠して、硬化物の曲げ強度を測定した。
JIS K6850に準拠して、硬化物の銅板せん断接着強度を測定した。標準試験片C1100P(日本テストパネル社製)の表面に、厚さ100μmのフッ素樹脂製耐熱テープを張り付けて、標準試験片の表面に25mm×5mmの隙間が形成されるようマスキングした。その隙間(25mm×5mm)にエポキシ樹脂組成物を塗布し、もう1枚の標準試験片C1100Pとで挟み込んだ。それを、180℃で2時間の条件で加熱することで、エポキシ樹脂組成物を熱硬化させてサンプルを得た。
得られたサンプルについて、23℃、50%RHの恒温恒湿室において、引張試験器AGS-H 5kNを用いて、ヒートサイクル試験前の銅板せん断接着強度(a)を測定した。
得られたサンプルについて、-40℃(15分保持)~+125℃(15分保持)のヒートサイクル試験を1000サイクル実施した。そして、ヒートサイクル試験後の銅板せん断接着強度(b)を測定した。
ヒートサイクル試験前の銅板せん断接着強度(a)に対するヒートサイクル試験後の銅板せん断接着強度(b)の割合を求めることによって、接着強度保持率(b/a)を算出した。
JACT試験法 RS-5及びJIS K-6910-1995に準拠して、ゲルタイムを測定した。具体的には、表3に従って調製したエポキシ樹脂組成物をサンプルとし、ゲル化試験機を用いてゲルタイムを測定した。サンプルを170℃のホットプレート上で撹拌しながら加熱し、サンプルと撹拌棒の間で糸を引かなくなるまでの時間をゲルタイムとした。
JIS K7209に準拠して、吸水率を測定した。
下記式に基づき、グリシジル化率を算出した。
グリシジル化率(%)=Et/Ea×100(%)
Et=理論エポキシ当量 (g/eq.)
Ea=実測エポキシ当量 (g/eq.)
理論エポキシ当量(Et)は、100%グリシジル化された構造式から求められる分子量から求めた。
実測エポキシ当量(Ea)は、上述したように、 JIS K7236に準拠して求めた。
表2に従って調製したエポキシ樹脂組成物を、100mm×100mm×2mmのフッ素樹脂板の型に流し込み、180℃で2時間硬化させて硬化物を得た。得られた硬化物を、デュポン衝撃試験機H50を使用して、衝撃試験を行った。硬化物上に突端の半径3.1mmの撃芯を置き、その上から重りを落として、硬化物が割れるかどうかで判定を行い、以下の基準に基づき評価した。
×:割れたときの重さ(kg)×高さ(cm)の積が3未満であった。
△:割れたときの重さ(g)×高さ(cm)の積が3以上7未満であった。
○:割れたときの重さ(g)×高さ(cm)の積が7以上20未満であった。
◎:割れたときの重さ(g)×高さ(cm)の積が20以上であった。
銀メッキ加工された標準試験片C1100P(日本テストパネル社製)を用いて、「銅板せん断接着強度」の項と同様にしてサンプル10枚を作製した(JIS K6850の準拠)。そのうちの5枚のサンプルについては、「吸湿試験前の銀メッキへの接着強度a」を測定した。接着強度aは、5枚のサンプルの測定値の算術平均であった。
別の5枚のサンプルについては、85℃、85RH%の恒温恒湿室に300時間静置して、吸湿させた。そして、吸湿させた後のサンプルを、「吸湿試験前の銀メッキへの接着強度a」の測定方法と同様にして、「吸湿試験後の銀メッキへの接着強度b」を測定した。接着強度bは、5枚の吸湿後のサンプルの測定値の算術平均であった。
接着強度aに対する接着強度bの比率を、接着強度保持率(b/a)とした。
ガラス板上に厚さ20μmのフッ素樹脂製シール2枚を30mm間隔で置き、もう1枚のガラス板で挟んだ。これを、150℃のホットプレート上に水平に置き、上側のガラス板の温度が145℃に達したところで、エポキシ樹脂組成物を2枚のガラス板の隙間に垂らして、15分間保持した。エポキシ樹脂組成物が浸透した距離を測定した。評価は以下の基準で行った。
◎:浸透した距離が30~100mmであり、エポキシ樹脂組成物が均一に硬化した。
○:浸透した距離が15~30mmであり、エポキシ樹脂組成物が均一に硬化した。
△:浸透した距離が30~100mmであり、硬化物の濁りやムラが発生した。
×:浸透した距離が15mm以下であったか、あるいは、硬化せずに100mm以上浸透した。
後述する方法にて製造した半導体装置を、コンクリートから100cmの高さより水平に10回落下させた。落下させた後の半導体装置内のエポキシ樹脂組成物の剥離の有無を、確認した。剥離の有無は、超音波探傷装置(日立建機社製、型式mi-scope hyper)を用いて確認した。硬化物落下試験の評価は以下の基準で行った。
◎:10回落下させても剥離しなかった。
○:6~9回目の落下で剥離した。
△:2~5回目の落下で剥離した。
×:1回目の落下で剥離した。
後述する方法にて製造した半導体装置を、JEDEC耐湿レベル3の吸湿処理(30℃、相対湿度60%で168時間処理)を行った後、IRリフロー処理(ピーク温度260℃、処理時間:60秒)を3回施した。そして、半導体装置内部でのエポキシ樹脂組成物の剥離の有無を確認した。剥離の有無は、超音波探傷装置(日立建機社製、型式mi-scope hyper)を用いて確認した。耐リフロー性の評価は以下の基準で行った。
○:剥離が観察されなかった。
×:剥離が観察された。
後述する方法にて製造した半導体装置に、-55℃で30分間保持し、続いて20分間で125℃まで昇温し、さらに125℃で30分間保持することを1サイクルとした冷熱サイクル処理を、1000サイクル行った。その際、250サイクル毎に半導体装置内部の半導体チップとエポキシ樹脂組成物との界面の剥離の有無を確認した。界面剥離の有無は、超音波探傷装置(日立建機社製、型式mi-scope hyper)を用いて、を用いて確認した。冷熱サイクル性の評価は以下の基準で行った。
◎:1000サイクル行っても剥離が観察されなかった。
○:750サイクル迄行った時点で剥離が観測された。
△:500サイクル迄行った時点で剥離が観測された。
×:250サイクル迄行った時点で剥離が観察された。
(グリシジル化反応)
温度計、滴下ロート、冷却管、及び撹拌機を備えたフラスコに、1モルのビスフェノールAに対してプロピレンオキサイド5モルを付加反応させて得られたジアルコール270g(水酸基1当量)、エピクロロヒドリン463g(5.00モル)、及び50質量%テトラメチルアンモニウムクロリド水溶液(10g)を混合し、減圧下に加熱して60~65℃で還流を行った。そして、50質量%水酸化ナトリウム水溶液400gを2時間かけて滴下した。滴下の際、水をエピクロロヒドリンとの共沸混合物として連続的に除去するとともに、凝縮したエピクロロヒドリン層のみを連続的に反応器に戻した。滴下後、さらに2時間反応させた後、混合物を冷却し、水洗を繰り返して副生した塩化ナトリウムを除去した。過剰のエピクロロヒドリンを減圧下で蒸留して除去し、粗樹脂組成物を得た。
(低塩素化反応)
得られた粗樹脂組成物100gをメチルイソブチルケトン200gに溶解し、0.22gの50質量%水酸化ナトリウム水溶液を加え、80℃で2時間反応させた。反応終了後、水洗によりメチルイソブチルケトンを除去してエポキシ樹脂組成物Aを得た。
一例として、図1に、実施例1で得られたエポキシ樹脂組成物AのNMRチャートを示し、図2に、実施例1で得られたエポキシ樹脂組成物AのMALDI-MSチャートを示す。エポキシ樹脂組成物Aを分析したところ、式(1)で表される構造であるエポキシ樹脂a1が100質量部に対して、式(2)で表される構造であるエポキシ樹脂a2が1.3質量部含まれていた。
エポキシ樹脂a1については、R1がイソプロピレン基であり、R2がビスフェノールAに由来する2価の基であり、G1がグリシジル基であり、G2の74モル%がグリシジル基であり、G2の26モル%が水素であることが確認された。式(1)のm及びnの範囲は6≦(m+n)≦12であった。そして、エポキシ樹脂a1における、式(1)のm及びnが6≦(m+n)≦12の関係を満たす成分(a成分)の割合は、48モル%であった
エポキシ樹脂a2については、R1がイソプロピレン基であり、R2がビスフェノールAに由来する2価の基であり、G1がグリシジル基であり、G2がグリシジル基であることが確認された。式(2)のm、n、m’及びn’については、6≦(m+n+m’+n’)≦15であることが確認された。
また、エポキシ樹脂Aのエポキシ当量は371g/eq.であり、25℃での粘度は952mPa・sであり、全塩素量は512ppmであり、加水分解性塩素量は56ppmであった。
製造例1において用いたジアルコールについて、「1モルのビスフェノールAに対してプロピレンオキサイド5モルを付加反応させて得られたジアルコール」から、「1モルのビフェノールに対してエポキシペンタン2モルを付加反応させて得られたジアルコール」に変更した。その他の条件は実施例1と同様に行い、エポキシ樹脂組成物Bを得た。
得られたエポキシ樹脂組成物Bを分析したところ、式(1)で表される構造であるエポキシ樹脂b1が100質量部に対して、式(2)で表されるエポキシ樹脂b2が2.5質量部含まれていた。
エポキシ樹脂b1については、R1がペンチル基(-CHCH(C3H7)-)であり、R2がビフェニル基であり、G1がグリシジル基であり、G2の99.5モル%がグリシジル基であり、G2の0.5モル%が水素であることが確認された。エポキシ樹脂b1の式(1)のm及びnの範囲は、1≦(m+n)≦9であった。そして、エポキシ樹脂b1における、式(1)のm及びnが6≦(m+n)≦12の関係を満たす成分(a成分)の割合は、18モル%であった。
エポキシ樹脂b2については、R1がペンチル基であり、R2がビフェニル基であり、G1がグリシジル基であり、G2がグリシジル基であることが確認された。式(2)のm、n、m’及びn’については、2≦(m+n+m’+n’)≦13であることが確認された。
エポキシ樹脂組成物Bのエポキシ当量は262g/eq.であり、25℃での粘度は1782mPa・sであり、全塩素量は423ppmであり、加水分解性塩素量は50ppmであった。
実施例1で製造したエポキシ樹脂組成物Aを270g仕込み、触媒として、三フッ化ホウ素ジエチルエーテル錯体1.8gを仕込んだ後、60℃に加熱し、フェニルグリシジルエーテル(ナガセケムテックス社製、「EX141」、エポキシ当量150g/eq.)36gを1時間かけて滴下した。滴下終了後、60℃で1.5時間反応させた後に、6.0gの50質量%水酸化ナトリウム水溶液を添加して、三フッ化ホウ素ジエチルエーテルを失活させたのち、300gの精製水にて触媒残渣を除去することにより、粗樹脂組成物を291g得た。
得られた粗樹脂組成物270gを、実施例1における、「1モルのビスフェノールAに対してプロピレンオキサイド5モル付加反応させて得られたジアルコール」の代わりに用いた点以外は、実施例1と同様に操作を行い、エポキシ樹脂組成物Cを得た。
得られたエポキシ樹脂組成物Cを分析したところ、式(1)で表される構造であるエポキシ樹脂c1が100質量部に対して、式(2)で表される構造であるエポキシ樹脂c2が1.2質量部含まれていた。
エポキシ樹脂c1については、R1はイソプロピレン基又はフェノキシイソプロピレン基(-CH2CH(CH2OC6H6)-)であり、R2はビスフェノールAに由来する2価の基であり、G1はグリシジル基であり、G2の71.8モル%がグリシジル基であり、G2の28.2%が水素原子であることが確認された。エポキシ樹脂c1の式(1)のm及びnの範囲は、3≦(m+n)≦12であった。そして、エポキシ樹脂c1における、式(1)のm及びnが6≦(m+n)≦12の関係を満たす成分(a成分)の割合は、48モル%であった。
エポキシ樹脂c2については、R1の86モル%がイソプレン基であり、R1の14モル%がフェノキシイソプレン基であり、R2がフェノキシイソプロピレン基であり、G1がグリシジル基であり、G2がグリシジル基であることが確認された。式(2)のm、n、m’及びn’については、6≦(m+n+m’+n’)≦15であることが確認された。
エポキシ樹脂組成物Cのエポキシ当量は385g/eq.であり、25℃での粘度は1245mPa・sであり、全塩素量は621ppmであり、加水分解性塩素量は57ppmであった。
温度計、及び撹拌機を備えたフラスコにレゾルシノール120gとトリエチレングリコールジビニルエーテル172gを仕込み、1時間かけて120℃まで昇温させた。その後、120℃で6時間反応させて、透明半固形の変性多価フェノール類290gを得た。得られた変性多価フェノール類290g、エピクロロヒドリン735g、n-ブタノール185gを仕込み、溶解させた。そして、減圧下に加熱して60~65℃で還流を行った。50質量%水酸化ナトリウム水溶液130.3gを2時間かけて滴下した。滴下の際、水をエピクロロヒドリンとの共沸混合物として連続的に除去するとともに、凝縮したエピクロロヒドリン層のみを連続的に反応器に戻した。その後、さらに2時間反応させた後、混合物を冷却し、水洗を繰り返して副生した塩化ナトリウムを除去した。そして、過剰のエピクロロヒドリンを減圧下で蒸留して除去し、粗樹脂を得た。
得られた粗樹脂100gをメチルイソブチルケトン200gに溶解させ、0.22gの50質量%水酸化ナトリウム水溶液を加え、80℃で2時間反応させ、水洗によりメチルイソブチルケトンを留去して、エポキシ樹脂Dを得た。
得られたエポキシ樹脂Dを分析したところ、式(1)で表される構造であって、R1がフェニレン基であり、R2がトリエチレン基であり、G1がグリシジル基であり、G2がグリシジル基であるエポキシ樹脂であることが確認された。エポキシ樹脂Dの式(1)のmは1であり、nは1であった。そして、エポキシ樹脂Dにおける、式(1)のm及びnが6≦(m+n)≦12の関係を満たす成分(a成分)の割合は、0モル%であった。
エポキシ樹脂Dのエポキシ当量は286g/eq.であり、25℃での粘度は12000mPa・sであり、全塩素量は877ppmであり、加水分解塩素量は72ppmであった。
グリシジル化反応において、50質量%水酸化ナトリウム水溶液の滴下後の反応時間を8時間に変更した点以外は実施例1と同様に行い、エポキシ樹脂組成物Eを得た。
得られたエポキシ樹脂組成物Eを分析したところ、式(1)で表される構造であるエポキシ樹脂e1が100質量部に対して、式(2)で表される構造であるエポキシ樹脂e2が2.4質量部含まれていた。
エポキシ樹脂a1については、R1がイソプロピレン基であり、R2がビスフェノールAに由来する2価の基であり、G1がグリシジル基であり、G2の80モル%がグリシジル基であり、20モル%が水素であることが確認された。エポキシ樹脂e1の式(1)のm及びnの範囲は、3≦(m+n)≦12であった。そして、エポキシ樹脂e1における、式(1)のm及びnが6≦(m+n)≦12の関係を満たす成分(a成分)の割合は、67モル%であった。
エポキシ樹脂e2については、R1がイソプロピレン基であり、R2がビスフェノールAに由来する2価の基であり、G1がグリシジル基であり、G2がグリシジル基であることが確認された。式(2)のm、n、m’及びn’については、6≦(m+n+m’+n’)≦15であることが確認された。
エポキシ樹脂組成物Eのエポキシ当量は420g/eq.であり、25℃での粘度は1481mPa・sであり、全塩素量は1273ppmであり、加水分解性塩素量は366ppmであった。
グリシジル化反応において、50質量%テトラメチルアンモニウムクロリド水溶液を加えなかった点以外は、実施例1と同様に行い、エポキシ樹脂組成物Fを得た。
得られたエポキシ樹脂組成物Fを分析したところ、式(1)で表される構造であるエポキシ樹脂f1が100質量部に対して、式(2)で表されるエポキシ樹脂f2が0.5質量部含まれていた。
エポキシ樹脂f1については、R1がイソプロピレン基であり、R2がビスフェノールAに由来する2価の基であり、G1がグリシジル基であり、G2の62モル%がグリシジル基であり、G2の38モル%が水素であることが確認された。エポキシ樹脂f1の式(1)のm及びnの範囲は、3≦(m+n)≦12であった。そして、エポキシ樹脂f1における、式(1)のm及びnが6≦(m+n)≦12の関係を満たす成分(a成分)の割合は、35モル%であった。
エポキシ樹脂f2については、R1がイソプロピレン基であり、R2がビスフェノールAに由来する2価の基であり、G1がグリシジル基であり、G2がグリシジル基であることが確認された。式(2)のm、n、m’及びn’については、6≦(m+n+m’+n’)≦14であることが確認された。
エポキシ樹脂組成物Fのエポキシ当量は332g/eq.であり、25℃での粘度は1213mPa・sであり、全塩素量は530ppmであり、加水分解性塩素量は242ppmであった。
グリシジル化反応において、50質量%水酸化ナトリウム水溶液400gの代わりに、50質量%水酸化カリウム水溶液640gを用いた点以外は実施例1と同様に行い、エポキシ樹脂組成物Gを得た。
得られたエポキシ樹脂組成物Gを分析したところ、式(1)で表される構造であるエポキシ樹脂g1が100質量部に対して、式(2)で表されるエポキシ樹脂g2が5.4質量部含まれていた。
エポキシ樹脂g1については、R1がイソプロピレン基であり、R2がビスフェノールAに由来する2価の基であり、G1がグリシジル基であり、G2の81モル%がグリシジル基であり、G2の19モル%が水素であることが確認された。エポキシ樹脂g1の式(1)のm及びnの範囲は、3≦(m+n)≦12であった。そして、エポキシ樹脂g1における、式(1)のm及びnが6≦(m+n)≦12の関係を満たす成分(a成分)の割合は、76モル%であった。
エポキシ樹脂g2については、R1がイソプロピレン基であり、R2がビスフェノールAに由来する2価の基であり、G1がグリシジル基であり、G2がグリシジル基であることが確認された。式(2)のm、n、m’及びn’については、6≦(m+n+m’+n’)≦18であることが確認された。
エポキシ樹脂組成物Gのエポキシ当量は495g/eq.であり、25℃での粘度は2093mPa・sであり、全塩素量は2883ppmであり、加水分解性塩素量は657ppmであった。
グリシジル化反応において、ジアルコールを、「1モルのビスフェノールAに対してプロピレンオキサイド5モルを付加反応させて得られたジアルコール」から、「1モルのビスフェノールAに対してプロピレンオキサイド3モルを付加反応させて得られたジアルコール」に変更した点以外は実施例1と同様に行い、エポキシ樹脂組成物Hを得た。
得られたエポキシ樹脂組成物Hを分析したところ、式(1)で表される構造であるエポキシ樹脂h1が100質量部に対して、式(2)で表されるエポキシ樹脂h2が1.4質量部含まれていた。
エポキシ樹脂h1については、R1がイソプロピレン基であり、R2がビスフェノールAに由来する2価の基であり、G1がグリシジル基であり、G2の90モル%がグリシジル基であり、G2の10モル%が水素であることが確認された。エポキシ樹脂h1の式(1)のm及びnの範囲は、1≦(m+n)≦10であった。そして、エポキシ樹脂h1における、式(1)のm及びnが6≦(m+n)≦12の関係を満たす成分(a成分)の割合は、22モル%であった。
エポキシ樹脂h2については、R1がイソプロピレン基であり、R2がビスフェノールAに由来する2価の基であり、G1がグリシジル基であり、G2がグリシジル基であることが確認された。式(2)のm、n、m’及びn’については、2≦(m+n+m’+n’)≦12であることが確認された。
エポキシ樹脂組成物Hのエポキシ当量309g/eq.であり、25℃での粘度は1565mPa・sであり、全塩素量は499ppmであり、加水分解性塩素量は50ppmであった。
(グリシジル化反応)
温度計、滴下ロート、冷却管及び撹拌機を備えたフラスコに、1モルのビスフェノールAに対してプロピレンオキサイド5モルを付加反応させて得られたジアルコール270g(水酸基1当量)、エピクロロヒドリン185g(2.00モル)、及び50質量%テトラメチルアンモニウムクロリド水溶液(10g)を混合し、減圧下に加熱して60~65℃で還流を行った。そして、50質量%水酸化ナトリウム水溶液80gを2時間かけて滴下した。滴下の際、水をエピクロロヒドリンとの共沸混合物として連続的に除去するとともに、凝縮したエピクロロヒドリン層のみを連続的に反応器に戻した。滴下後、エピクロロヒドリン370gを一気に投入し、その後50質量%水酸化ナトリウム水溶液320gを2時間かけて滴下した。滴下終了後、さらに2時間反応させた後、混合物を冷却し、水洗を繰り返して副生した塩化ナトリウムを除去した。過剰のエピクロロヒドリンを減圧下で蒸留して除去し、粗樹脂組成物を得た。
得られた粗樹脂組成物100gをメチルイソブチルケトン200gに溶解し、0.22gの50質量%水酸化ナトリウム水溶液を加え、80℃で2時間反応させた。反応終了後、水洗によりメチルイソブチルケトンを除去してエポキシ樹脂組成物Iを得た。
得られたエポキシ樹脂組成物Iを分析したところ、式(1)で表される構造であるエポキシ樹脂i1が100質量部に対して、式(2)で表されるエポキシ樹脂i2が12.1質量部含まれていた。
エポキシ樹脂i1については、R1がイソプロピレン基であり、R2がビスフェノールAに由来する2価の基であり、G1がグリシジル基であり、G2の87モル%がグリシジル基であり、G2の13モル%が水素であることが確認された。エポキシ樹脂i1の式(1)のm及びnの範囲は、3≦(m+n)≦12であった。そして、エポキシ樹脂i1における、式(1)のm及びnが6≦(m+n)≦12の関係を満たす成分(a成分)の割合は、56モル%であった。
エポキシ樹脂i2については、R1がイソプロピレン基であり、R2がビスフェノールAに由来する2価の基であり、G1がグリシジル基であり、G2がグリシジル基であることが確認された。式(2)のm、n、m’及びn’については、6≦(m+n+m’+n’)≦20であることが確認された。
エポキシ樹脂組成物Iのエポキシ当量は335g/eq.であり、25℃での粘度は8052mPa・sであり、全塩素量は612ppmであり、加水分解性塩素量は56ppmであった。
グリシジル化反応時に、凝縮したエピクロロヒドリンを回収することなく、全て反応器に戻した点以外は、実施例1と同様にして、エポキシ樹脂組成物Jを得た。
得られたエポキシ樹脂組成物Jを分析したところ、式(1)で表される構造であるエポキシ樹脂j1が100質量部に対して、式(2)で表される構造であるエポキシ樹脂j2が0.05質量部含まれていた。
エポキシ樹脂j1については、R1がイソプロピレン基であり、R2がビスフェノールAに由来する2価の基であり、G1がグリシジル基であり、G2の82モル%がグリシジル基であり、G2の18モル%が水素であることが確認された。エポキシ樹脂j1の式(1)のm及びnの範囲は、3≦(m+n)≦12であった。そして、エポキシ樹脂j1における、式(1)のm及びnが6≦(m+n)≦12の関係を満たす成分(a成分)の割合は、59モル%であった。
エポキシ樹脂j2については、R1がイソプロピレン基であり、R2がビスフェノールAに由来する2価の基であり、G1がグリシジル基であり、G2がグリシジル基であることが確認された。式(2)のm、n、m’及びn’については、6≦(m+n+m’+n’)≦15であることが確認された。
エポキシ当量は385g/eq.であり、25℃での粘度は1020mPa・sであり、全塩素量は486ppmであり、加水分解性塩素量は47ppmであった。
(グリシジル化反応)
温度計、滴下ロート、冷却管及び撹拌機を備えたフラスコに、固形ビスフェノールA型エポキシ(旭化成イーマテリアルズ社製「AER6061」;エポキシ当量425g/eq.)425g、エピクロロヒドリン463g(5.00モル)を混合し、室温で溶解させた。その後、50質量%テトラメチルアンモニウムクロリド水溶液(10g)を混合し、加熱していき、減圧下に加熱して60~65℃で還流を行った。そして、50質量%水酸化ナトリウム水溶液80gを2時間かけて滴下した。滴下の際、水をエピクロロヒドリンとの共沸混合物として連続的に除去するとともに、凝縮したエピクロロヒドリン層のみを連続的に反応器に戻した。滴下後、さらに2時間反応させた後、混合物を冷却し、水洗を繰り返して副生した塩化ナトリウムを除去した。過剰のエピクロロヒドリンを減圧下で蒸留して除去し、エポキシ樹脂Kを得た。
得られたエポキシ樹脂Kを分析したところ、少なくとも式(1)及び式(2)で表される構造に該当しないことが確認された。
エポキシ樹脂Kのエポキシ当量は392g/eq.であり、25℃での粘度は1400000mPa・sであり、全塩素量は1512ppmであり、加水分解性塩素量は253ppmであった。
実施例1~3、5~10及び比較例1、2のエポキシ樹脂組成物、あるいは、実施例4のエポキシ樹脂に対して、表3、4に記載の条件で各材料を混合して、エポキシ樹脂組成物を調製した。なお、実施例11では、エポキシ樹脂組成物Aを単独で用いた。
得られたエポキシ樹脂組成物に、エポキシ基1当量に対して活性水素(>NH)が1当量となる割合で、ジアミノジフェニルメタン(表3、4参照)を添加し、180℃、2時間の条件で硬化させてエポキシ樹脂硬化物を得た。このエポキシ樹脂硬化物について、表3~4に示す評価を行った。
表5、6に記載の条件で各材料を混合し、エポキシ樹脂組成物を調製した。得られたエポキシ樹脂組成物を封止用エポキシ樹脂組成物として用いて、半導体装置を製造した。
実施例22~31、比較例9~13の封止用エポキシ樹脂組成物をそれぞれ用いて、図3に示す半導体装置1を作製した。図3は、実施例で作製した、半導体チップ3が搭載された半導体装置1の断面概略図を示す。予め基板2(住友ベークライト社製、「ELC4782」)と半導体チップ3(パナソニック社製、「BGA377」)が半田バンプ4(三菱マテリアル社製、「MULαS」;半田バンプ4の組成はSn/Ag/Cu)によってフリップチップ接続されている半導体チップ搭載基板とした。半導体チップ3のサイズは10mm×10mm×0.2mmであり、基板2のサイズは20mm×20mm×0.4mmであった。基板2と半導体チップ3は、176個の半田バンプ4によりペリフェラル(外周部のみにバンプがある形状)に接合されており、半田バンプ4の高さは0.08mmであり、ピッチ間距離は0.04mmであった。半導体チップ3の回路保護膜5には窒化珪素(SiN)が用いられ、基板2上のソルダーレジスト6には太陽インキ社製の「AUS308」を用いた。
半導体チップ3が搭載された基板2に封止用エポキシ樹脂組成物7を充填する前に、プラズマ処理を行った。プラズマ装置としては、March Plasma Systems社製、「AP-1000」を用いた。処理条件は、以下のとおりであった。
ガス種:Ar
ガス流量:50mL/m
処理強さ:350W
処理時間:420秒
ダイレクトプラズマモード
Claims (15)
- 前記式(1)で表されるエポキシ樹脂100質量部と、
前記式(2)で表されるエポキシ樹脂0.1~10質量部と、
を含む、請求項1に記載のエポキシ樹脂組成物。 - 前記式(5)のG4が、グリシジル基である、請求項5に記載のエポキシ樹脂組成物。
- 前記エポキシ樹脂中における、前記式(1)のG2がグリシジル基である成分の割合が、10モル%以上100モル%以下である、請求項7に記載のエポキシ樹脂。
- 全塩素量が、1000質量ppm以下である、請求項7~9のいずれか一項に記載のエポキシ樹脂。
- 請求項1~6のいずれか一項に記載のエポキシ樹脂組成物、又は請求項7~10のいずれか一項に記載のエポキシ樹脂と、
硬化剤と、
を含有する、エポキシ樹脂組成物。 - 請求項11に記載のエポキシ樹脂組成物を硬化させて得られる硬化物。
- 下記式(1)で表されるエポキシ樹脂から得られる硬化物であって、
前記硬化物を、動的粘弾性装置を用いて振動数1Hzの硬化物測定をする場合、下記数式(a)で表される関係と下記数式(b)で表される関係とを満たす、硬化物。
E’/(273+T1/3)<8.5 ・・・(a)
(数式(a)中、T1は、得られた損失正接のピークトップの温度であり、E’(MPa)は、30℃で測定した貯蔵弾性率である。)
E’(T1-20)>10×E’(T1+20) ・・・(b)
(数式(b)中、E’(T1-20)は、(T1-20)℃で測定した貯蔵弾性率であり、E’(T1+20)は、(T1+20)℃で測定した貯蔵弾性率である。) - 前記硬化物が、下記数式(c)で表される関係と、下記数式(d)で表される関係とを更に満たす、請求項13に記載の硬化物。
E’/(273+T1/3)<7 ・・・(c)
(数式(c)中、E’は、30℃で測定した貯蔵弾性率であり、T1は、得られた損失正接のピークトップの温度である。)
E’(T1-20)>20×E’(T1+20)・・・(d)
(数式(d)中、E’は、30℃で測定した貯蔵弾性率であり、T1は、得られた損失正接のピークトップの温度である。) - 請求項12~14のいずれか一項に記載の硬化物を含む電子部材。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13825198.8A EP2881414B1 (en) | 2012-07-31 | 2013-07-31 | Epoxy resin composition and cured article |
KR1020157000432A KR101758535B1 (ko) | 2012-07-31 | 2013-07-31 | 에폭시 수지 조성물, 에폭시 수지 및 경화물 |
JP2014528198A JP5860151B2 (ja) | 2012-07-31 | 2013-07-31 | エポキシ樹脂組成物、エポキシ樹脂、及び硬化物 |
US14/416,605 US9574045B2 (en) | 2012-07-31 | 2013-07-31 | Epoxy resin composition, epoxy resin, and cured product |
SG11201500414SA SG11201500414SA (en) | 2012-07-31 | 2013-07-31 | Epoxy resin composition, epoxy resin, and cured product |
CN201380039499.0A CN104487475B (zh) | 2012-07-31 | 2013-07-31 | 环氧树脂组合物、环氧树脂和固化物 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012170493 | 2012-07-31 | ||
JP2012-170493 | 2012-07-31 | ||
JP2012184476 | 2012-08-23 | ||
JP2012-184476 | 2012-08-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014021386A1 true WO2014021386A1 (ja) | 2014-02-06 |
Family
ID=50028056
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/070774 WO2014021386A1 (ja) | 2012-07-31 | 2013-07-31 | エポキシ樹脂組成物、エポキシ樹脂、及び硬化物 |
Country Status (8)
Country | Link |
---|---|
US (1) | US9574045B2 (ja) |
EP (1) | EP2881414B1 (ja) |
JP (1) | JP5860151B2 (ja) |
KR (1) | KR101758535B1 (ja) |
CN (1) | CN104487475B (ja) |
SG (1) | SG11201500414SA (ja) |
TW (1) | TWI502016B (ja) |
WO (1) | WO2014021386A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9051465B1 (en) | 2012-02-21 | 2015-06-09 | Park Electrochemical Corporation | Thermosetting resin composition containing a polyphenylene ether and a brominated fire retardant compound |
US9243164B1 (en) | 2012-02-21 | 2016-01-26 | Park Electrochemical Corporation | Thermosetting resin composition containing a polyphenylene ether and a brominated fire retardant compound |
JP2017110128A (ja) * | 2015-12-17 | 2017-06-22 | Dic株式会社 | 熱硬化性接着シート、物品及び物品の製造方法 |
JP2017128657A (ja) * | 2016-01-20 | 2017-07-27 | 日立化成株式会社 | 封止用エポキシ樹脂組成物、半導体装置及びその製造方法 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10141084B2 (en) * | 2010-10-08 | 2018-11-27 | Cheil Industries, Inc. | Electronic device |
CN105849187A (zh) * | 2014-07-18 | 2016-08-10 | 积水化学工业株式会社 | 半导体元件保护用材料及半导体装置 |
KR101704793B1 (ko) * | 2016-07-12 | 2017-02-08 | 김인섭 | 에폭시 수지 조성물을 이용한 회로기판과 그 제조방법 |
US10703854B2 (en) | 2017-12-05 | 2020-07-07 | Raytheon Technologies Corporation | Epoxy formula for integral capacitance probe |
US10800948B2 (en) * | 2018-08-02 | 2020-10-13 | Xerox Corporation | Conductive adhesive compositions and method for the same |
CN111640567B (zh) * | 2020-05-29 | 2022-02-11 | 深圳顺络电子股份有限公司 | 一种软磁合金材料的制备方法及软磁合金材料 |
CN112979925B (zh) * | 2021-02-24 | 2022-10-18 | 中国工程物理研究院化工材料研究所 | 一种中低温固化型环氧类玻璃高分子 |
CN114045137A (zh) * | 2022-01-12 | 2022-02-15 | 武汉市三选科技有限公司 | 面板驱动电路底部填充胶、其制备方法及芯片封装结构 |
Citations (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62141083A (ja) | 1985-12-13 | 1987-06-24 | Sony Chem Kk | フイルム状熱硬化型接着剤 |
JPH01113480A (ja) | 1987-10-27 | 1989-05-02 | Sony Chem Corp | 熱硬化型異方性導電接着剤 |
JPH01275621A (ja) * | 1988-04-27 | 1989-11-06 | New Japan Chem Co Ltd | エポキシ樹脂組成物 |
WO1992006116A1 (en) | 1990-09-28 | 1992-04-16 | Ortho Pharmaceutical Corporation | Hybrid growth factors |
JPH0543661A (ja) | 1991-08-14 | 1993-02-23 | Matsushita Electric Ind Co Ltd | 一液型熱硬化性エポキシ樹脂組成物 |
JPH05295329A (ja) | 1992-04-20 | 1993-11-09 | Hitachi Chem Co Ltd | フィルム状接着剤の製造方法 |
JPH06136244A (ja) | 1992-10-23 | 1994-05-17 | Furukawa Electric Co Ltd:The | エポキシ樹脂組成物 |
JPH07304931A (ja) | 1994-05-13 | 1995-11-21 | Taiyo Ink Mfg Ltd | 熱硬化性樹脂組成物並びに該組成物を用いた多層プリント配線板及びその製造方法 |
JPH0864960A (ja) | 1994-08-22 | 1996-03-08 | Sumitomo Bakelite Co Ltd | 多層プリント配線板の製造方法 |
JPH08333357A (ja) * | 1995-06-09 | 1996-12-17 | Asahi Chiba Kk | 新規グリシジル化合物および該化合物を含有する硬化性組成物 |
JPH0971633A (ja) | 1995-09-07 | 1997-03-18 | Mitsubishi Rayon Co Ltd | プリプレグ用エポキシ樹脂組成物 |
JPH1077330A (ja) * | 1996-09-03 | 1998-03-24 | Nippon Kayaku Co Ltd | エポキシ樹脂、エポキシ樹脂組成物及びその硬化物 |
JPH10237410A (ja) | 1997-02-27 | 1998-09-08 | Hitachi Chem Co Ltd | 熱伝導性接着剤組成物及び該組成物を用いた熱伝導性接着フィルム |
WO1998044017A1 (fr) | 1997-03-27 | 1998-10-08 | Mitsubishi Rayon Co., Ltd. | Composition de resine epoxyde pour plastique renforce de fibre de verre, preimpregne et moulage tubulaire produit au moyen de cette composition |
JPH11323247A (ja) | 1998-05-13 | 1999-11-26 | Nippon Petrochem Co Ltd | 防食塗料組成物 |
JP2000003987A (ja) | 1998-06-16 | 2000-01-07 | Sumitomo Metal Mining Co Ltd | 熱伝導性樹脂ペースト |
WO2000064960A1 (en) | 1999-04-22 | 2000-11-02 | Ajinomoto Co., Inc. | Thermosetting resin composition and flexible-circuit overcoating material comprising the same |
JP2001302759A (ja) * | 2000-04-25 | 2001-10-31 | Matsushita Electric Works Ltd | 液状封止用エポキシ樹脂組成物及び半導体装置 |
JP2002226675A (ja) | 2001-02-05 | 2002-08-14 | Toshiba Chem Corp | 絶縁性ペースト |
JP2002332328A (ja) | 2001-05-10 | 2002-11-22 | Nisshinbo Ind Inc | 射出成形用コンパウンドおよび燃料電池セパレータの製造方法 |
JP2003201334A (ja) * | 2002-01-07 | 2003-07-18 | Asahi Denka Kogyo Kk | エポキシ樹脂組成物 |
JP2003246838A (ja) | 2002-02-27 | 2003-09-05 | Arakawa Chem Ind Co Ltd | エポキシ樹脂組成物、電子材料用樹脂組成物、電子材料用樹脂、コーティング剤およびコーティング剤硬化膜の製造方法 |
JP2003246837A (ja) | 2002-02-26 | 2003-09-05 | Asahi Kasei Epoxy Kk | エポキシ樹脂および硬化性樹脂組成物 |
JP2004075954A (ja) | 2002-08-22 | 2004-03-11 | Sumitomo Bakelite Co Ltd | 燃料電池セパレーター用エポキシ樹脂組成物 |
JP2005113103A (ja) | 2003-10-06 | 2005-04-28 | Toho Chem Ind Co Ltd | エポキシ塗料組成物 |
JP2006137838A (ja) | 2004-11-11 | 2006-06-01 | Fujikura Ltd | エポキシ系樹脂組成物、エポキシ樹脂系接着剤組成物、フレキシブルプリント回路基板用カバーレイ、フレキシブルプリント回路基板用銅張積層板、フレキシブルプリント回路基板、プリプレグ、銅張積層板、感光性ドライフィルム、感光性液状レジスト、プリント配線板 |
JP2008250305A (ja) | 2007-03-05 | 2008-10-16 | Nippon Shokubai Co Ltd | ソルダーレジスト、そのドライフィルム及び硬化物ならびにプリント配線板 |
JP2009203425A (ja) * | 2008-02-29 | 2009-09-10 | Sanyo Chem Ind Ltd | グリシジルエーテルの製造方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002088229A (ja) | 2000-09-18 | 2002-03-27 | Asahi Denka Kogyo Kk | 水性樹脂組成物 |
JP2004083839A (ja) | 2001-12-19 | 2004-03-18 | Asahi Denka Kogyo Kk | 低温硬化性エポキシ樹脂およびその製造方法、並びにこれを用いた粉体塗料用組成物 |
JP2009107992A (ja) * | 2007-10-31 | 2009-05-21 | Sanyo Chem Ind Ltd | 精製グリシジル化物の製造方法及び精製グリシジル化物 |
JP2013538918A (ja) * | 2010-09-30 | 2013-10-17 | ダウ グローバル テクノロジーズ エルエルシー | エポキシ樹脂アダクトおよびその熱硬化樹脂 |
WO2013006250A1 (en) * | 2011-07-01 | 2013-01-10 | Dow Global Technologies Llc | Hybrid epoxy resin adducts |
-
2013
- 2013-07-31 EP EP13825198.8A patent/EP2881414B1/en active Active
- 2013-07-31 KR KR1020157000432A patent/KR101758535B1/ko active IP Right Grant
- 2013-07-31 JP JP2014528198A patent/JP5860151B2/ja active Active
- 2013-07-31 WO PCT/JP2013/070774 patent/WO2014021386A1/ja active Application Filing
- 2013-07-31 SG SG11201500414SA patent/SG11201500414SA/en unknown
- 2013-07-31 TW TW102127491A patent/TWI502016B/zh active
- 2013-07-31 CN CN201380039499.0A patent/CN104487475B/zh active Active
- 2013-07-31 US US14/416,605 patent/US9574045B2/en active Active
Patent Citations (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62141083A (ja) | 1985-12-13 | 1987-06-24 | Sony Chem Kk | フイルム状熱硬化型接着剤 |
JPH01113480A (ja) | 1987-10-27 | 1989-05-02 | Sony Chem Corp | 熱硬化型異方性導電接着剤 |
JPH01275621A (ja) * | 1988-04-27 | 1989-11-06 | New Japan Chem Co Ltd | エポキシ樹脂組成物 |
WO1992006116A1 (en) | 1990-09-28 | 1992-04-16 | Ortho Pharmaceutical Corporation | Hybrid growth factors |
JPH0543661A (ja) | 1991-08-14 | 1993-02-23 | Matsushita Electric Ind Co Ltd | 一液型熱硬化性エポキシ樹脂組成物 |
JPH05295329A (ja) | 1992-04-20 | 1993-11-09 | Hitachi Chem Co Ltd | フィルム状接着剤の製造方法 |
JPH06136244A (ja) | 1992-10-23 | 1994-05-17 | Furukawa Electric Co Ltd:The | エポキシ樹脂組成物 |
JPH07304931A (ja) | 1994-05-13 | 1995-11-21 | Taiyo Ink Mfg Ltd | 熱硬化性樹脂組成物並びに該組成物を用いた多層プリント配線板及びその製造方法 |
JPH0864960A (ja) | 1994-08-22 | 1996-03-08 | Sumitomo Bakelite Co Ltd | 多層プリント配線板の製造方法 |
JPH08333357A (ja) * | 1995-06-09 | 1996-12-17 | Asahi Chiba Kk | 新規グリシジル化合物および該化合物を含有する硬化性組成物 |
JPH0971633A (ja) | 1995-09-07 | 1997-03-18 | Mitsubishi Rayon Co Ltd | プリプレグ用エポキシ樹脂組成物 |
JPH1077330A (ja) * | 1996-09-03 | 1998-03-24 | Nippon Kayaku Co Ltd | エポキシ樹脂、エポキシ樹脂組成物及びその硬化物 |
JPH10237410A (ja) | 1997-02-27 | 1998-09-08 | Hitachi Chem Co Ltd | 熱伝導性接着剤組成物及び該組成物を用いた熱伝導性接着フィルム |
WO1998044017A1 (fr) | 1997-03-27 | 1998-10-08 | Mitsubishi Rayon Co., Ltd. | Composition de resine epoxyde pour plastique renforce de fibre de verre, preimpregne et moulage tubulaire produit au moyen de cette composition |
JPH11323247A (ja) | 1998-05-13 | 1999-11-26 | Nippon Petrochem Co Ltd | 防食塗料組成物 |
JP2000003987A (ja) | 1998-06-16 | 2000-01-07 | Sumitomo Metal Mining Co Ltd | 熱伝導性樹脂ペースト |
WO2000064960A1 (en) | 1999-04-22 | 2000-11-02 | Ajinomoto Co., Inc. | Thermosetting resin composition and flexible-circuit overcoating material comprising the same |
JP2001302759A (ja) * | 2000-04-25 | 2001-10-31 | Matsushita Electric Works Ltd | 液状封止用エポキシ樹脂組成物及び半導体装置 |
JP2002226675A (ja) | 2001-02-05 | 2002-08-14 | Toshiba Chem Corp | 絶縁性ペースト |
JP2002332328A (ja) | 2001-05-10 | 2002-11-22 | Nisshinbo Ind Inc | 射出成形用コンパウンドおよび燃料電池セパレータの製造方法 |
JP2003201334A (ja) * | 2002-01-07 | 2003-07-18 | Asahi Denka Kogyo Kk | エポキシ樹脂組成物 |
JP2003246837A (ja) | 2002-02-26 | 2003-09-05 | Asahi Kasei Epoxy Kk | エポキシ樹脂および硬化性樹脂組成物 |
JP2003246838A (ja) | 2002-02-27 | 2003-09-05 | Arakawa Chem Ind Co Ltd | エポキシ樹脂組成物、電子材料用樹脂組成物、電子材料用樹脂、コーティング剤およびコーティング剤硬化膜の製造方法 |
JP2004075954A (ja) | 2002-08-22 | 2004-03-11 | Sumitomo Bakelite Co Ltd | 燃料電池セパレーター用エポキシ樹脂組成物 |
JP2005113103A (ja) | 2003-10-06 | 2005-04-28 | Toho Chem Ind Co Ltd | エポキシ塗料組成物 |
JP2006137838A (ja) | 2004-11-11 | 2006-06-01 | Fujikura Ltd | エポキシ系樹脂組成物、エポキシ樹脂系接着剤組成物、フレキシブルプリント回路基板用カバーレイ、フレキシブルプリント回路基板用銅張積層板、フレキシブルプリント回路基板、プリプレグ、銅張積層板、感光性ドライフィルム、感光性液状レジスト、プリント配線板 |
JP2008250305A (ja) | 2007-03-05 | 2008-10-16 | Nippon Shokubai Co Ltd | ソルダーレジスト、そのドライフィルム及び硬化物ならびにプリント配線板 |
JP2009203425A (ja) * | 2008-02-29 | 2009-09-10 | Sanyo Chem Ind Ltd | グリシジルエーテルの製造方法 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9051465B1 (en) | 2012-02-21 | 2015-06-09 | Park Electrochemical Corporation | Thermosetting resin composition containing a polyphenylene ether and a brominated fire retardant compound |
US9243164B1 (en) | 2012-02-21 | 2016-01-26 | Park Electrochemical Corporation | Thermosetting resin composition containing a polyphenylene ether and a brominated fire retardant compound |
JP2017110128A (ja) * | 2015-12-17 | 2017-06-22 | Dic株式会社 | 熱硬化性接着シート、物品及び物品の製造方法 |
JP2017128657A (ja) * | 2016-01-20 | 2017-07-27 | 日立化成株式会社 | 封止用エポキシ樹脂組成物、半導体装置及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
TW201412865A (zh) | 2014-04-01 |
JP5860151B2 (ja) | 2016-02-16 |
EP2881414A1 (en) | 2015-06-10 |
TWI502016B (zh) | 2015-10-01 |
CN104487475B (zh) | 2017-04-12 |
US20150183924A1 (en) | 2015-07-02 |
US9574045B2 (en) | 2017-02-21 |
EP2881414A4 (en) | 2015-07-15 |
JPWO2014021386A1 (ja) | 2016-07-21 |
KR20150029690A (ko) | 2015-03-18 |
KR101758535B1 (ko) | 2017-07-14 |
EP2881414B1 (en) | 2018-07-11 |
CN104487475A (zh) | 2015-04-01 |
SG11201500414SA (en) | 2015-04-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5860151B2 (ja) | エポキシ樹脂組成物、エポキシ樹脂、及び硬化物 | |
TWI425019B (zh) | Liquid epoxy resin, epoxy resin composition and hardened product | |
TWI445726B (zh) | Epoxy resin, epoxy resin composition and hardened product thereof | |
JPWO2008020594A1 (ja) | 変性液状エポキシ樹脂、並びにそれを用いたエポキシ樹脂組成物及びその硬化物 | |
JP5142180B2 (ja) | エポキシ樹脂組成物、およびその硬化物 | |
JP2000007891A (ja) | 新規液状エポキシ樹脂組成物、その硬化物並びに半導体封止装置 | |
JP5368707B2 (ja) | 液状エポキシ樹脂、エポキシ樹脂組成物、および硬化物 | |
JP5734603B2 (ja) | フェノール性樹脂、エポキシ樹脂、それらの製造方法、エポキシ樹脂組成物及び硬化物 | |
JP2000007757A (ja) | 新規エポキシ樹脂 | |
JP4259834B2 (ja) | エポキシ樹脂、エポキシ樹脂組成物及びその硬化物 | |
WO2013035808A1 (ja) | エポキシ樹脂、エポキシ樹脂組成物、およびその硬化物 | |
JP3907140B2 (ja) | 変性エポキシ樹脂、エポキシ樹脂組成物及びその硬化物 | |
WO2005078001A1 (ja) | エポキシ樹脂の製造方法、エポキシ樹脂組成物及び硬化物 | |
JP2016008218A (ja) | エポキシ樹脂及びその組成物、並びに化合物 | |
JP4942384B2 (ja) | エポキシ樹脂、硬化性樹脂組成物、およびその硬化物 | |
JP2010053293A (ja) | エポキシ樹脂組成物 | |
JP5299976B2 (ja) | 変性エポキシ樹脂及びエポキシ樹脂組成物 | |
JP4404821B2 (ja) | 変性エポキシ樹脂、エポキシ樹脂組成物及びその硬化物 | |
JP5131961B2 (ja) | エポキシ樹脂、エポキシ樹脂組成物、およびその硬化物 | |
JP2010001379A (ja) | エポキシ樹脂、エポキシ樹脂組成物、およびその硬化物 | |
JP4776446B2 (ja) | エポキシ樹脂、エポキシ樹脂組成物、およびその硬化物 | |
JP2000007756A (ja) | エポキシ樹脂、エポキシ樹脂組成物及びその硬化物 | |
JP2007254581A (ja) | エポキシ樹脂、エポキシ樹脂組成物及びその硬化物 | |
JPH09157351A (ja) | エポキシ樹脂、エポキシ樹脂組成物及びその硬化物 | |
JP2007045978A (ja) | エポキシ樹脂、エポキシ樹脂組成物、およびその硬化物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13825198 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014528198 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20157000432 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14416605 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013825198 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |