WO2014199655A1 - リン原子含有活性エステル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム - Google Patents
リン原子含有活性エステル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム Download PDFInfo
- Publication number
- WO2014199655A1 WO2014199655A1 PCT/JP2014/052743 JP2014052743W WO2014199655A1 WO 2014199655 A1 WO2014199655 A1 WO 2014199655A1 JP 2014052743 W JP2014052743 W JP 2014052743W WO 2014199655 A1 WO2014199655 A1 WO 2014199655A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- active ester
- epoxy resin
- carbon atoms
- phosphorus atom
- Prior art date
Links
- 0 CC(*)P1(Oc(cccc2)c2-c2ccccc12)=O Chemical compound CC(*)P1(Oc(cccc2)c2-c2ccccc12)=O 0.000 description 3
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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/423—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof containing an atom other than oxygen belonging to a functional groups to C08G59/42, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Definitions
- the present invention provides a phosphorus atom-containing active ester resin having all of flame retardancy, heat resistance, and dielectric properties in a cured product, an epoxy resin composition using the same as a curing agent, a cured product thereof, a prepreg, a circuit board, and Related to build-up film.
- a curable resin composition comprising an epoxy resin and its curing agent is widely used as an insulating material for semiconductor encapsulants and printed wiring boards because the cured product is excellent in heat resistance, moisture resistance, insulation, and the like. Yes.
- the problem to be solved by the present invention is a phosphorus atom-containing active ester resin having all of flame retardancy, heat resistance and dielectric properties in a cured product, an epoxy resin composition using this as a curing agent, and curing thereof. It is to provide an object, a prepreg, a circuit board, and a build-up film.
- a structural unit ( ⁇ ) in which a plurality of aromatic nuclei (X) are knotted via an aliphatic cyclic hydrocarbon group is linked via an arylene carbonyloxy group As a result of intensive studies to solve the above problems, the present inventors have found that a structural unit ( ⁇ ) in which a plurality of aromatic nuclei (X) are knotted via an aliphatic cyclic hydrocarbon group is linked via an arylene carbonyloxy group.
- An active ester resin having a structure (I) knotted with another structural unit ( ⁇ ), wherein a part or all of the aromatic nucleus (X) present in the resin is represented by the following structural formulas (y1) to (y4): )
- R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
- R 5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a naphthyl group, an anthryl group, or 1 to 4 carbon atoms on the aromatic nucleus. Or a phenyl group, a naphthyl group, an anthryl group, or an aralkyl group having one or more alkyl groups or alkoxy groups.
- a structural unit ( ⁇ ) in which a plurality of aromatic nuclei (X) are knotted through an aliphatic cyclic hydrocarbon group is knotted with another structural unit ( ⁇ ) through an arylene carbonyloxy group.
- At least one of the aromatic nuclei (X) having the structure (I) and present in the resin is represented by the following structural formulas (y1) to (y4)
- R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
- R 5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a naphthyl group, an anthryl group, or 1 to 4 carbon atoms on the aromatic nucleus. Or a phenyl group, a naphthyl group, an anthryl group, or an aralkyl group having one or more alkyl groups or alkoxy groups.
- the present invention relates to a phosphorus atom-containing active ester resin characterized by having a structural moiety (Y) represented by any of the above as a substituent on an aromatic nucleus.
- the present invention further includes a phenolic compound (A) having a structure in which a plurality of aromatic nuclei (X) are knotted via an aliphatic cyclic hydrocarbon group, and an aromatic dicarboxylic acid or a dihalide (B) thereof,
- the total number of carboxyl groups or acid halide groups contained in the aromatic dicarboxylic acid or its dihalide (B) is in the range of 0.25 to 0.75 mol with respect to 1 mol in total of the hydroxyl groups contained in the functional compound (A).
- the phenol resin intermediate (C) is obtained by reacting at a ratio, and then the phenol resin intermediate (C), the aldehyde compound (D), and the following structural formula (e1) or (e2)
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. It is any one of an alkoxy group, a halogen atom, a phenyl group, and an aralkyl group, and z is a hydrogen atom or a hydroxyl group.
- the present invention further relates to a phosphorus atom-containing active ester resin obtained by the production method.
- the present invention further relates to an epoxy resin composition containing the novel active ester resin and an epoxy resin.
- the present invention further relates to a cured product obtained by curing the epoxy resin composition.
- the present invention further relates to a prepreg obtained by impregnating a reinforcing base material with the epoxy resin composition diluted in an organic solvent and semi-curing the resulting impregnated base material.
- the present invention further relates to a circuit board obtained by obtaining a varnish obtained by diluting the epoxy resin composition in an organic solvent, and heating and press-molding a varnish shaped into a plate shape and a copper foil.
- the present invention further relates to a build-up film obtained by applying a solution obtained by diluting the epoxy resin composition in an organic solvent on a base film and drying it.
- a phosphorus atom-containing active ester resin having all of flame retardancy, heat resistance, and dielectric properties in a cured product, an epoxy resin composition using this as a curing agent, a cured product thereof, a prepreg, and a circuit board , And build-up films can be provided.
- FIG. 1 is a GPC chart of the active ester resin (1) obtained in Synthesis Example 1.
- FIG. FIG. 2 is a 13 C-NMR chart of the active ester resin (1) obtained in Synthesis Example 1.
- FIG. 3 is a MALDI-MS spectrum of the active ester resin (1) obtained in Synthesis Example 1.
- 4 is a GPC chart of the phosphorus atom-containing active ester resin (1) obtained in Example 1.
- FIG. 5 is a GPC chart of the phosphorus atom-containing active ester resin (2) obtained in Example 2.
- the structural unit ( ⁇ ) in which a plurality of aromatic nuclei (X) are knotted via an aliphatic cyclic hydrocarbon group is bonded to another structural unit (arylene carbonyloxy group).
- ⁇ )) and at least one of the aromatic nuclei (X) present in the resin has the structure (I) and the following structural formulas (y1) to (y4)
- R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
- R 5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a naphthyl group, an anthryl group, or 1 to 4 carbon atoms on the aromatic nucleus. Or a phenyl group, a naphthyl group, an anthryl group, or an aralkyl group having one or more alkyl groups or alkoxy groups.
- It has the structure part (Y) represented by either of these as a substituent on an aromatic nucleus, It is characterized by the above-mentioned.
- the arylene carbonyloxy group is a so-called active ester group, which is cured by blocking the secondary hydroxyl group generated during the curing reaction with the epoxy resin by the ester residue.
- the dielectric constant and dielectric loss tangent of the object can be reduced.
- the structural site (Y) represented by the structural formulas (y1) to (y4) has a structure containing a phosphorus atom and a high aromatic ring concentration. This contributes to the effect of improving the flame retardancy of the resin.
- Conventionally known active ester resins having an aliphatic cyclic hydrocarbon group in the molecular structure are excellent in dielectric properties in cured products, but are easy to burn and have insufficient heat resistance.
- a resin having a bulky substituent structure such as the structural formulas (y1) to (y4) has a lower concentration of active groups involved in the curing reaction than a resin having no such substituent. Therefore, the heat resistance of the cured product tends to be inferior, and the phosphorus atom-containing active ester resin of the present invention has not only dielectric properties and flame retardancy but also excellent heat resistance, and has various performances. It is a resin material.
- the structural unit ( ⁇ ) in which a plurality of aromatic nuclei (X) are linked via an aliphatic cyclic hydrocarbon group of the phosphorus atom-containing active ester resin of the present invention contains, for example, two double bonds in one molecule. And a structure obtained by polyaddition reaction of an unsaturated aliphatic cyclic hydrocarbon compound and a phenolic compound.
- the aromatic nucleus (X) in the phosphorus atom-containing active ester resin is derived from the phenolic compound. Will be.
- the unsaturated aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule includes, for example, dicyclopentadiene, cyclopentadiene multimer, tetrahydroindene, 4-vinylcyclohexene, 5-vinyl-2-norbornene. , Limonene and the like, and each may be used alone or in combination of two or more.
- dicyclopentadiene is preferable because a cured product having high heat resistance can be obtained.
- dicyclopentadiene is contained in petroleum fractions, industrial dicyclopentadiene may contain cyclopentadiene multimers or other aliphatic or aromatic diene compounds as impurities.
- the phenolic compound is, for example, phenol, cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, 1-naphthol, 2-naphthol, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, etc. You may use, and may use 2 or more types together. Among these, phenol is preferable because it becomes a phosphorus atom-containing active ester resin having excellent curability.
- the phosphorus atom-containing active ester resin of the present invention has an arylene carbonyloxy group as a nodule group of the structural unit ( ⁇ ).
- the arylene carbonyloxy group include a benzene-1,2-dicarbonyloxy group, a benzene-1,3-dicarbonyloxy group, a benzene-1,4-dicarbonyloxy group, and a naphthalene-1,4-di Carbonyloxy groups, naphthalene-2,3-dicarbonyloxy groups, naphthalene-2,6-dicarbonyloxy groups, naphthalene-2,7-dicarbonyloxy groups, and alkyls having 1 to 4 carbon atoms in these aromatic nuclei Examples thereof include those substituted with a group or an alkoxy group.
- a phosphorus atom-containing active ester resin having excellent curability is obtained, and since it is easy to produce, it is a benzene-1,3-dicarbonyloxy group or a benzene-1,4-dicarbonyloxy group. Is preferable, and a benzene-1,3-dicarbonyloxy group is more preferable.
- At least one of the aromatic nuclei (X) has the following structural formulas (y1) to (y4)
- R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
- R 5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a naphthyl group, an anthryl group, or 1 to 4 carbon atoms on the aromatic nucleus. Or a phenyl group, a naphthyl group, an anthryl group, or an aralkyl group having one or more alkyl groups or alkoxy groups.
- the structural site (Y) represented by any of the above has a substituent on the aromatic nucleus.
- R 1 , R 2 , R 3 and R 4 are all preferably hydrogen atoms because they are excellent in heat resistance in the cured product.
- R 5 in the structural formulas (y1) to (y4) provides a cured product excellent in flame retardancy and heat resistance in the cured product, so that phenyl group, naphthyl group, anthryl group, aromatic nucleus It is preferably a phenyl group having one or more alkyl groups or alkoxy groups of 1 to 4 carbon atoms, a naphthyl group or an anthryl group, and a phenyl group having one or more alkoxy groups on the aromatic nucleus It is more preferable that
- the aliphatic cyclic hydrocarbon group is [Z]
- the aromatic nucleus (X) is [X]
- the arylene carbonyloxy group is [V].
- At least one of [X] in the general formula (1) has a molecular structure having the structural site (Y) as a substituent on the aromatic nucleus.
- the structural unit ( ⁇ ) in which a plurality of aromatic nuclei (X) are linked via an aliphatic cyclic hydrocarbon group, which the phosphorus atom-containing active ester resin of the present invention has, has a double bond in one molecule mentioned above.
- molecules Two aromatic nuclei located at the terminal have phenolic hydroxyl groups.
- a plurality of aromatic nuclei At least one of the two aromatic nuclei positioned at the terminal of the structure (I) is a structural site (Y) represented by any one of the above (y1) to (y4) as a substituent on the aromatic nuclei. It is preferable to have.
- m in the general formula (1) is preferably 0 because the phosphorus atom-containing active ester resin is excellent in solvent solubility.
- the more preferred molecular structure of the phosphorus atom-containing active ester resin of the present invention is specifically the following structural formula (2)
- R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a phenyl group or an aralkyl group.
- Y is a hydrogen atom or the following structural formulas (y1) to (y4)
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
- R 5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a naphthyl group, an anthryl group, or 1 to 4 carbon atoms on the aromatic nucleus. Or a phenyl group, a naphthyl group, an anthryl group, or an aralkyl group having one or more alkyl groups or alkoxy groups.
- At least one of two Ys in the molecular structure is a structural part represented by any one of the structural formulas (y1) to (y4).
- K is 0 or 1
- 1 is 0.25 to 1.5 on the average of repeating units. ] The thing represented by is mentioned.
- l represents an average value of repeating units, and becomes a phosphorus atom-containing active ester resin that is excellent in solubility in various solvents, and is preferably in the range of 0.25 to 1.5.
- the range of 0.25 to 1.2 is more preferable.
- the phosphorus atom-containing active ester resin of the present invention preferably has a phosphorus atom content in the range of 2.0 to 5.0% by mass because of excellent flame retardancy.
- the phosphorus atom-containing active ester resin of the present invention has high solubility in various organic solvents, and since it is excellent in any performance of dielectric properties, heat resistance, and flame retardancy in a cured product,
- the softening point is preferably in the range of 100 to 250 ° C.
- the active group equivalent of the phosphorus atom-containing active ester resin of the present invention is excellent in curability, dielectric constant and dielectric constant when the total number of arylcarbonyloxy groups and phenolic hydroxyl groups in the resin structure is the number of functional groups of the resin. Since a cured product having a low tangent is obtained, 240 to 450 g / eq. In the range of 260 to 400 g / eq. More preferably, it is the range.
- the phosphorus atom-containing active ester resin of the present invention can be produced, for example, by the following method. That is, a phenolic compound (A) having a structure in which a plurality of aromatic nuclei having a phenolic hydroxyl group are linked via an aliphatic cyclic hydrocarbon group, and an aromatic dicarboxylic acid or a dihalide thereof (B) The total number of carboxyl groups or acid halide groups contained in the aromatic dicarboxylic acid or its dihalide (B) is in the range of 0.25 to 0.75 mol with respect to 1 mol in total of the hydroxyl groups contained in the functional compound (A).
- the phenol resin intermediate (C), the aldehyde compound (D), and the following step (hereinafter abbreviated as “Step 1”) are obtained by reacting at a ratio.
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. It is any one of an alkoxy group, a halogen atom, a phenyl group, and an aralkyl group, and z is a hydrogen atom or a hydroxyl group.
- the method of manufacturing by the process (henceforth abbreviated as "the process 2") with which the phosphorus atom containing compound (E) represented by either is made to react is mentioned.
- the phenolic compound (A) having a structure in which a plurality of aromatic nuclei (X) are knotted through the aliphatic cyclic hydrocarbon group used in the step 1 is, for example, a non-containing compound containing two double bonds in one molecule. Examples thereof include those obtained by polyaddition reaction of a saturated aliphatic cyclic hydrocarbon compound and a phenolic compound.
- the unsaturated aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule includes, for example, dicyclopentadiene, cyclopentadiene multimer, tetrahydroindene, 4-vinylcyclohexene, 5-vinyl-2-norbornene. , Limonene and the like, and each may be used alone or in combination of two or more.
- dicyclopentadiene is preferable because a cured product having high heat resistance can be obtained.
- dicyclopentadiene is contained in petroleum fractions, industrial dicyclopentadiene may contain cyclopentadiene multimers or other aliphatic or aromatic diene compounds as impurities.
- the phenolic compound is, for example, phenol, cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, 1-naphthol, 2-naphthol, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, etc. You may use, and may use 2 or more types together. Among these, phenol is preferable because it becomes a phosphorus atom-containing active ester resin having excellent curability.
- the aromatic dicarboxylic acid or its halide (B) used in Step 1 is, for example, isophthalic acid, terephthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6.
- isophthalic acid dichloride or terephthalic acid dichloride is preferable, and isophthalic acid dichloride. Is more preferable.
- the step 1 can be performed, for example, under the temperature condition of 40 to 65 ° C. in the presence of an alkali catalyst.
- alkali catalyst examples include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. Among these, sodium hydroxide or potassium hydroxide is preferable because of high reaction efficiency. These catalysts may be used as a 3.0 to 30% aqueous solution.
- the step 1 is preferably performed in an organic solvent because the reaction can be easily controlled.
- organic solvent used herein include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, cellosolve, butyl carbitol, and the like.
- Examples thereof include carbitol solvents, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.
- Step 1 After completion of Step 1, when an aqueous solution of an alkali catalyst is used, the reaction solution is allowed to stand and remove the aqueous layer, and the remaining organic layer is washed with water until the aqueous layer becomes almost neutral. By repeating the water washing, the phenol resin intermediate (C) can be obtained.
- the aliphatic cyclic hydrocarbon group is [Z]
- the aromatic nucleus (X) is [X]
- the arylene carbonyloxy group is [ V]
- a value obtained by multiplying the number average molecular weight (Mn) obtained as a result of the GPC measurement by this average value is used as an average molecular weight, and a value l corresponding to the average molecular weight is calculated.
- GPC measurement conditions Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation Column: Guard column “HXL-L” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + Tosoh Corporation “TSK-GEL G3000HXL” + “TSK-GEL G4000HXL” manufactured by Tosoh Corporation Detector: RI (Differential refraction diameter)
- Data processing “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation Measurement conditions: Column temperature 40 ° C Developing solvent Tetrahydrofuran Flow rate 1.0 ml / min
- l obtained here is equivalent to l in the structural formula (2), which is a specific example of the phosphorus atom-containing active ester resin of the present invention, and has a phosphorus atom-containing active ester excellent in solubility in various solvents. Since it becomes a resin, it is preferably in the range of 0.25 to 1.5, and more preferably in the range of 0.25 to 1.2.
- step 2 the phenol resin intermediate (C) obtained in step 1, the aldehyde compound (D), and the following structural formula (e1) or (e2)
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. It is any one of an alkoxy group, a halogen atom, a phenyl group, and an aralkyl group, and z is a hydrogen atom or a hydroxyl group.
- a phosphorus atom-containing compound (E) represented by any one of
- the reaction ratio of the phenol resin intermediate (C), the aldehyde compound (D), and the phosphorus atom-containing compound (E) is any of dielectric properties, heat resistance, and flame retardancy in the cured product. Since a phosphorus atom-containing active ester resin having excellent performance can be obtained, the aromatic aldehyde (D) is 0.1 to 0.7 mol relative to 1 mol of the hydroxyl group contained in the phenol resin intermediate (C). The range is preferably such that the phosphorus atom-containing compound (E) is in the range of 0.1 to 0.7 mol.
- the aldehyde compound (D) is in the range of 0.2 to 0.6 mol and the phosphorus atom-containing compound (E) is 0.1 mol per mol of the hydroxyl group contained in the phenol resin intermediate (C).
- the ratio is more preferably in the range of 2 to 0.6 mol.
- the aldehyde compound (D) used in Step 2 is, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentylaldehyde, hexylaldehyde, cyclohexylaldehyde, benzaldehyde, o-tolualdehyde, p-tolualdehyde, o-ethyl.
- Examples thereof include those having an alkoxy group as a substituent of an aromatic aldehyde such as aldehyde, p-ethyl aldehyde, p-isopropyl aldehyde, naphthaldehyde, anthracene aldehyde, and phenylacetaldehyde.
- an aromatic aldehyde having an alkoxy group on the aromatic nucleus is preferable because a phosphorus atom-containing active ester resin having excellent heat resistance in the cured product is obtained.
- R is an alkyl group having 1 to 4 carbon atoms
- R 5 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- n is the number of substituents OR on the aromatic nucleus, and 1 to 3 Integer
- n 1
- R is a methyl group
- para anisaldehyde in which R 5 is a hydrogen atom is the other phenolic intermediate (C)
- the reactivity with the phosphorus atom-containing compound (E) is preferred.
- the phosphorus atom-containing compound (E) used in the step 2 is a compound that is laminated by the structural formula (e1) or (e2).
- Phenanthrene-10-oxide is preferable because of its excellent reactivity with the phenol resin intermediate (C) and the aromatic aldehyde (D), which are other reaction raw materials.
- the step 2 can be performed, for example, under a temperature condition of 140 to 200 ° C. in the presence of no catalyst or an acid catalyst.
- the reaction performed in Step 2 is highly reactive and proceeds sufficiently even under non-catalytic conditions.
- an acid catalyst may be used if necessary, specifically, an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, Examples thereof include organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride.
- the reaction in Step 2 is usually performed under solvent-free conditions, but may be performed in an organic solvent as necessary.
- organic solvent used herein include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, cellosolve, butyl carbitol, and the like.
- Examples thereof include carbitol solvents, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.
- the target phosphorus atom-containing active ester resin can be obtained by removing water under heating and decompression conditions.
- the epoxy resin composition of the present invention contains the aforementioned phosphorus atom-containing active ester resin and an epoxy resin as essential components.
- epoxy resin used in the present invention examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type.
- Epoxy resin triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol Condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol Fat type epoxy resins, biphenyl-modified novolak type epoxy resins.
- epoxy resins tetramethylbiphenol type epoxy resin, biphenyl aralkyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, and novolac type epoxy resin are used in that a cured product having excellent flame retardancy can be obtained.
- a dicyclopentadiene-phenol addition reaction type epoxy resin is preferable in that a cured product having excellent dielectric properties is obtained.
- the compounding amount of the phosphorus atom-containing active ester resin and the epoxy resin is excellent in curability, and a cured product having a low dielectric constant and dielectric loss tangent is obtained. It is preferable that the ratio of the epoxy groups in the epoxy resin is 0.8 to 1.2 equivalents with respect to a total of 1 equivalent of active groups in the resin.
- the active group in the phosphorus atom-containing active ester resin refers to an arylcarbonyloxy group and a phenolic hydroxyl group in the resin structure.
- curing agents used here are, for example, amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF 3 -amine complex, guanidine derivatives: dicyandiamide, linolenic acid 2
- Amide compounds such as polyamide resin synthesized from a monomer and ethylenediamine: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, Acid anhydrides such as hexahydrophthalic anhydride and methylhexahydrophthalic anhydride: phenol novol
- phenol novolac resins cresol novolak resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins Phenol aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, and aminotriazine-modified phenol resin are preferable.
- the amount used is preferably in the range of 10 to 50 parts by mass in a total of 100 parts by mass of the phosphorus atom-containing active ester resin and the other curing agent.
- the epoxy resin composition of the present invention may contain a curing accelerator as necessary.
- the curing accelerator used here include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like.
- dimethylaminopyridine and imidazole are preferable because of excellent heat resistance, dielectric characteristics, solder resistance, and the like.
- the organic solvent used for varnishing is an aromatic hydrocarbon solvent such as toluene or xylene, or a ketone such as acetone, methyl ethyl ketone, or cyclohexanone.
- Solvent acetate solvent such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, alcohol solvent such as ethanol, propanol, butanol, carbitol solvent such as cellosolve, butyl carbitol, dimethylformamide, Examples thereof include dimethylacetamide and N-methylpyrrolidone.
- the epoxy resin composition of the present invention is used for printed wiring board applications, it is preferably a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol, etc., and has a nonvolatile content of 40 to 80 It is preferable to use at a ratio of mass%.
- a polar solvent having a boiling point of 160 ° C. or lower such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol, etc.
- ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, etc.
- acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, ethanol, propanol
- an alcohol solvent such as butanol, a carbitol solvent such as cellosolve or butyl carbitol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone or the like, and a non-volatile content of 30 to 60% by mass is preferably used.
- a non-volatile content of 30 to 60% by mass is preferably used. preferable.
- the epoxy resin composition of the present invention may be used in combination with other thermosetting resins as needed.
- other thermosetting resins that can be used here include cyanate ester compounds, vinylbenzyl compounds, acrylic compounds, maleimide compounds, and copolymers of styrene and maleic anhydride.
- the amount used is not particularly limited as long as the effects of the present invention are not impaired, but is in the range of 1 to 50 parts by weight per 100 parts by weight of the epoxy resin composition. It is preferable.
- a non-halogen flame retardant containing substantially no halogen atom may be blended.
- non-halogen flame retardant examples include a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an inorganic flame retardant, an organic metal salt flame retardant, and the like. It is not intended to be used alone, and a plurality of the same type of flame retardants may be used, or different types of flame retardants may be used in combination.
- the phosphorous flame retardant can be either inorganic or organic.
- the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .
- the red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like.
- the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide
- a method of double coating with a resin may be used.
- organic phosphorus compounds examples include 9,10-dihydro, as well as general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-containing phosphorus compounds.
- the compounding amount of these phosphorus flame retardants is preferably in the range of 0.1 to 2.0 parts by mass in the case of using red phosphorus in 100 parts by mass of the epoxy resin composition. When used, it is preferably blended in the range of 0.1 to 10.0 parts by mass, and more preferably in the range of 0.5 to 6.0 parts by mass.
- the phosphorous flame retardant when using the phosphorous flame retardant, may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.
- nitrogen flame retardant examples include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.
- triazine compound examples include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, sulfuric acid such as guanylmelamine sulfate, melem sulfate, melam sulfate, etc.
- examples thereof include aminotriazine compounds, aminotriazine-modified phenol resins, and aminotriazine-modified phenol resins that are further modified with tung oil, isomerized linseed oil, and the like.
- cyanuric acid compound examples include cyanuric acid and melamine cyanurate.
- the compounding amount of the nitrogen-based flame retardant is preferably in the range of 0.05 to 10 parts by mass, for example, in the range of 0.1 to 5 parts by mass in 100 parts by mass of the epoxy resin composition. Is more preferable.
- a metal hydroxide, a molybdenum compound or the like may be used in combination.
- the silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.
- the compounding amount of the silicone flame retardant is preferably in the range of 0.05 to 20 parts by mass in 100 parts by mass of the epoxy resin composition, for example. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.
- inorganic flame retardant examples include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.
- metal hydroxide examples include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.
- metal oxide examples include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, Examples thereof include chromium oxide, nickel oxide, copper oxide, and tungsten oxide.
- metal carbonate compound examples include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.
- metal powder examples include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.
- Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.
- low melting point glass examples include, for example, Shipley (Bokusui Brown), hydrated glass SiO 2 —MgO—H 2 O, PbO—B 2 O 3 system, ZnO—P 2 O 5 —MgO system, and P 2 O. Glass forms such as 5- B 2 O 3 —PbO—MgO, P—Sn—O—F, PbO—V 2 O 5 —TeO 2 , Al 2 O 3 —H 2 O, lead borosilicate A compound can be mentioned.
- the amount of the inorganic flame retardant blended is, for example, preferably in the range of 0.05 to 20 parts by weight and in the range of 0.5 to 15 parts by weight in 100 parts by weight of the epoxy resin composition. Is more preferable.
- organic metal salt flame retardant examples include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound. And the like.
- the amount of the organometallic salt flame retardant is preferably in the range of 0.005 to 10 parts by mass, for example, in 100 parts by mass of the epoxy resin composition.
- the epoxy resin composition of the present invention can be blended with an inorganic filler as necessary.
- the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.
- fused silica When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica.
- the fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape.
- the filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 20% by mass or more with respect to the total amount of the thermosetting resin composition.
- electroconductive fillers such as silver powder and copper powder, can be used.
- the epoxy resin composition of the present invention may contain various compounding agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier, if necessary.
- the epoxy resin composition of the present invention is obtained by uniformly mixing the above-described components, and can be easily made into a cured product by a method similar to the curing of a conventionally known epoxy resin composition.
- the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.
- the epoxy resin composition of the present invention has a low dielectric constant and dielectric loss tangent of the cured product and is excellent in heat resistance and flame retardancy, it is a hard printed wiring board material, a resin composition for flexible wiring board, build It can be suitably used for various electronic material applications such as insulating materials for circuit boards such as interlayer insulating materials for up-boards, semiconductor sealing materials, conductive pastes, build-up adhesive films, resin casting materials, adhesives and the like.
- insulating materials for circuit boards such as interlayer insulating materials for up-boards, semiconductor sealing materials, conductive pastes, build-up adhesive films, resin casting materials, adhesives and the like.
- circuit board materials such as hard printed wiring board materials, resin compositions for flexible wiring boards, and interlayer insulation materials for build-up boards. It can be preferably used.
- a varnish obtained by diluting the epoxy resin composition of the present invention in an organic solvent is obtained, and this is formed into a plate shape, laminated with copper foil, and heated and pressed. Can be manufactured.
- a prepreg is obtained by impregnating a reinforcing base material with a varnish-like epoxy resin composition containing an organic solvent and semi-curing it, and copper foil is laminated on it and heated. It can be manufactured by a method of pressure bonding.
- the reinforcing substrate that can be used here include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth.
- the varnish-like epoxy resin composition described above is first heated at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C. to obtain a prepreg that is a cured product.
- the mass ratio of the thermosetting resin composition to be used and the reinforcing substrate is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60 mass%.
- the prepreg obtained as described above is laminated by a conventional method, and a copper foil is appropriately stacked, and heat-pressed at 170 to 250 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa, A target circuit board can be obtained.
- an epoxy resin composition containing an organic solvent is applied to an electrically insulating film using a coating machine such as a reverse roll coater or a comma coater.
- a coating machine such as a reverse roll coater or a comma coater.
- heating is performed at 60 to 170 ° C. for 1 to 15 minutes using a heater to volatilize the solvent, and the epoxy resin composition is B-staged.
- the metal foil is thermocompression bonded to the resin composition layer using a heating roll or the like.
- the pressure for pressure bonding is preferably 2 to 200 N / cm, and the temperature for pressure bonding is preferably 40 to 200 ° C. If sufficient adhesion performance can be obtained, the process may be completed here. However, if complete curing is required, post-curing is preferably performed at 100 to 200 ° C. for 1 to 24 hours.
- the thickness of the resin composition layer after final curing is preferably in the range of 5 to 100 ⁇ m.
- an epoxy resin composition appropriately blended with rubber, filler or the like is applied to a wiring board on which a circuit is formed by a spray coating method or curtain coating. After applying using a method or the like, it is cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness
- the plating method electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent.
- a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern.
- the through-hole portion is formed after the outermost resin insulating layer is formed.
- a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is heat-pressed at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and a plating process. It is also possible to produce a build-up board without the above.
- the method for producing an adhesive film for buildup from the epoxy resin composition of the present invention is, for example, an adhesive for multilayer printed wiring boards by applying the epoxy resin composition of the present invention on a support film to form a resin composition layer.
- the method of using a film is mentioned.
- the adhesive film is softened under the lamination temperature condition (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and simultaneously with the circuit board lamination, It is important to show fluidity (resin flow) capable of filling the via hole or through hole in the substrate, and it is preferable to blend the above-described components so as to exhibit such characteristics.
- lamination temperature condition usually 70 ° C. to 140 ° C.
- the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. Usually, it is preferable that the resin can be filled in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.
- the method for producing the adhesive film described above is, after preparing the varnish-like epoxy resin composition of the present invention, coating the varnish-like composition on the surface of the support film and further heating, or It can manufacture by drying an organic solvent by hot air spraying etc. and forming the layer ((alpha)) of an epoxy resin composition.
- the thickness of the layer ( ⁇ ) to be formed is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 ⁇ m, the thickness of the resin composition layer is preferably 10 to 100 ⁇ m.
- the said layer ((alpha)) may be protected with the protective film mentioned later.
- a protective film By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.
- the above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil.
- the support film and the protective film may be subjected to a release treatment in addition to the mat treatment and the corona treatment.
- the thickness of the support film is not particularly limited, but is usually 10 to 150 ⁇ m, preferably 25 to 50 ⁇ m.
- the thickness of the protective film is preferably 1 to 40 ⁇ m.
- the support film described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.
- the method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer ( ⁇ ) is protected with a protective film, Lamination is performed on one or both sides of the circuit board by, for example, vacuum laminating so that ⁇ ) is in direct contact with the circuit board.
- the laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.
- the lamination conditions are such that the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 1 to 11 kgf / cm 2 (9.8 ⁇ 10 4 to 107.9 ⁇ 10 4 N / m 2), Lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.
- the epoxy resin composition of the present invention is used as a conductive paste, for example, a method in which fine conductive particles are dispersed in an epoxy resin composition to form a composition for an anisotropic conductive film, a circuit that is liquid at room temperature
- a paste resin composition for connection and an anisotropic conductive adhesive examples thereof include a paste resin composition for connection and an anisotropic conductive adhesive.
- the epoxy resin composition of the present invention can also be used as a resist ink.
- a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent are blended in the epoxy resin composition, and further a pigment, talc, and filler are added to obtain a resist ink composition. Then, after apply
- Softening point measurement method compliant with JIS K7234.
- GPC Measured under the following conditions. Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation Column: Guard column “HXL-L” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + Tosoh Corporation “TSK-GEL G3000HXL” + “TSK-GEL G4000HXL” manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation Measurement conditions: Column temperature 40 ° C Developing solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of “GPC-8020 model II version 4.10”.
- MALDI-MS Measured by “AXIMA-TOF2” manufactured by Shimadzu Biotech.
- Production Example 1 Production of phenol resin intermediate (C1) Polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g / equivalent, to a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer (Softening point 85 ° C.) 165 parts by mass and 590 parts by mass of toluene were charged, and the inside of the system was purged with nitrogen under reduced pressure and dissolved. Next, 50 parts by mass of isophthalic acid chloride was charged, and then the inside of the system was controlled to 60 ° C.
- the softening point of the phenol resin intermediate (C1) was 125 ° C., the hydroxyl equivalent calculated from the amount of raw material charged was 395 g / equivalent, and the softening point was 125 ° C.
- the GPC chart of the obtained phenol resin intermediate (C1) is shown in FIG. 1, the C 13 NMR chart is shown in FIG. 2, and the MS spectrum is shown in FIG. A peak derived from the carbonyl carbon of the ester group was confirmed around 165 ppm by 13 C-NMR. Further, in the obtained phenol resin intermediate (C1), the value corresponding to l in the general formula (1) calculated from the GPC chart was 0.95.
- Example 1 Production of Phosphorus Atom-Containing Active Ester Resin (1) 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10- Into a flask equipped with a thermometer, condenser, fractionator, and stirrer 154 parts by mass of oxide, 97 parts by mass of p-anisaldehyde, and 395 parts by mass of a phenol resin intermediate (C1) were charged, and the mixture was heated to 90 ° C. and stirred while blowing nitrogen. Then, after heating up to 180 degreeC and stirring for 5 hours, it heated up further to 190 degreeC and stirred for 9 hours.
- a phenol resin intermediate C1
- a phosphorus atom-containing active ester resin (1) Water was removed from the reaction mixture under heating and reduced pressure to obtain a phosphorus atom-containing active ester resin (1).
- the obtained phosphorus atom-containing active ester resin (1) had a softening point of 180 ° C., an active group equivalent calculated from the amount of raw materials charged, 323 g / equivalent, and a phosphorus atom content of 3.6% by mass.
- the active group in a phosphorus atom containing active ester resin refers to the arylcarbonyloxy group and phenolic hydroxyl group which have in a resin structure.
- a GPC chart of the phosphorus atom-containing active ester resin (1) is shown in FIG.
- Example 2 Production of Phosphorus Atom-Containing Active Ester Resin (2) 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was changed to 216 parts by mass and p-anisaldehyde was changed to 136 parts by mass. Except for the above, a phosphorus atom-containing active ester resin (2) was obtained in the same manner as in Example 1. The obtained phosphorus atom-containing active ester resin (2) had a softening point of 200 ° C., an active group equivalent calculated from the amount of raw materials charged, 370 g / equivalent, and a phosphorus atom content of 4.4% by mass. A GPC chart of the phosphorus atom-containing active ester resin (2) is shown in FIG.
- Example 3 Production of Phosphorus Atom-Containing Active Ester Resin (3) 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was changed to 108 parts by mass and p-anisaldehyde was changed to 68 parts by mass. Except for the above, a phosphorus atom-containing active ester resin (3) was obtained in the same manner as in Example 1. The obtained phosphorus atom-containing active ester resin (3) had a softening point of 150 ° C., an active group equivalent calculated from the amount of raw materials charged, 281 g / equivalent, and a phosphorus atom content of 2.9% by mass.
- the inside of the system was controlled to 60 ° C. or less, and 210 parts by mass of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hour under these conditions. After completion of the reaction, the solution was allowed to stand for separation, and the aqueous layer was removed. Further, water was added to the toluene layer in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes, followed by standing and separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer became 7.
- the obtained active ester resin (1 ′) had a softening point of 150 ° C. and an active group equivalent calculated from the amount of raw materials charged was 223 g / equivalent.
- Examples 4 to 6 and Comparative Example 1 ⁇ Preparation of epoxy resin composition and evaluation of physical properties>
- an epoxy resin “N-680” (cresol novolak type epoxy resin, epoxy equivalent: 215 g / equivalent) manufactured by DIC Corporation, and the phosphorus atom-containing active ester resins (1) to (3) or active ester resins ( 1 ′) is added at a ratio shown in Table 1 below, 0.05 phr of dimethylaminopyridine is added as a curing catalyst, and finally the nonvolatile content (NV) of each composition is 58% by mass.
- NV nonvolatile content
- ⁇ Laminate production conditions > Base material: Glass cloth “# 2116” (210 ⁇ 280 mm) manufactured by Nitto Boseki Co., Ltd. Number of plies: 6 Condition of prepreg: 160 ° C Curing conditions: 200 ° C., 40 kg / cm 2 for 1.5 hours, post-molding plate thickness: 0.8 mm
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
- Polyesters Or Polycarbonates (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
の何れかで表される構造部位(Y)を芳香核上の置換基として有するものは、誘電特性に優れる活性エステルの特徴を損なうことなく、耐熱性及び難燃性にも優れることを見出し、本発明を完成するに至った。
の何れかで表される構造部位(Y)を芳香核上の置換基として有することを特徴とするリン原子含有活性エステル樹脂に関する。
の何れかで表されるリン原子含有化合物(E)とを反応させることを特徴とするリン原子含有活性エステル樹脂の製造方法に関する。
本発明のリン原子含有活性エステル樹脂は、脂肪族環状炭化水素基を介して芳香核(X)が複数結節された構造ユニット(α)が、アリーレンジカルボニルオキシ基を介して他の構造ユニット(α)と結節した構造(I)を有し、樹脂中に存在する前記芳香核(X)の少なくとも一つが下記構造式(y1)~(y4)
の何れかで表される構造部位(Y)を芳香核上の置換基として有することを特徴とする。
の何れかで表される構造部位(Y)を芳香核上の置換基として有する。
の何れかで表される構造部位であり、分子構造中の2つのYのうち少なくとも一方は前記構造式(y1)~(y4)の何れかで表される構造部位である。また、kは0又は1であり、lは繰り返し単位の平均で0.25~1.5である。]
で表されるものが挙げられる。
の何れかで表されるリン原子含有化合物(E)とを反応させる工程(以下「工程2」と略記する。)により製造する方法が挙げられる。
下記条件でのGPC測定により得られるl=1、l=2、l=3、l=4のそれぞれに対応するスチレン換算分子量(α1、α2、α3、α4)の値と、l=1、l=2、l=3、l=4のそれぞれの理論分子量(β1、β2、β3、β4)との比率(β1/α1、β2/α2、β3/α3、β4/α4)を求め、これら(β1/α1~β4/α4)の平均値を求める。GPC測定の結果得られる数平均分子量(Mn)に、この平均値を掛け合わせた値を平均分子量とし、この平均分子量に相当するlの値を算出する。
(GPC測定条件)
測定装置 :東ソー株式会社製「HLC-8220 GPC」、
カラム:東ソー株式会社製ガードカラム「HXL-L」
+東ソー株式会社製「TSK-GEL G2000HXL」
+東ソー株式会社製「TSK-GEL G2000HXL」
+東ソー株式会社製「TSK-GEL G3000HXL」
+東ソー株式会社製「TSK-GEL G4000HXL」
検出器: RI(示差屈折径)
データ処理:東ソー株式会社製「GPC-8020モデルIIバージョン4.10」
測定条件: カラム温度 40℃
展開溶媒 テトラヒドロフラン
流速 1.0ml/分
標準 : 前記「GPC-8020モデルIIバージョン4.10」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
(使用ポリスチレン)
東ソー株式会社製「A-500」
東ソー株式会社製「A-1000」
東ソー株式会社製「A-2500」
東ソー株式会社製「A-5000」
東ソー株式会社製「F-1」
東ソー株式会社製「F-2」
東ソー株式会社製「F-4」
東ソー株式会社製「F-10」
東ソー株式会社製「F-20」
東ソー株式会社製「F-40」
東ソー株式会社製「F-80」
東ソー株式会社製「F-128」
試料 : 樹脂固形分換算で1.0質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(50μl)。
の何れかで表されるリン原子含有化合物(E)とを反応させる。
測定装置 :東ソー株式会社製「HLC-8220 GPC」、
カラム:東ソー株式会社製ガードカラム「HXL-L」
+東ソー株式会社製「TSK-GEL G2000HXL」
+東ソー株式会社製「TSK-GEL G2000HXL」
+東ソー株式会社製「TSK-GEL G3000HXL」
+東ソー株式会社製「TSK-GEL G4000HXL」
検出器: RI(示差屈折計)
データ処理:東ソー株式会社製「GPC-8020モデルIIバージョン4.10」
測定条件: カラム温度 40℃
展開溶媒 テトラヒドロフラン
流速 1.0ml/分
標準 : 前記「GPC-8020モデルIIバージョン4.10」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
東ソー株式会社製「A-500」
東ソー株式会社製「A-1000」
東ソー株式会社製「A-2500」
東ソー株式会社製「A-5000」
東ソー株式会社製「F-1」
東ソー株式会社製「F-2」
東ソー株式会社製「F-4」
東ソー株式会社製「F-10」
東ソー株式会社製「F-20」
東ソー株式会社製「F-40」
東ソー株式会社製「F-80」
東ソー株式会社製「F-128」
試料 : 樹脂固形分換算で1.0質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(50μl)。
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコにジシクロペンタジエンとフェノールの重付加反応樹脂(水酸基当量:165g/当量、軟化点85℃)165質量部とトルエン590質量部を仕込み、系内を減圧窒素置換し溶解させた。次いで、イソフタル酸クロライド50質量部を仕込みその後、窒素ガスパージを施しながら、系内を60℃以下に制御して、20%水酸化ナトリウム水溶液102質量部を3時間かけて滴下した。次いでこの条件下で1.0時間撹拌を続けた。反応終了後、静置分液し、水層を取り除いた。更に反応物が溶解しているトルエン層に水を投入して約15分間撹拌混合し、静置分液して水層を取り除いた。水層のPHが7になるまでこの操作を繰り返した。その後、デカンタ脱水で水分を除去し、続いて減圧脱水でトルエンを除去し、フェノール樹脂中間体(C1)を得た。フェノール樹脂中間体(C1)の軟化点は125℃、原料の仕込み量から計算される水酸基当量は395g/当量、軟化点は125℃であった。得られたフェノール樹脂中間体(C1)のGPCチャートを図1に、C13NMRチャートを図2に、MSスペクトルを図3に示す。13C-NMRにてエステル基のカルボニル炭素由来のピークが165ppm付近に確認された。また、得られたフェノール樹脂中間体(C1)において、GPCチャートから算出される前記一般式(1)中のlに相当する値は0.95であった。
温度計、冷却管、分留管、撹拌器を取り付けたフラスコに、9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキサイドを154質量部、p-アニスアルデヒド97質量部、フェノール樹脂中間体(C1)395質量部を仕込み、90℃に昇温して窒素を吹き込みながら撹拌した。その後、180℃にまで昇温し5時間攪拌した後、更に190℃まで昇温して9時間撹拌した。反応混合物から水を加熱減圧下で除去し、リン原子含有活性エステル樹脂(1)を得た。得られたリン原子含有活性エステル樹脂(1)の軟化点は180℃、原料の仕込み量から計算される活性基当量は323g/当量、リン原子含有量は3.6質量%であった。なお、リン原子含有活性エステル樹脂中の活性基とは、樹脂構造中に有するアリールカルボニルオキシ基及びフェノール性水酸基を指す。リン原子含有活性エステル樹脂(1)のGPCチャートを図4に示す。
9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキサイドを216質量部に、p-アニスアルデヒドを136質量部に変えた以外は実施例1と同様の方法により、リン原子含有活性エステル樹脂(2)を得た。得られたリン原子含有活性エステル樹脂(2)の軟化点は200℃、原料の仕込み量から計算される活性基当量は370g/当量、リン原子含有量は4.4質量%であった。リン原子含有活性エステル樹脂(2)のGPCチャートを図5に示す。
9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキサイドを108質量部に、p-アニスアルデヒドを68質量部に変えた以外は実施例1と同様の方法により、リン原子含有活性エステル樹脂(3)を得た。得られたリン原子含有活性エステル樹脂(3)の軟化点は150℃、原料の仕込み量から計算される活性基当量は281g/当量、リン原子含有量は2.9質量%であった。
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコにジシクロペンタジエンとフェノールの重付加反応樹脂(水酸基当量:165g/当量、軟化点85℃)165質量部、ナフトール72質量部、トルエン630質量部を仕込み、系内を減圧窒素置換し溶解させた。次いで、イソフタル酸クロライド151.5質量部を仕込み、系内を減圧窒素置換し溶解させた。その後、窒素ガスパージを施しながら、系内を60℃以下に制御して、20%水酸化ナトリウム水溶液210質量部を3時間かけて滴下した。次いでこの条件下で1.0時間撹拌を続けた。反応終了後、静置分液し、水層を取り除いた。更に反応物が溶解しているトルエン層に水を投入して約15分間撹拌混合し、静置分液して水層を取り除いた。水層のPHが7になるまでこの操作を繰り返した。その後、デカンタ脱水で水分を除去し、続いて減圧脱水でトルエンを除去し、活性エステル樹脂(1’)を合成した。得られた活性エステル樹脂(1’)の軟化点は150℃、原料の仕込み量から計算される活性基当量は223g/当量であった。
<エポキシ樹脂組成物の調整及び物性評価>
エポキシ樹脂として、DIC株式会社製「N-680」(クレゾールノボラック型エポキシ樹脂、エポキシ当量:215g/当量)、硬化剤として前記リン原子含有活性エステル樹脂(1)~(3)又は活性エステル樹脂(1’)を、下記表1に示す割合でそれぞれ配合し、硬化触媒としてジメチルアミノピリジン0.05phrを加え、最終的に各組成物の不揮発分(N.V.)が58質量%となるようにメチルエチルケトンを配合して調整した。次いで、下記の如き条件で積層板を作成し、後述する方法で各種評価試験を行った。結果を表1に示す。
基材:日東紡績株式会社製 ガラスクロス「#2116」(210×280mm)
プライ数:6 プリプレグ化条件:160℃
硬化条件:200℃、40kg/cm2で1.5時間、成型後板厚:0.8mm
粘弾性測定装置(DMA:レオメトリック社製固体粘弾性測定装置RSAII、レクタンギュラーテンション法;周波数1Hz、昇温速度3℃/min)を用いて、弾性率変化が最大となる(tanδ変化率が最も大きい)温度をガラス転移温度として評価した。
T288:試験法はIPC TM650に準拠し評価した。
JIS-C-6481に準拠し、アジレント・テクノロジー株式会社製インピーダンス・マテリアル・アナライザ「HP4291B」により、絶乾後23℃、湿度50%の室内に24時間保管した後の試験片の1GHzでの誘電率および誘電正接を測定した。
UL-94試験法に準拠し、試験片5本を用いて燃焼試験を行った。
Claims (10)
- 脂肪族環状炭化水素基を介して芳香核(X)が複数結節された構造ユニット(α)が、アリーレンジカルボニルオキシ基を介して他の構造ユニット(α)と結節した構造(I)を有し、樹脂中に存在する前記芳香核(X)の少なくとも一つが下記構造式(y1)~(y4)
の何れかで表される構造部位(Y)を芳香核上の置換基として有することを特徴とするリン原子含有活性エステル樹脂。 - 分子構造中に複数存在する前記芳香核(X)のうち、前記構造(I)の末端に位置する2つの芳香核(X)が共にフェノール性水酸基を有しており、かつ、該2つの芳香核(X)の少なくとも一方が前記(y1)~(y4)の何れかで表される構造部位(Y)を芳香核上の置換基として有する請求項1記載のリン原子含有活性エステル樹脂。
- 脂肪族環状炭化水素基を介して芳香核(X)が複数結節された構造を有するフェノール性化合物(A)と、芳香族ジカルボン酸又はそのジハライド(B)とを、前記フェノール性化合物(A)が含有する水酸基の合計1モルに対し、芳香族ジカルボン酸又はそのジハライド(B)が含有するカルボキシル基又は酸ハライド基の合計が0.25~0.75モルの範囲となる割合で反応させてフェノール樹脂中間体(C)を得、次いで、前記フェノール樹脂中間体(C)と、アルデヒド化合物(D)と、下記構造式(e1)又は(e2)
の何れかで表されるリン原子含有化合物(E)とを反応させることを特徴とするリン原子含有活性エステル樹脂の製造方法。 - 請求項3記載の製造方法により得られるリン原子含有活性エステル樹脂。
- 下記構造式(2)
の何れかで表される構造部位であり、分子構造中の2つのYのうち少なくとも一方は前記構造式(y1)~(y4)の何れかで表される構造部位である。また、kは0又は1であり、lは繰り返し単位の平均で0.25~1.5である。]
で表される分子構造を有する請求項1、2又は4記載のリン原子含有活性エステル樹脂。 - 請求項1、2、4又は5に記載のリン原子含有活性エステル樹脂とエポキシ樹脂とを含有するエポキシ樹脂組成物。
- 請求項6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。
- 請求項6記載のエポキシ樹脂組成物を有機溶剤に希釈したものを補強基材に含浸し、得られる含浸基材を半硬化させることにより得られるプリプレグ。
- 請求項6記載のエポキシ樹脂組成物を有機溶剤に希釈したワニスを得、これを板状に賦形したものと銅箔とを加熱加圧成型することにより得られる回路基板。
- 請求項6記載のエポキシ樹脂組成物を有機溶剤に希釈したものを基材フィルム上に塗布し、乾燥させることにより得られるビルドアップフィルム。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/897,100 US9963544B2 (en) | 2013-06-10 | 2014-02-06 | Active ester resin containing phosphorus atom, epoxy resin composition and cured product thereof, prepreg, circuit board, and build-up film |
KR1020157034260A KR102046767B1 (ko) | 2013-06-10 | 2014-02-06 | 인 원자 함유 활성 에스테르 수지, 에폭시 수지 조성물, 그 경화물, 프리프레그, 회로 기판, 및 빌드업 필름 |
CN201480033214.7A CN105392817B (zh) | 2013-06-10 | 2014-02-06 | 含磷原子活性酯树脂、环氧树脂组合物、其固化物、预浸料、电路基板和积层薄膜 |
JP2014531436A JP5637418B1 (ja) | 2013-06-10 | 2014-02-06 | リン原子含有活性エステル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013-121752 | 2013-06-10 | ||
JP2013121752 | 2013-06-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014199655A1 true WO2014199655A1 (ja) | 2014-12-18 |
Family
ID=52021964
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/052743 WO2014199655A1 (ja) | 2013-06-10 | 2014-02-06 | リン原子含有活性エステル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム |
Country Status (6)
Country | Link |
---|---|
US (1) | US9963544B2 (ja) |
JP (1) | JP5637418B1 (ja) |
KR (1) | KR102046767B1 (ja) |
CN (1) | CN105392817B (ja) |
TW (1) | TWI600676B (ja) |
WO (1) | WO2014199655A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015054868A (ja) * | 2013-09-10 | 2015-03-23 | Dic株式会社 | リン原子含有活性エステル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム |
CN108368216A (zh) * | 2015-12-08 | 2018-08-03 | Dic株式会社 | 恶嗪化合物、组合物及固化物 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105646862B (zh) * | 2016-01-14 | 2017-11-10 | 广东广山新材料股份有限公司 | 含磷腈的聚酯、预浸板、复合金属基板以及线路板 |
CN108291008B (zh) * | 2016-03-28 | 2022-05-03 | 积水化学工业株式会社 | 树脂组合物和多层基板 |
EP3466925A4 (en) * | 2016-06-03 | 2019-11-13 | DIC Corporation | SUBSTITUTED OR UNSUBSTITUTED ALLYL GROUP CONTAINING MALEIMIDE COMPOUND, MANUFACTURING METHOD, AND COMPOSITION AND CURED PRODUCT USING THE SAID COMPOUND |
TWI808064B (zh) * | 2016-11-30 | 2023-07-11 | 美商Icl-Ip美國股份有限公司 | 熱固性樹脂之活性酯硬化劑、含彼之阻燃組成物及由彼製成的物品 |
CN108164685B (zh) * | 2016-12-07 | 2019-08-27 | 广东生益科技股份有限公司 | 一种热固性树脂组合物 |
CN108250676B (zh) * | 2016-12-28 | 2019-08-27 | 广东生益科技股份有限公司 | 一种含磷活性酯及其无卤组合物与覆铜箔基板 |
KR102287602B1 (ko) | 2017-06-29 | 2021-08-10 | 코오롱인더스트리 주식회사 | 인계 난연성 중합체 및 이를 포함하는 난연성 수지 조성물 |
KR102346010B1 (ko) | 2019-09-19 | 2021-12-31 | 코오롱인더스트리 주식회사 | 말단이 불포화기로 캡핑된 인 함유 수지, 이의 제조방법 및 상기 말단이 불포화기로 캡핑된 인 함유 수지를 포함하는 수지 조성물 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009242560A (ja) * | 2008-03-31 | 2009-10-22 | Dic Corp | エポキシ樹脂組成物、及びその硬化物 |
WO2010106698A1 (ja) * | 2009-03-18 | 2010-09-23 | Dic株式会社 | リン原子含有フェノール類の製造方法、新規リン原子含有フェノール類、硬化性樹脂組成物、その硬化物、プリント配線基板、及び半導体封止材料 |
JP2012246367A (ja) * | 2011-05-26 | 2012-12-13 | Dic Corp | 熱硬化性樹脂組成物、その硬化物、半導体封止材料、プリプレグ、回路基板、及びビルドアップフィルム |
JP2013040270A (ja) * | 2011-08-15 | 2013-02-28 | Dic Corp | 熱硬化性樹脂組成物、その硬化物、活性エステル樹脂、半導体封止材料、プリプレグ、回路基板、及びビルドアップフィルム |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7141627B2 (en) * | 2002-10-31 | 2006-11-28 | Dainippon Ink And Chemicals, Inc. | Epoxy resin composition |
JP3905820B2 (ja) | 2002-11-08 | 2007-04-18 | 互応化学工業株式会社 | 難燃性エポキシ樹脂組成物、並びにそれを含有するプリプレグ、積層板、銅張積層板およびプリント配線板 |
JP2008239675A (ja) * | 2007-03-26 | 2008-10-09 | Toray Ind Inc | 難燃性樹脂組成物、それを用いた接着剤シート、カバーレイフィルムおよび銅張り積層板 |
JP5181769B2 (ja) | 2008-03-26 | 2013-04-10 | Dic株式会社 | エポキシ樹脂組成物、及びその硬化物 |
JP5640588B2 (ja) | 2010-09-09 | 2014-12-17 | Dic株式会社 | リン原子含有エポキシ樹脂の製造方法、硬化性樹脂組成物、その硬化物、プリント配線基板用樹脂組成物、プリント配線基板、フレキシブル配線基板用樹脂組成物、半導体封止材料用樹脂組成物、及びビルドアップ基板用層間絶縁材料用樹脂組成物 |
-
2014
- 2014-02-06 WO PCT/JP2014/052743 patent/WO2014199655A1/ja active Application Filing
- 2014-02-06 KR KR1020157034260A patent/KR102046767B1/ko active IP Right Grant
- 2014-02-06 JP JP2014531436A patent/JP5637418B1/ja active Active
- 2014-02-06 CN CN201480033214.7A patent/CN105392817B/zh active Active
- 2014-02-06 US US14/897,100 patent/US9963544B2/en active Active
- 2014-03-19 TW TW103110198A patent/TWI600676B/zh active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009242560A (ja) * | 2008-03-31 | 2009-10-22 | Dic Corp | エポキシ樹脂組成物、及びその硬化物 |
WO2010106698A1 (ja) * | 2009-03-18 | 2010-09-23 | Dic株式会社 | リン原子含有フェノール類の製造方法、新規リン原子含有フェノール類、硬化性樹脂組成物、その硬化物、プリント配線基板、及び半導体封止材料 |
JP2012246367A (ja) * | 2011-05-26 | 2012-12-13 | Dic Corp | 熱硬化性樹脂組成物、その硬化物、半導体封止材料、プリプレグ、回路基板、及びビルドアップフィルム |
JP2013040270A (ja) * | 2011-08-15 | 2013-02-28 | Dic Corp | 熱硬化性樹脂組成物、その硬化物、活性エステル樹脂、半導体封止材料、プリプレグ、回路基板、及びビルドアップフィルム |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015054868A (ja) * | 2013-09-10 | 2015-03-23 | Dic株式会社 | リン原子含有活性エステル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム |
CN108368216A (zh) * | 2015-12-08 | 2018-08-03 | Dic株式会社 | 恶嗪化合物、组合物及固化物 |
CN108368216B (zh) * | 2015-12-08 | 2020-09-18 | Dic株式会社 | 恶嗪化合物、组合物及固化物 |
US11117873B2 (en) | 2015-12-08 | 2021-09-14 | Dic Corporation | Oxazine compound, composition, and cured product |
Also Published As
Publication number | Publication date |
---|---|
US9963544B2 (en) | 2018-05-08 |
KR102046767B1 (ko) | 2019-11-20 |
CN105392817B (zh) | 2017-01-25 |
JPWO2014199655A1 (ja) | 2017-02-23 |
CN105392817A (zh) | 2016-03-09 |
KR20160018507A (ko) | 2016-02-17 |
TWI600676B (zh) | 2017-10-01 |
TW201446832A (zh) | 2014-12-16 |
JP5637418B1 (ja) | 2014-12-10 |
US20160130391A1 (en) | 2016-05-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5152445B2 (ja) | 活性エステル樹脂、その製造方法、熱硬化性樹脂組成物、その硬化物、半導体封止材料、プリプレグ、回路基板、及びビルドアップフィルム | |
JP5637418B1 (ja) | リン原子含有活性エステル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム | |
JP5510764B1 (ja) | 活性エステル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム | |
JP6042054B2 (ja) | 熱硬化性樹脂組成物、その硬化物、半導体封止材料、プリプレグ、回路基板、及びビルドアップフィルム | |
JP5262915B2 (ja) | 硬化性樹脂組成物、その硬化物、プリント配線基板、エステル化合物、エステル系樹脂、及びその製造方法 | |
JP5500408B2 (ja) | 活性エステル樹脂、熱硬化性樹脂組成物、その硬化物、半導体封止材料、プリプレグ、回路基板、及びビルドアップフィルム | |
WO2011102211A1 (ja) | リン原子含有オリゴマー、その製造方法、硬化性樹脂組成物、その硬化物、及びプリント配線基板 | |
WO2011096273A1 (ja) | フェノール樹脂組成物、その製造方法、硬化性樹脂組成物、その硬化物、及びプリント配線基板 | |
JP5729605B2 (ja) | 熱硬化性樹脂組成物、その硬化物、活性エステル樹脂、半導体封止材料、プリプレグ、回路基板、及びビルドアップフィルム | |
JP6171760B2 (ja) | リン原子含有活性エステル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム | |
JP5907319B2 (ja) | 活性エステル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム | |
JP5146793B2 (ja) | リン原子含有オリゴマー組成物、硬化性樹脂組成物、その硬化物、及びプリント配線基板 | |
JP6278239B2 (ja) | 活性エステル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム | |
JP2011099049A (ja) | エポキシ樹脂組成物、その硬化物、新規エポキシ樹脂、新規フェノール樹脂、プリプレグ、及び回路基板 | |
JP5910866B2 (ja) | 活性エステル樹脂、熱硬化性樹脂組成物、その硬化物、半導体封止材料、プリプレグ、回路基板、及びビルドアップフィルム | |
JP6255624B2 (ja) | 活性エステル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム | |
JP5850228B2 (ja) | 硬化性樹脂組成物、その硬化物、シアン酸エステル樹脂、半導体封止材料、プリプレグ、回路基板、及び、ビルドアップフィルム | |
JP5880921B2 (ja) | 硬化性樹脂組成物、その硬化物、プリント配線基板 | |
JP6257020B2 (ja) | フェニルフェノール−ナフトール樹脂、硬化性樹脂組成物、その硬化物、及びプリント配線基板 | |
JP6127640B2 (ja) | 変性ポリアリーレンエーテル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム | |
JP2014065829A (ja) | クレゾール−ナフトール樹脂、硬化性樹脂組成物、その硬化物、及びプリント配線基板 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480033214.7 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 2014531436 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14810387 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20157034260 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14897100 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14810387 Country of ref document: EP Kind code of ref document: A1 |