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WO2018008412A1 - Active ester resin and cured product thereof - Google Patents

Active ester resin and cured product thereof Download PDF

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Publication number
WO2018008412A1
WO2018008412A1 PCT/JP2017/022998 JP2017022998W WO2018008412A1 WO 2018008412 A1 WO2018008412 A1 WO 2018008412A1 JP 2017022998 W JP2017022998 W JP 2017022998W WO 2018008412 A1 WO2018008412 A1 WO 2018008412A1
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WO
WIPO (PCT)
Prior art keywords
group
active ester
ester resin
resin
phenol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/022998
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French (fr)
Japanese (ja)
Inventor
泰 佐藤
和久 矢本
顕人 河崎
竜也 岡本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to KR1020197000301A priority Critical patent/KR102197902B1/en
Priority to JP2017564144A priority patent/JP6332721B1/en
Priority to CN201780042056.5A priority patent/CN109476821B/en
Publication of WO2018008412A1 publication Critical patent/WO2018008412A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • 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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/133—Hydroxy compounds containing aromatic 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
    • C08G59/18—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
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
    • C08G59/4276—Polyesters
    • 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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/127—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • 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
    • 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

Definitions

  • the present invention relates to an active ester resin having high heat resistance and moisture absorption resistance in a cured product and excellent in dielectric properties, a curable resin composition containing the same, a cured product thereof, a printed wiring board, and a semiconductor sealing material.
  • Patent Document 1 As a resin material having a relatively low dielectric constant and dielectric loss tangent in a cured product, there is a technique in which an active ester resin obtained by esterifying dicyclopentadiene phenol resin and ⁇ -naphthol with phthalic acid chloride is used as a curing agent for an epoxy resin. It is known (see Patent Document 1 below).
  • the active ester resin described in Patent Document 1 has characteristics of low dielectric constant and dielectric loss tangent in a cured product as compared with the case where a conventional curing agent such as a phenol novolac resin is used, but satisfies the recent market demand. It was not a thing. Further, the heat resistance evaluated by the glass transition temperature of the cured product has been required to be further improved.
  • the problem to be solved by the present invention is an active ester resin having high heat resistance and moisture absorption resistance in a cured product and excellent in dielectric characteristics, a curable resin composition containing the same, a cured product thereof, and a printed wiring board. And providing a semiconductor sealing material.
  • the inventors of the present invention essentially require a phenol resin having a molecular structure in which a phenol compound (b) having one or more hydrocarbon groups on an aromatic ring is knotted by a methylene group.
  • the active ester resin used as a reaction raw material of the present invention has been found to have high heat resistance and moisture absorption resistance in a cured product and excellent dielectric properties, and has completed the present invention.
  • the present invention relates to a phenolic hydroxyl group-containing compound (A), a phenol resin (B) having a molecular structure in which a phenol compound (b) having one or more hydrocarbon groups on an aromatic ring is knotted by a methylene group. And an active ester resin characterized by using an aromatic polycarboxylic acid or an acid halide (C) thereof as an essential reaction raw material.
  • the present invention further relates to a curable resin composition containing the active ester resin and a curing agent.
  • the present invention further relates to a cured product of the curable resin composition.
  • the present invention further relates to a printed wiring board using the curable resin composition.
  • the present invention further relates to a semiconductor sealing material using the curable resin composition.
  • an active ester resin having high heat resistance and moisture absorption resistance in a cured product and excellent in dielectric properties a curable resin composition containing the same, a cured product thereof, a printed wiring board, and a semiconductor sealing material are provided.
  • a curable resin composition containing the same a curable resin composition containing the same, a cured product thereof, a printed wiring board, and a semiconductor sealing material are provided.
  • FIG. 1 is a GPC chart of the active ester resin (1) obtained in Example 1.
  • FIG. FIG. 2 is a GPC chart of the active ester resin (2) obtained in Example 2.
  • the active ester resin of the present invention includes a phenolic hydroxyl group-containing compound (A), a phenol resin (B) having a molecular structure in which a phenol compound (b) having one or more hydrocarbon groups on an aromatic ring is knotted by a methylene group. And an aromatic polycarboxylic acid or an acid halide (C) thereof as an essential reaction raw material.
  • the phenolic hydroxyl group-containing compound (A) may be any compound as long as it is an aromatic compound having a hydroxyl group on the aromatic ring, and other specific structures are not particularly limited.
  • a phenolic hydroxyl group containing compound (A) may be used individually by 1 type, and may be used in combination of 2 or more types.
  • Specific examples of the phenolic hydroxyl group-containing compound (A) include phenol, naphthol, anthracenol, and compounds having one or more substituents on these aromatic nuclei.
  • Substituents on the aromatic nucleus are, for example, methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl Group, aliphatic hydrocarbon group such as dodecyl group; alkoxy group such as methoxy group, ethoxy group, propyloxy group, butoxy group; halogen atom such as fluorine atom, chlorine atom, bromine atom; phenyl group, naphthyl group, anthryl group An aryl group such as phenylmethyl group, phenylethyl group, naphthylmethyl group, naphthylethyl group, and the like.
  • the phenolic compound (a) having one or more hydrocarbon groups on the aromatic ring is preferable because it becomes an active ester resin having high heat resistance and moisture absorption in the cured product and excellent dielectric properties.
  • the number of hydrocarbon groups on the aromatic ring is preferably 1 or 2.
  • the hydrocarbon group that the phenol compound (a) has on the aromatic ring include the aliphatic hydrocarbon group, the aryl group, and the aralkyl group. Among them, the heat resistance and hygroscopicity in the cured product are high. From the standpoint of an active ester resin having excellent dielectric properties, an aliphatic hydrocarbon group or an aryl group is preferable, and the number of carbon atoms is preferably in the range of 1 to 12.
  • the aliphatic hydrocarbon group preferably has a branched structure, and in this case, the number of carbon atoms is preferably in the range of 3 to 12.
  • Specific examples of the aliphatic hydrocarbon group having a branched structure include isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, and tertiary octyl group.
  • the hydrocarbon group of the phenol compound (b) having one or more hydrocarbon groups on the aromatic ring is, for example, a methyl group, an ethyl group, a vinyl group, a propyl group, or a butyl group.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group or an aryl group, since it becomes an active ester resin having high heat resistance and moisture absorption resistance in a cured product and excellent dielectric properties, and the number of carbon atoms thereof.
  • the number of hydrocarbon groups on the aromatic ring is preferably 1 or 2.
  • the aliphatic hydrocarbon group preferably has a branched structure, and in this case, the number of carbon atoms is preferably in the range of 3 to 12.
  • Specific examples of the aliphatic hydrocarbon group having a branched structure include isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, and tertiary octyl group.
  • phenol resin (B) having a molecular structure in which a phenol compound (b) having one or more hydrocarbon groups on the aromatic ring is knotted by a methylene group include, for example, one on the aromatic ring. And a polycondensation product of phenol compound (b) having one or more hydrocarbon groups and formaldehyde.
  • the polycondensation product of the phenol compound (b) and formaldehyde can be produced, for example, by a method similar to the production of a normal phenol novolac resin. Specifically, a method of reacting the phenol compound (b) with formaldehyde in the presence of an acid catalyst under a temperature condition of 100 to 200 ° C. can be mentioned. After completion of the reaction, an excess amount of the phenol compound (b) may be distilled off as desired. Moreover, you may use the unreacted phenol compound in reaction mixture as a phenolic hydroxyl-containing compound (A) as it is.
  • the formaldehyde used in the above method may be used as a formalin solution or as paraformaldehyde.
  • the reaction ratio between the phenol compound (b) and the aldehyde is such that the reaction is easy to control, so that the formaldehyde is in the range of 0.01 to 0.9 mole per mole of the phenol compound (b). Is preferred.
  • the acid catalyst examples include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Is mentioned. These may be used alone or in combination of two or more. The amount of these acid catalysts used is preferably in the range of 0.1 to 5% by mass relative to the total mass of the reaction raw materials.
  • the reaction between the phenol compound (b) and formaldehyde may be performed in an organic solvent as necessary.
  • the organic solvent used here is not particularly limited as long as it is an organic solvent that can be used under the above temperature conditions. Specific examples include methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. . When these organic solvents are used, they are preferably used in the range of 10 to 500% by mass relative to the total mass of the reaction raw materials.
  • antioxidants and reducing agents may be used for the purpose of suppressing coloring of the novolak resin obtained.
  • the antioxidant include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing a trivalent phosphorus atom.
  • the reducing agent include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, salts thereof, and zinc.
  • the target phenol resin (B) can be obtained by neutralizing the reaction mixture or washing with water, and then distilling off unreacted raw materials and by-products.
  • the hydroxyl equivalent of the phenol resin (B) is preferably in the range of 110 to 250 g / equivalent because it is an active ester resin that has high solvent solubility and can be easily used for various purposes.
  • the softening point of the phenol resin (B) is preferably in the range of 40 to 130 ° C.
  • the aromatic polycarboxylic acid or its acid halide (C) reacts with the phenolic hydroxyl group of the phenolic hydroxyl group-containing compound (A) and the phenol resin (B) to form an ester bond.
  • the specific structure is not particularly limited, and any compound may be used.
  • Specific examples include benzenedicarboxylic acids such as isophthalic acid and terephthalic acid, benzenetricarboxylic acids such as trimellitic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, and naphthalene-2,6.
  • -Naphthalene dicarboxylic acids such as dicarboxylic acids and naphthalene-2,7-dicarboxylic acids, acid halides thereof, and compounds in which the aliphatic hydrocarbon group, alkoxy group, halogen atom, etc. are substituted on the aromatic nucleus, etc.
  • the acid halide include acid chloride, acid bromide, acid fluoride, and acid iodide. These may be used alone or in combination of two or more.
  • benzenedicarboxylic acids such as isophthalic acid and terephthalic acid or acid halides thereof are preferable because they are active ester resins having high reaction activity and excellent curability.
  • the reaction of the phenolic hydroxyl group-containing compound (A), the phenol resin (B), and the aromatic polycarboxylic acid or its acid halide (C) is, for example, about 40 to 65 ° C. in the presence of an alkali catalyst. It can carry out by the method of heating and stirring under temperature conditions. You may perform reaction in an organic solvent as needed. Further, after completion of the reaction, the reaction product may be purified by washing, reprecipitation or the like, if desired.
  • alkali catalyst examples include sodium hydroxide, potassium hydroxide, triethylamine, pyridine and the like. These may be used alone or in combination of two or more. Further, it may be used as an aqueous solution of about 3.0 to 30%. Among these, sodium hydroxide or potassium hydroxide having high catalytic ability is preferable.
  • organic solvent examples 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; and carbitols such as cellosolve and butyl carbitol.
  • 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
  • carbitols such as cellosolve and butyl carbitol.
  • solvents aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, and N-methyl
  • the reaction ratio of the phenolic hydroxyl group-containing compound (A), the phenol resin (B), and the aromatic polycarboxylic acid or acid halide (C) thereof can be appropriately changed according to the desired molecular design. .
  • the number of moles of hydroxyl group (A OH ) of the phenolic hydroxyl group-containing compound (A) and the phenol resin (B) The ratio of [(A OH ) / (B OH )] to the number of moles of hydroxyl groups (B OH ) possessed is preferably 10/90 to 75/25, preferably 20/80 to 50/50 It is more preferable that Moreover, with respect to 1 mol in total of the carboxyl group or acid halide group which aromatic polycarboxylic acid or its acid halide (C) has, the number of moles of the hydroxyl group which said phenolic hydroxyl group containing compound (
  • the active ester resin of the present invention may contain an ester compound (AC) of the phenolic hydroxyl group-containing compound (A) and the aromatic polycarboxylic acid or its acid halide (C).
  • the ester compound (AC) is prepared, for example, by adjusting the reaction ratio of the phenolic hydroxyl group-containing compound (A), the phenol resin (B), and the aromatic polycarboxylic acid or acid halide (C) thereof. Can be produced as a component of an active ester resin.
  • ester compound (AC) for example, a phenol compound (a) having one or more hydrocarbon groups on an aromatic ring is used as the phenolic hydroxyl group-containing compound (A).
  • a structural example in the case of using benzenedicarboxylic acid or its acid halide as the polycarboxylic acid or its acid halide (C) is shown in the following structural formula (1).
  • the following structural formula (1) is merely an example of the specific structure of the ester compound (AC), and does not exclude diester compounds having other molecular structures.
  • each R 1 independently represents a hydrocarbon group, which may be bonded to any carbon atom on the benzene ring, and n is 0 or an integer of 1 to 5).
  • the content is preferably less than 40% of the active ester resin, and more preferably in the range of 0.5 to 30%.
  • the content of the ester compound (AC) in the active ester resin is a value calculated from the area ratio of the GPC chart 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”.
  • the functional group equivalent of the active ester resin of the present invention is preferably in the range of 150 to 350 g / equivalent because it becomes an active ester resin having a low cure shrinkage and excellent curability.
  • the functional group in the active ester resin means an ester bond site and a phenolic hydroxyl group in the active ester resin.
  • the functional group equivalent of the active ester resin is a value calculated from the charged amount of the reaction raw material.
  • the softening point of the active ester resin of the present invention is preferably in the range of 85 to 160 ° C., more preferably in the range of 100 to 150 ° C., as measured based on JIS K7234.
  • the curable resin composition of the present invention contains the aforementioned active ester resin and a curing agent.
  • the curing agent may be a compound that can react with the active ester resin of the present invention, and various compounds can be used without any particular limitation.
  • An example of the curing agent is an epoxy resin.
  • epoxy resin examples include phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, bisphenol novolac type epoxy resin, biphenol novolac type epoxy resin, bisphenol type epoxy resin, biphenyl type epoxy resin, and triphenolmethane.
  • Type epoxy resin tetraphenolethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin and the like.
  • epoxy resin curing agents used herein include, for example, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF 3 -amine complexes, guanidine derivatives and other amine compounds; dicyandiamide, linolene Amide compounds such as polyamide resin synthesized from dimer of acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl anhydride Acid anhydrides such as nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; phenol
  • the active ester resin, the epoxy resin, and the curing agent composition for other epoxy resins of the present invention are blended in a proportion of 1 mol in total for the epoxy groups in the epoxy resin.
  • the ratio is preferably such that the total of functional groups in the agent is 0.7 to 1.5 mol.
  • the curable resin composition of the present invention includes cyanate ester resins, bismaleimide resins, benzoxazine resins, styrene-maleic anhydride resins, allyl group-containing resins represented by diallyl bisphenol and triallyl isocyanurate, polyphosphorus An acid ester or a phosphate ester-carbonate copolymer may be contained. These may be used alone or in combination of two or more.
  • the curable resin composition of the present invention may contain various additives such as a curing accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a release agent, a pigment, and an emulsifier, if necessary.
  • the curing accelerator examples include phosphorus compounds, tertiary amines, imidazole compounds, pyridine compounds, organic acid metal salts, Lewis acids, amine complex salts, and the like.
  • triphenylphosphine is used for phosphorus compounds
  • 1,8-diazabicyclo- [5.4.0] -undecene (DBU is used for tertiary amines because of its excellent curability, heat resistance, electrical properties, moisture resistance reliability, and the like.
  • 2-ethyl-4-methylimidazole is preferred for imidazole compounds
  • 4-dimethylaminopyridine is preferred for pyridine compounds.
  • the flame retardant is, for example, red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, inorganic phosphorus compounds such as phosphate amide; phosphate ester compound, phosphonic acid Compound, phosphinic acid compound, phosphine oxide compound, phosphorane compound, organic nitrogen-containing phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) ) Cyclic organic phosphorus such as -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide Compound and its compound such as epoxy resin and phenol resin Organophosphorus compounds such as derivatives reacted with nitrogen; nitrogen
  • the inorganic filler is blended, for example, when the curable resin composition of the present invention is used for semiconductor sealing materials.
  • the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.
  • the said fused silica is preferable.
  • the fused silica can be used in either crushed or spherical shape, but in order to increase the blending amount of the fused silica and to suppress an increase in the melt viscosity of the curable composition, a spherical one is mainly used. It is preferable.
  • the filling rate is preferably in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition.
  • a conductive filler such as silver powder or copper powder can be used.
  • the active ester resin of the present invention is characterized by high heat resistance and moisture absorption resistance in a cured product and excellent dielectric properties.
  • the general required performance required for resin materials such as solubility in general-purpose organic solvents and curability with epoxy resins, is sufficiently high, such as printed wiring boards, semiconductor encapsulation materials, resist materials, etc.
  • it can be widely used for applications such as paints, adhesives and molded products.
  • the curable resin composition of the present invention When the curable resin composition of the present invention is used for printed wiring board applications or build-up adhesive film applications, it is generally preferable to mix and dilute with an organic solvent.
  • the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate and the like.
  • the type and blending amount of the organic solvent can be adjusted as appropriate according to the use environment of the curable resin composition.
  • methyl ethyl ketone, acetone, dimethylformamide and the like are polar solvents having a boiling point of 160 ° C. or lower.
  • the non-volatile content is preferably 40 to 80% by mass.
  • 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, carbitols such as cellosolve, butyl carbitol, etc.
  • a solvent an aromatic hydrocarbon solvent such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like, and it is preferable to use them in a proportion that the nonvolatile content is 30 to 60% by mass.
  • the method of manufacturing a printed wiring board using the curable resin composition of the present invention includes, for example, impregnating a curable composition into a reinforcing base material and curing it to obtain a prepreg, and stacking this with a copper foil.
  • the method of carrying out thermocompression bonding is mentioned.
  • the reinforcing substrate include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth.
  • the amount of impregnation of the curable resin composition is not particularly limited, but it is usually preferable to prepare so that the resin content in the prepreg is 20 to 60% by mass.
  • the curable resin composition of the present invention when used for a semiconductor sealing material, it is preferable to blend an inorganic filler.
  • the semiconductor encapsulating material containing the active ester resin of the present invention, a curing agent, an inorganic filler, and other optional components may be prepared by mixing the compound using, for example, an extruder, a kneader, or a roll. it can.
  • a method for molding a semiconductor package using the obtained semiconductor sealing material includes, for example, molding the semiconductor sealing material using a casting or transfer molding machine, injection molding machine, etc., and further a temperature of 50 to 200 ° C. Examples of the method include heating for 2 to 10 hours under conditions, and by such a method, a semiconductor device which is a molded product can be obtained.
  • Example 1 Production of Active Ester Resin (1)
  • a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer 234.3 parts by mass of paratertiary butylphenol, 52.8 parts of toluene, 37 parts by mass 52.8 parts by weight of a formalin aqueous solution and 4.8 parts by weight of 49% sodium hydroxide were charged, the temperature was raised from room temperature to 75 ° C. with stirring, and the mixture was stirred at the same temperature for 1 hour for reaction.
  • 7.1 parts by mass of first sodium phosphate was added for neutralization, 363.2 parts by mass of toluene was added, and the mixture was washed 3 times with 121.1 parts by mass of water.
  • the mixture was dried under heating and reduced pressure to obtain 234.8 parts by mass of a mixture (1) containing unreacted paratertiary butylphenol and phenol resin (B-1).
  • the hydroxyl equivalent of mixture (1) was 155 g / equivalent.
  • a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was charged with 141.4 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene, and dissolved in the system while substituting with nitrogen under reduced pressure.
  • 217.0 parts by mass of the previously obtained mixture (1) was charged, and the system was dissolved while substituting with nitrogen under reduced pressure.
  • dissolving 0.4 parts by mass of tetrabutylammonium bromide and applying a nitrogen gas purge the inside of the system was controlled to 60 ° C. or less, and 280 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours.
  • an active ester resin (1) The functional group equivalent of the active ester resin (1) was 220 g / equivalent, and the softening point measured based on JIS K7234 was 132 ° C.
  • the content of bis (paratertiary butylphenyl) isophthalate in the active ester resin (1) calculated from the GPC chart was 10.1%.
  • Example 2 Production of Active Ester Resin (2)
  • a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer 321.9 parts by mass of paratertiary octylphenol, 52.8 parts by mass of toluene, 37 52.8 parts by mass of an aqueous formalin solution and 6.6 parts by mass of 49% sodium hydroxide were added, the temperature was raised from room temperature to 75 ° C., and the mixture was stirred at the same temperature for 1 hour for reaction.
  • the mixture was neutralized by adding 9.7 parts by mass of first sodium phosphate, added with 494.6 parts by mass of toluene, and washed with 164.9 parts by mass of water three times.
  • the mixture was dried under heating under reduced pressure to obtain 319.8 parts by mass of a mixture (2) containing unreacted paratertiaryoctylphenol and phenol resin (B-2).
  • the hydroxyl equivalent of the mixture (2) was 211 g / equivalent.
  • Example 2 In the same manner as in Example 1 except that instead of 217.0 parts by mass of the mixture (1) 217.0 parts by mass in Example 1, the mixture was changed to 295.4 parts by mass, the active ester resin (2) 374.8 parts by mass. Obtained.
  • the functional group equivalent of the active ester resin (2) was 276 g / equivalent, and the softening point measured based on JIS K7234 was 101 ° C.
  • the content of bis (paratertiary octylphenyl) isophthalate in the active ester resin (2) calculated from the GPC chart was 14.8%.
  • Examples 3 and 4 and Comparative Example 1 An active ester resin, an epoxy resin (*), and dimethylaminopyridine were blended in the proportions shown in Table 1 below, and the nonvolatile content was adjusted to 58% by mass with methyl ethyl ketone to obtain a curable resin composition. About the obtained curable resin composition, various evaluation tests were done in the following way. The results are shown in Table 1.
  • the laminated board was created on condition of the following.
  • Base material Nitto Boseki Co., Ltd. glass cloth “# 2116” (210 ⁇ 280 mm)
  • the laminate obtained above was cut into a size of 5 mm in width and 54 mm in length, and this was used as a test piece, using a viscoelasticity measuring device (“Solid Viscoelasticity Measuring Device RSAII” manufactured by Rheometric), Under the measurement conditions of the rectangular tension method, the frequency of 1 Hz, and the heating rate of 3 ° C./min, the temperature at which the elastic modulus change was maximum (the tan ⁇ change rate was the largest) was evaluated as the glass transition temperature.
  • RSAII Solid Viscoelasticity Measuring Device
  • the laminate obtained at the evaluation destination of moisture absorption resistance was cut into a size of 25 mm in width and 75 mm in length, and this was used as a test piece.
  • the sample was left for 168 hours in an atmosphere of 85 ° C./85% RH, and a moisture absorption test was performed.
  • the mass of the test piece before and after the test was measured, and the weight change rate was evaluated as the moisture absorption rate.

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Abstract

Provided are: an active ester resin having high heat resistance and moisture-absorption resistance and having excellent dielectric properties, etc., in a cured product; a curable resin composition containing same; a cured product thereof; a printed wiring board; and a semiconductor sealing material. An active ester resin, a curable resin composition containing same, a cured product thereof, a printed wiring board, and a semiconductor sealing material, said active ester resin being characterized by having, as essential reactive raw materials thereof: (A) a phenolic hydroxyl group-containing compound; (B) a phenol resin having a molecular structure whereby a phenol compound (b) having at least one hydrocarbon group on an aromatic ring is nodular at a methylene group; and (C) an aromatic polycarboxylic acid or an acid halide thereof.

Description

活性エステル樹脂とその硬化物Active ester resin and its cured product

　本発明は、硬化物における耐熱性や耐吸湿性が高く、誘電特性にも優れる活性エステル樹脂、これを含有する硬化性樹脂組成物、その硬化物、プリント配線基板及び半導体封止材料に関する。 The present invention relates to an active ester resin having high heat resistance and moisture absorption resistance in a cured product and excellent in dielectric properties, a curable resin composition containing the same, a cured product thereof, a printed wiring board, and a semiconductor sealing material.

　半導体や多層プリント基板等に用いられる絶縁材料の技術分野では、各種電子部材の薄型化や信号の高速化及び高周波数化に伴い、これらの市場動向に合わせた新たな樹脂材料の開発が求められている。樹脂材料に求められる性能としては、耐熱性や耐吸湿性等の基本的な性能はもちろんのこと、信号の高速や高周波数化が進む中、発熱等によるエネルギー損失を低減させるために、硬化物における誘電率と誘電正接との両値が低いことも重要な性能の一つである。 In the technical field of insulating materials used for semiconductors and multilayer printed circuit boards, development of new resin materials that meet these market trends is required as various electronic components become thinner and signals become faster and higher in frequency. ing. In addition to basic performance such as heat resistance and moisture absorption, as well as performance required for resin materials, cured materials are used to reduce energy loss due to heat generation as signal speed and frequency increase. One of the important performances is that both values of dielectric constant and dielectric loss tangent are low.

　硬化物における誘電率と誘電正接とが比較的低い樹脂材料として、ジシクロペンタジエンフェノール樹脂とα－ナフトールとをフタル酸クロライドでエステル化して得られる活性エステル樹脂をエポキシ樹脂の硬化剤として用いる技術が知られている（下記特許文献１参照）。特許文献１記載の活性エステル樹脂は、フェノールノボラック樹脂のような従来型の硬化剤を用いた場合と比較すると、硬化物における誘電率や誘電正接が低い特徴を有するが、昨今の市場要求を満たすものではなかった。また、硬化物のガラス転移温度で評価される耐熱性についても、更なる向上が求められていた。 As a resin material having a relatively low dielectric constant and dielectric loss tangent in a cured product, there is a technique in which an active ester resin obtained by esterifying dicyclopentadiene phenol resin and α-naphthol with phthalic acid chloride is used as a curing agent for an epoxy resin. It is known (see Patent Document 1 below). The active ester resin described in Patent Document 1 has characteristics of low dielectric constant and dielectric loss tangent in a cured product as compared with the case where a conventional curing agent such as a phenol novolac resin is used, but satisfies the recent market demand. It was not a thing. Further, the heat resistance evaluated by the glass transition temperature of the cured product has been required to be further improved.

特開２００４－１６９０２１号公報JP 2004-169021 A

　従って、本発明が解決しようとする課題は、硬化物における耐熱性や耐吸湿性が高く、誘電特性にも優れる活性エステル樹脂、これを含有する硬化性樹脂組成物、その硬化物、プリント配線基板及び半導体封止材料を提供することにある。 Accordingly, the problem to be solved by the present invention is an active ester resin having high heat resistance and moisture absorption resistance in a cured product and excellent in dielectric characteristics, a curable resin composition containing the same, a cured product thereof, and a printed wiring board. And providing a semiconductor sealing material.

　本発明者らは前記課題を解決すべく鋭意検討した結果、芳香環上に一つ乃至複数の炭化水素基を有するフェノール化合物（ｂ）がメチレン基で結節された分子構造を有するフェノール樹脂を必須の反応原料とする活性エステル樹脂は、硬化物における耐熱性や耐吸湿性が高く、誘電特性にも優れることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention essentially require a phenol resin having a molecular structure in which a phenol compound (b) having one or more hydrocarbon groups on an aromatic ring is knotted by a methylene group. The active ester resin used as a reaction raw material of the present invention has been found to have high heat resistance and moisture absorption resistance in a cured product and excellent dielectric properties, and has completed the present invention.

　即ち、本発明は、フェノール性水酸基含有化合物（Ａ）、芳香環上に一つ乃至複数の炭化水素基を有するフェノール化合物（ｂ）がメチレン基で結節された分子構造を有するフェノール樹脂（Ｂ）、及び芳香族ポリカルボン酸又はその酸ハロゲン化物（Ｃ）を必須の反応原料とすることを特徴とする活性エステル樹脂に関する。 That is, the present invention relates to a phenolic hydroxyl group-containing compound (A), a phenol resin (B) having a molecular structure in which a phenol compound (b) having one or more hydrocarbon groups on an aromatic ring is knotted by a methylene group. And an active ester resin characterized by using an aromatic polycarboxylic acid or an acid halide (C) thereof as an essential reaction raw material.

　本発明は更に、前記活性エステル樹脂と、硬化剤とを含有する硬化性樹脂組成物に関する。 The present invention further relates to a curable resin composition containing the active ester resin and a curing agent.

　本発明は更に、前記硬化性樹脂組成物の硬化物に関する。 The present invention further relates to a cured product of the curable resin composition.

　本発明は更に、前記硬化性樹脂組成物を用いてなるプリント配線基板に関する。 The present invention further relates to a printed wiring board using the curable resin composition.

　本発明は更に、前記硬化性樹脂組成物を用いてなる半導体封止材料に関する。 The present invention further relates to a semiconductor sealing material using the curable resin composition.

　本発明によれば、硬化物における耐熱性や耐吸湿性が高く、誘電特性にも優れる活性エステル樹脂、これを含有する硬化性樹脂組成物、その硬化物、プリント配線基板及び半導体封止材料を提供することができる。 According to the present invention, an active ester resin having high heat resistance and moisture absorption resistance in a cured product and excellent in dielectric properties, a curable resin composition containing the same, a cured product thereof, a printed wiring board, and a semiconductor sealing material are provided. Can be provided.

図１は、実施例１で得られた活性エステル樹脂（１）のＧＰＣチャート図である。1 is a GPC chart of the active ester resin (1) obtained in Example 1. FIG. 図２は、実施例２で得られた活性エステル樹脂（２）のＧＰＣチャート図である。FIG. 2 is a GPC chart of the active ester resin (2) obtained in Example 2.

　以下、本発明を詳細に説明する。
　本発明の活性エステル樹脂はフェノール性水酸基含有化合物（Ａ）、芳香環上に一つ乃至複数の炭化水素基を有するフェノール化合物（ｂ）がメチレン基で結節された分子構造を有するフェノール樹脂（Ｂ）、及び芳香族ポリカルボン酸又はその酸ハロゲン化物（Ｃ）を必須の反応原料とすることを特徴とする。 Hereinafter, the present invention will be described in detail.
The active ester resin of the present invention includes a phenolic hydroxyl group-containing compound (A), a phenol resin (B) having a molecular structure in which a phenol compound (b) having one or more hydrocarbon groups on an aromatic ring is knotted by a methylene group. And an aromatic polycarboxylic acid or an acid halide (C) thereof as an essential reaction raw material.

　前記フェノール性水酸基含有化合物（Ａ）は、芳香環上に水酸基を有する芳香族化合物であれば何れの化合物でもよく、その他の具体構造は特に限定されない。本発明では、フェノール性水酸基含有化合物（Ａ）は一種類を単独で用いてもよいし、２種類以上を併用して用いてもよい。前記フェノール性水酸基含有化合物（Ａ）は、具体的には、フェノール、ナフトール、アントラセノール、これらの芳香核上に一つ乃至複数の置換基を有する化合物が挙げられる。芳香核上の置換基は、例えば、メチル基、エチル基、ビニル基、プロピル基、ブチル基、ペンチル基、へキシル基、シクロへキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等の脂肪族炭化水素基；メトキシ基、エトキシ基、プロピルオキシ基、ブトキシ基等のアルコキシ基；フッ素原子、塩素原子、臭素原子等のハロゲン原子；フェニル基、ナフチル基、アントリル基等のアリール基；フェニルメチル基、フェニルエチル基、ナフチルメチル基、ナフチルエチル基等のアラルキル基等が挙げられる。 The phenolic hydroxyl group-containing compound (A) may be any compound as long as it is an aromatic compound having a hydroxyl group on the aromatic ring, and other specific structures are not particularly limited. In this invention, a phenolic hydroxyl group containing compound (A) may be used individually by 1 type, and may be used in combination of 2 or more types. Specific examples of the phenolic hydroxyl group-containing compound (A) include phenol, naphthol, anthracenol, and compounds having one or more substituents on these aromatic nuclei. Substituents on the aromatic nucleus are, for example, methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl Group, aliphatic hydrocarbon group such as dodecyl group; alkoxy group such as methoxy group, ethoxy group, propyloxy group, butoxy group; halogen atom such as fluorine atom, chlorine atom, bromine atom; phenyl group, naphthyl group, anthryl group An aryl group such as phenylmethyl group, phenylethyl group, naphthylmethyl group, naphthylethyl group, and the like.

　これらの中でも、硬化物における耐熱性や吸湿性が高く、誘電特性にも優れる活性エステル樹脂となることから、芳香環上に一つ乃至複数の炭化水素基を有するフェノール化合物（ａ）が好ましい。また、芳香環上の炭化水素基の数は１又は２であることが好ましい。前記フェノール化合物（ａ）が芳香環上に有する炭化水素基は、前記脂肪族炭化水素基や、前記アリール基、前記アラルキル基等が挙げられるが、中でも、硬化物における耐熱性や吸湿性が高く、誘電特性にも優れる活性エステル樹脂となることから、脂肪族炭化水素基又はアリール基であることが好ましく、その炭素原子数は１～１２の範囲であることが好ましい。更に、前記脂肪族炭化水素基は分岐構造を有することがより好ましく、この場合、炭素原子数は３～１２の範囲であることが好ましい。分岐構造を有する脂肪族炭化水素基の具体例としては、イソプロピル基、イソブチル基、セカンダリーブチル基、ターシャリーブチル基、イソペンチル基、ネオペンチル基、ターシャリーペンチル基、ターシャリーオクチル基等が挙げられる。 Among these, the phenolic compound (a) having one or more hydrocarbon groups on the aromatic ring is preferable because it becomes an active ester resin having high heat resistance and moisture absorption in the cured product and excellent dielectric properties. The number of hydrocarbon groups on the aromatic ring is preferably 1 or 2. Examples of the hydrocarbon group that the phenol compound (a) has on the aromatic ring include the aliphatic hydrocarbon group, the aryl group, and the aralkyl group. Among them, the heat resistance and hygroscopicity in the cured product are high. From the standpoint of an active ester resin having excellent dielectric properties, an aliphatic hydrocarbon group or an aryl group is preferable, and the number of carbon atoms is preferably in the range of 1 to 12. Further, the aliphatic hydrocarbon group preferably has a branched structure, and in this case, the number of carbon atoms is preferably in the range of 3 to 12. Specific examples of the aliphatic hydrocarbon group having a branched structure include isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, and tertiary octyl group.

　前記フェノール樹脂（Ｂ）について、芳香環上に一つ乃至複数の炭化水素基を有するフェノール化合物（ｂ）が有する炭化水素基は、例えば、メチル基、エチル基、ビニル基、プロピル基、ブチル基、ペンチル基、へキシル基、シクロへキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等の脂肪族炭化水素基；フェニル基、ナフチル基、アントリル基等のアリール基；フェニルメチル基、フェニルエチル基、ナフチルメチル基、ナフチルエチル基等のアラルキル基等が挙げられる。中でも、硬化物における耐熱性や耐吸湿性が高く、誘電特性にも優れる活性エステル樹脂となることから、前記炭化水素基は脂肪族炭化水素基又はアリール基であることが好ましく、その炭素原子数は１～１２の範囲であることが好ましい。また、芳香環上の炭化水素基の数は１又は２であることが好ましい。更に、前記脂肪族炭化水素基は分岐構造を有することがより好ましく、この場合、炭素原子数は３～１２の範囲であることが好ましい。分岐構造を有する脂肪族炭化水素基の具体例としては、イソプロピル基、イソブチル基、セカンダリーブチル基、ターシャリーブチル基、イソペンチル基、ネオペンチル基、ターシャリーペンチル基、ターシャリーオクチル基等が挙げられる。 Regarding the phenol resin (B), the hydrocarbon group of the phenol compound (b) having one or more hydrocarbon groups on the aromatic ring is, for example, a methyl group, an ethyl group, a vinyl group, a propyl group, or a butyl group. , Pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and other aliphatic hydrocarbon groups; phenyl group, naphthyl group, anthryl group and the like aryl groups An aralkyl group such as a phenylmethyl group, a phenylethyl group, a naphthylmethyl group, and a naphthylethyl group; Among them, the hydrocarbon group is preferably an aliphatic hydrocarbon group or an aryl group, since it becomes an active ester resin having high heat resistance and moisture absorption resistance in a cured product and excellent dielectric properties, and the number of carbon atoms thereof. Is preferably in the range of 1-12. The number of hydrocarbon groups on the aromatic ring is preferably 1 or 2. Further, the aliphatic hydrocarbon group preferably has a branched structure, and in this case, the number of carbon atoms is preferably in the range of 3 to 12. Specific examples of the aliphatic hydrocarbon group having a branched structure include isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, and tertiary octyl group.

　前記芳香環上に一つ乃至複数の炭化水素基を有するフェノール化合物（ｂ）がメチレン基で結節された分子構造を有するフェノール樹脂（Ｂ）の具体例としては、例えば、前記芳香環上に一つ乃至複数の炭化水素基を有するフェノール化合物（ｂ）とホルムアルデヒドとの重縮合物が挙げられる。 Specific examples of the phenol resin (B) having a molecular structure in which a phenol compound (b) having one or more hydrocarbon groups on the aromatic ring is knotted by a methylene group include, for example, one on the aromatic ring. And a polycondensation product of phenol compound (b) having one or more hydrocarbon groups and formaldehyde.

　前記フェノール化合物（ｂ）とホルムアルデヒドとの重縮合物は、例えば、通常のフェノールノボラック樹脂の製造と同様の方法にて製造することができる。具体的には、前記フェノール化合物（ｂ）とホルムアルデヒドとを、酸触媒の存在下、１００～２００℃の温度条件下で反応させる方法が挙げられる。反応終了後は所望に応じて、過剰量の前記フェノール化合物（ｂ）を留去するなどしても良い。また、反応混合中の未反応フェノール化合物をそのままフェノール性水酸基含有化合物（Ａ）として用いても良い。 The polycondensation product of the phenol compound (b) and formaldehyde can be produced, for example, by a method similar to the production of a normal phenol novolac resin. Specifically, a method of reacting the phenol compound (b) with formaldehyde in the presence of an acid catalyst under a temperature condition of 100 to 200 ° C. can be mentioned. After completion of the reaction, an excess amount of the phenol compound (b) may be distilled off as desired. Moreover, you may use the unreacted phenol compound in reaction mixture as a phenolic hydroxyl-containing compound (A) as it is.

　前記方法で用いるホルムアルデヒドは、ホルマリン溶液として用いても、パラホルムアルデヒドとして用いてもよい。前記フェノール化合物（ｂ）と前記アルデヒドとの反応割合は、反応を制御しやすいことから、フェノール化合物（ｂ）１モルに対しホルムアルデヒドが０．０１～０．９モルの範囲となる割合であることが好ましい。 The formaldehyde used in the above method may be used as a formalin solution or as paraformaldehyde. The reaction ratio between the phenol compound (b) and the aldehyde is such that the reaction is easy to control, so that the formaldehyde is in the range of 0.01 to 0.9 mole per mole of the phenol compound (b). Is preferred.

　前記酸触媒は、例えば、塩酸、硫酸、リン酸などの無機酸、メタンスルホン酸、パラトルエンスルホン酸、シュウ酸などの有機酸、三フッ化ホウ素、無水塩化アルミニウム、塩化亜鉛などのルイス酸などが挙げられる。これらはそれぞれ単独で用いてもよいし、２種類以上を併用してもよい。これら酸触媒の使用量は、反応原料の総質量に対して０．１～５質量％の範囲であることが好ましい。 Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Is mentioned. These may be used alone or in combination of two or more. The amount of these acid catalysts used is preferably in the range of 0.1 to 5% by mass relative to the total mass of the reaction raw materials.

　前記フェノール化合物（ｂ）とホルムアルデヒドとの反応は、必要に応じて有機溶剤中で行っても良い。ここで用いる有機溶剤は、前記温度条件下で使用可能な有機溶剤であれば特に限定されるものではなく、具体的には、メチルセロソルブ、エチルセロソルブ、トルエン、キシレン、メチルイソブチルケトン等が挙げられる。これら有機溶剤を用いる場合には反応原料の総質量に対し１０～５００質量％の範囲で用いることが好ましい。 The reaction between the phenol compound (b) and formaldehyde may be performed in an organic solvent as necessary. The organic solvent used here is not particularly limited as long as it is an organic solvent that can be used under the above temperature conditions. Specific examples include methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. . When these organic solvents are used, they are preferably used in the range of 10 to 500% by mass relative to the total mass of the reaction raw materials.

　前記フェノール化合物（ｂ）とホルムアルデヒドとの反応では、得られるノボラック型樹脂の着色を抑制する目的で、各種の酸化防止剤や還元剤を用いても良い。前記酸化防止剤は、例えば、２，６－ジアルキルフェノール誘導体などのヒンダードフェノール化合物、２価の硫黄化合物、３価のリン原子を含む亜リン酸エステル化合物等が挙げられる。前記還元剤は、例えば、次亜リン酸、亜リン酸、チオ硫酸、亜硫酸、ハイドロサルファイト、これらの塩や亜鉛等が挙げられる。 In the reaction of the phenol compound (b) with formaldehyde, various antioxidants and reducing agents may be used for the purpose of suppressing coloring of the novolak resin obtained. Examples of the antioxidant include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing a trivalent phosphorus atom. Examples of the reducing agent include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, salts thereof, and zinc.

　反応終了後は、反応混合物を中和処理或いは水洗した後、未反応の反応原料や副生成物等を留去するなどして、目的のフェノール樹脂（Ｂ）を得ることができる。
After completion of the reaction, the target phenol resin (B) can be obtained by neutralizing the reaction mixture or washing with water, and then distilling off unreacted raw materials and by-products.

　前記フェノール樹脂（Ｂ）の水酸基当量は、溶剤溶解性が高く、様々な用途に利用しやすい活性エステル樹脂となることから、１１０～２５０ｇ/当量の範囲であることが好ましい。また、前記フェノール樹脂（Ｂ）の軟化点は、４０～１３０℃の範囲であることが好ましい。 The hydroxyl equivalent of the phenol resin (B) is preferably in the range of 110 to 250 g / equivalent because it is an active ester resin that has high solvent solubility and can be easily used for various purposes. The softening point of the phenol resin (B) is preferably in the range of 40 to 130 ° C.

　前記芳香族ポリカルボン酸又はその酸ハロゲン化物（Ｃ）は、前記フェノール性水酸基含有化合物（Ａ）及び前記フェノール樹脂（Ｂ）が有するフェノール性水酸基と反応してエステル結合を形成し得る芳香族化合物であれば、具体構造は特に限定されず、何れの化合物であっても良い。具体例としては、例えば、イソフタル酸、テレフタル酸等のベンゼンジカルボン酸、トリメリット酸等のベンゼントリカルボン酸、ナフタレン－１，４－ジカルボン酸、ナフタレン－２，３－ジカルボン酸、ナフタレン－２，６－ジカルボン酸、ナフタレン－２，７－ジカルボン酸等のナフタレンジカルボン酸、これらの酸ハロゲン化物、及びこれらの芳香核上に前記脂肪族炭化水素基やアルコキシ基、ハロゲン原子等が置換した化合物等が挙げられる。酸ハロゲン化物は、例えば、酸塩化物、酸臭化物、酸フッ化物、酸ヨウ化物等が挙げられる。これらはそれぞれ単独で用いても良いし、2種類以上を併用しても良い。中でも、反応活性が高く硬化性に優れる活性エステル樹脂となることから、イソフタル酸やテレフタル酸等のベンゼンジカルボン酸又はその酸ハロゲン化物が好ましい。 The aromatic polycarboxylic acid or its acid halide (C) reacts with the phenolic hydroxyl group of the phenolic hydroxyl group-containing compound (A) and the phenol resin (B) to form an ester bond. If so, the specific structure is not particularly limited, and any compound may be used. Specific examples include benzenedicarboxylic acids such as isophthalic acid and terephthalic acid, benzenetricarboxylic acids such as trimellitic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, and naphthalene-2,6. -Naphthalene dicarboxylic acids such as dicarboxylic acids and naphthalene-2,7-dicarboxylic acids, acid halides thereof, and compounds in which the aliphatic hydrocarbon group, alkoxy group, halogen atom, etc. are substituted on the aromatic nucleus, etc. Can be mentioned. Examples of the acid halide include acid chloride, acid bromide, acid fluoride, and acid iodide. These may be used alone or in combination of two or more. Among these, benzenedicarboxylic acids such as isophthalic acid and terephthalic acid or acid halides thereof are preferable because they are active ester resins having high reaction activity and excellent curability.

　前記フェノール性水酸基含有化合物（Ａ）、前記フェノール樹脂（Ｂ）、及び前記芳香族ポリカルボン酸又はその酸ハロゲン化物（Ｃ）の反応は、例えば、アルカリ触媒の存在下、４０～６５℃程度の温度条件下で加熱撹拌する方法により行うことができる。反応は必要に応じて有機溶媒中で行っても良い。また、反応終了後は所望に応じて、水洗や再沈殿等により反応生成物を精製しても良い。 The reaction of the phenolic hydroxyl group-containing compound (A), the phenol resin (B), and the aromatic polycarboxylic acid or its acid halide (C) is, for example, about 40 to 65 ° C. in the presence of an alkali catalyst. It can carry out by the method of heating and stirring under temperature conditions. You may perform reaction in an organic solvent as needed. Further, after completion of the reaction, the reaction product may be purified by washing, reprecipitation or the like, if desired.

　前記アルカリ触媒は、例えば、水酸化ナトリウム、水酸化カリウム、トリエチルアミン、ピリジン等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。また、３．０～３０％程度の水溶液として用いても良い。中でも、触媒能の高い水酸化ナトリウム又は水酸化カリウムが好ましい。 Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, triethylamine, pyridine and the like. These may be used alone or in combination of two or more. Further, it may be used as an aqueous solution of about 3.0 to 30%. Among these, sodium hydroxide or potassium hydroxide having high catalytic ability is preferable.

　前記有機溶媒は、例えば、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン溶媒、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル溶媒、セロソルブ、ブチルカルビトール等のカルビトール溶媒、トルエン、キシレン等の芳香族炭化水素溶媒、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上の混合溶媒としても良い。 Examples of the organic solvent 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; and carbitols such as cellosolve and butyl carbitol. Examples include solvents, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These may be used alone or as a mixed solvent of two or more.

　前記フェノール性水酸基含有化合物（Ａ）、前記フェノール樹脂（Ｂ）、及び前記芳香族ポリカルボン酸又はその酸ハロゲン化物（Ｃ）の反応割合は、所望の分子設計に応じて適宜変更することができる。中でも、溶剤溶解性が高く、様々な用途に利用しやすい活性エステル樹脂となることから、前記フェノール性水酸基含有化合物（Ａ）が有する水酸基のモル数（ＡＯＨ）と前記フェノール樹脂（Ｂ）が有する水酸基のモル数（ＢＯＨ）との割合［（ＡＯＨ）/（ＢＯＨ）］が１０/９０～７５/２５となる割合であることが好ましく、２０/８０～５０/５０となる割合であることがより好ましい。また、芳香族ポリカルボン酸又はその酸ハロゲン化物（Ｃ）が有するカルボキシル基又は酸ハライド基の合計１モルに対し、前記フェノール性水酸基含有化合物（Ａ）が有する水酸基のモル数と前記フェノール樹脂（Ｂ）が有する水酸基のモル数との合計が０．９～１．１モルとなる割合であることが好ましい。 The reaction ratio of the phenolic hydroxyl group-containing compound (A), the phenol resin (B), and the aromatic polycarboxylic acid or acid halide (C) thereof can be appropriately changed according to the desired molecular design. . Among them, since it becomes an active ester resin that has high solvent solubility and can be easily used for various applications, the number of moles of hydroxyl group (A OH ) of the phenolic hydroxyl group-containing compound (A) and the phenol resin (B) The ratio of [(A OH ) / (B OH )] to the number of moles of hydroxyl groups (B OH ) possessed is preferably 10/90 to 75/25, preferably 20/80 to 50/50 It is more preferable that Moreover, with respect to 1 mol in total of the carboxyl group or acid halide group which aromatic polycarboxylic acid or its acid halide (C) has, the number of moles of the hydroxyl group which said phenolic hydroxyl group containing compound (A) has, and said phenol resin ( It is preferable that the sum of the number of moles of hydroxyl groups of B) is 0.9 to 1.1 moles.

　本発明の活性エステル樹脂は、前記フェノール性水酸基含有化合物（Ａ）と、前記芳香族ポリカルボン酸又はその酸ハロゲン化物（Ｃ）とのエステル化合物（ＡＣ）を含有していても良い。前記エステル化合物（ＡＣ）は、例えば、前記フェノール性水酸基含有化合物（Ａ）、前記フェノール樹脂（Ｂ）、及び前記芳香族ポリカルボン酸又はその酸ハロゲン化物（Ｃ）の反応割合を調製することにより、活性エステル樹脂の一成分として製造することができる。 The active ester resin of the present invention may contain an ester compound (AC) of the phenolic hydroxyl group-containing compound (A) and the aromatic polycarboxylic acid or its acid halide (C). The ester compound (AC) is prepared, for example, by adjusting the reaction ratio of the phenolic hydroxyl group-containing compound (A), the phenol resin (B), and the aromatic polycarboxylic acid or acid halide (C) thereof. Can be produced as a component of an active ester resin.

　前記エステル化合物（ＡＣ）の具体構造の一例として、例えば、前記フェノール性水酸基含有化合物（Ａ）として芳香環上に一つ乃至複数の炭化水素基を有するフェノール化合物（ａ）を用い、前記芳香族ポリカルボン酸又はその酸ハロゲン化物（Ｃ）としてベンゼンジカルボン酸又はその酸ハロゲン化物を用いた場合の構造例を下記構造式（１）に示す。なお、下記構造式（１）は前記エステル化合物（ＡＣ）の具体構造の一例に過ぎず、その他の分子構造を有するジエステル化合物を排除するものではない。 As an example of the specific structure of the ester compound (AC), for example, a phenol compound (a) having one or more hydrocarbon groups on an aromatic ring is used as the phenolic hydroxyl group-containing compound (A). A structural example in the case of using benzenedicarboxylic acid or its acid halide as the polycarboxylic acid or its acid halide (C) is shown in the following structural formula (1). The following structural formula (1) is merely an example of the specific structure of the ester compound (AC), and does not exclude diester compounds having other molecular structures.

Figure JPOXMLDOC01-appb-C000001
（式中Ｒ１はそれぞれ独立して炭化水素基を表し、ベンゼン環上のどの炭素原子に結合していても良く、ｎは０又は１～５の整数である。）
Figure JPOXMLDOC01-appb-C000001
 (In the formula, each R 1 independently represents a hydrocarbon group, which may be bonded to any carbon atom on the benzene ring, and n is 0 or an integer of 1 to 5).

　活性エステル樹脂が前記エステル化合物（ＡＣ）を含有する場合、その含有量は活性エステル樹脂の４０％未満であることが好ましく、０．５～３０％の範囲であることがより好ましい。 When the active ester resin contains the ester compound (AC), the content is preferably less than 40% of the active ester resin, and more preferably in the range of 0.5 to 30%.

　活性エステル樹脂中の前記エステル化合物（ＡＣ）の含有量は、下記条件で測定されるＧＰＣチャート図の面積比から算出される値である。 The content of the ester compound (AC) in the active ester resin is a value calculated from the area ratio of the GPC chart measured under the following conditions.

　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。
　　（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） 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”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
“A-1000” manufactured by Tosoh Corporation
“A-2500” manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
“F-2” manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids, filtered through a microfilter (50 μl)

　本発明の活性エステル樹脂の官能基当量は、硬化収縮率が低く、かつ、硬化性にも優れる活性エステル樹脂となることから、１５０～３５０ｇ/当量の範囲であることが好ましい。なお、本発明において活性エステル樹脂中の官能基とは、活性エステル樹脂中のエステル結合部位とフェノール性水酸基とのことを言う。また、活性エステル樹脂の官能基当量は、反応原料の仕込み量から算出される値である。 The functional group equivalent of the active ester resin of the present invention is preferably in the range of 150 to 350 g / equivalent because it becomes an active ester resin having a low cure shrinkage and excellent curability. In the present invention, the functional group in the active ester resin means an ester bond site and a phenolic hydroxyl group in the active ester resin. The functional group equivalent of the active ester resin is a value calculated from the charged amount of the reaction raw material.

　本発明の活性エステル樹脂の軟化点は、ＪＩＳ　Ｋ７２３４に基づいて測定される値で８５～１６０℃の範囲であることが好ましく、１００～１５０℃の範囲であることがより好ましい。 The softening point of the active ester resin of the present invention is preferably in the range of 85 to 160 ° C., more preferably in the range of 100 to 150 ° C., as measured based on JIS K7234.

　本発明の硬化性樹脂組成物は、前述の活性エステル樹脂と硬化剤とを含有する。前記硬化剤は本発明の活性エステル樹脂と反応し得る化合物であれば良く、特に限定なく様々な化合物が利用できる。硬化剤の一例としては、例えば、エポキシ樹脂が挙げられる。 The curable resin composition of the present invention contains the aforementioned active ester resin and a curing agent. The curing agent may be a compound that can react with the active ester resin of the present invention, and various compounds can be used without any particular limitation. An example of the curing agent is an epoxy resin.

　前記エポキシ樹脂は、例えば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ビスフェノールノボラック型エポキシ樹脂、ビフェノールノボラック型エポキシ樹脂、ビスフェノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、テトラフェノールエタン型エポキシ樹脂、ジシクロペンタジエン－フェノール付加反応型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂等が挙げられる。 Examples of the epoxy resin include phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, bisphenol novolac type epoxy resin, biphenol novolac type epoxy resin, bisphenol type epoxy resin, biphenyl type epoxy resin, and triphenolmethane. Type epoxy resin, tetraphenolethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin and the like.

　前記硬化剤としてエポキシ樹脂を用いる場合、本発明の活性エステル樹脂以外に、その他のエポキシ樹脂用硬化剤を併用してもよい。ここで用いるその他のエポキシ樹脂用硬化剤は、例えば、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、イミダゾ－ル、ＢＦ３－アミン錯体、グアニジン誘導体等のアミン化合物；ジシアンジアミド、リノレン酸の２量体とエチレンジアミンとより合成されるポリアミド樹脂等のアミド化合物；無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等の酸無水物；フェノールノボラック樹脂、クレゾールノボラック樹脂、ナフトールノボラック樹脂、ビスフェノールノボラック樹脂、ビフェニルノボラック樹脂、ジシクロペンタジエン－フェノール付加型樹脂、フェノールアラルキル樹脂、ナフトールアラルキル樹脂、トリフェノールメタン型樹脂、テトラフェノールエタン型樹脂、アミノトリアジン変性フェノール樹脂等のフェノール樹脂等が挙げられる。 When using an epoxy resin as the curing agent, in addition to the active ester resin of the present invention, other epoxy resin curing agents may be used in combination. Other epoxy resin curing agents used herein include, for example, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF 3 -amine complexes, guanidine derivatives and other amine compounds; dicyandiamide, linolene Amide compounds such as polyamide resin synthesized from dimer of acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl anhydride Acid anhydrides such as nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; phenol novolak resin, cresol novolak resin, naphthol novolak resin, bisphenol novolak Fat, biphenyl novolac resins, dicyclopentadiene - phenol addition type resins, phenol aralkyl resins, naphthol aralkyl resins, triphenolmethane resins, tetraphenolethane type resins, phenolic resins such as aminotriazine-modified phenolic resin.

　本発明の活性エステル樹脂、エポキシ樹脂、及びその他のエポキシ樹脂用硬化剤組成物の配合割合は、エポキシ樹脂中のエポキシ基の合計１モルに対して、前記活性エステル樹脂及びその他のエポキシ樹脂用硬化剤中の官能基の合計が０．７～１．５モルとなる割合であることが好ましい。 The active ester resin, the epoxy resin, and the curing agent composition for other epoxy resins of the present invention are blended in a proportion of 1 mol in total for the epoxy groups in the epoxy resin. The ratio is preferably such that the total of functional groups in the agent is 0.7 to 1.5 mol.

　本発明の硬化性樹脂組成物は、この他、シアン酸エステル樹脂、ビスマレイミド樹脂、ベンゾオキサジン樹脂、スチレン－無水マレイン酸樹脂、ジアリルビスフェノールやトリアリルイソシアヌレートに代表されるアリル基含有樹脂、ポリリン酸エステルやリン酸エステル－カーボネート共重合体等を含有しても良い。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。 In addition, the curable resin composition of the present invention includes cyanate ester resins, bismaleimide resins, benzoxazine resins, styrene-maleic anhydride resins, allyl group-containing resins represented by diallyl bisphenol and triallyl isocyanurate, polyphosphorus An acid ester or a phosphate ester-carbonate copolymer may be contained. These may be used alone or in combination of two or more.

　本発明の硬化性樹脂組成物は必要に応じて硬化促進剤、難燃剤、無機質充填材、シランカップリング剤、離型剤、顔料、乳化剤等の各種添加剤を含有しても良い。 The curable resin composition of the present invention may contain various additives such as a curing accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a release agent, a pigment, and an emulsifier, if necessary.

　前記硬化促進剤は、例えば、リン系化合物、第３級アミン、イミダゾール化合物、ピリジン化合物、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。中でも、硬化性、耐熱性、電気特性、耐湿信頼性等に優れる点から、リン系化合物ではトリフェニルホスフィン、第３級アミンでは１，８－ジアザビシクロ－［５．４．０］－ウンデセン（ＤＢＵ）、イミダゾール化合物では２－エチル－４－メチルイミダゾール、ピリジン化合物では４－ジメチルアミノピリジンが好ましい。 Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazole compounds, pyridine compounds, organic acid metal salts, Lewis acids, amine complex salts, and the like. Of these, triphenylphosphine is used for phosphorus compounds, and 1,8-diazabicyclo- [5.4.0] -undecene (DBU is used for tertiary amines because of its excellent curability, heat resistance, electrical properties, moisture resistance reliability, and the like. ), 2-ethyl-4-methylimidazole is preferred for imidazole compounds, and 4-dimethylaminopyridine is preferred for pyridine compounds.

　前記難燃剤は、例えば、赤リン、リン酸一アンモニウム、リン酸二アンモニウム、リン酸三アンモニウム、ポリリン酸アンモニウム等のリン酸アンモニウム、リン酸アミド等の無機リン化合物；リン酸エステル化合物、ホスホン酸化合物、ホスフィン酸化合物、ホスフィンオキシド化合物、ホスホラン化合物、有機系含窒素リン化合物、９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド、１０－（２，５―ジヒドロオキシフェニル）―１０Ｈ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド、１０―（２，７－ジヒドロオキシナフチル）－１０Ｈ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド等の環状有機リン化合物、及びそれをエポキシ樹脂やフェノール樹脂等の化合物と反応させた誘導体等の有機リン化合物；トリアジン化合物、シアヌル酸化合物、イソシアヌル酸化合物、フェノチアジン等の窒素系難燃剤；シリコーンオイル、シリコーンゴム、シリコーン樹脂等のシリコーン系難燃剤；金属水酸化物、金属酸化物、金属炭酸塩化合物、金属粉、ホウ素化合物、低融点ガラス等の無機難燃剤等が挙げられる。これら難燃剤を用いる場合は、硬化性樹脂組成物中０．１～２０質量％の範囲であることが好ましい。 The flame retardant is, for example, red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, inorganic phosphorus compounds such as phosphate amide; phosphate ester compound, phosphonic acid Compound, phosphinic acid compound, phosphine oxide compound, phosphorane compound, organic nitrogen-containing phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) ) Cyclic organic phosphorus such as -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide Compound and its compound such as epoxy resin and phenol resin Organophosphorus compounds such as derivatives reacted with nitrogen; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds and phenothiazines; silicone-based flame retardants such as silicone oil, silicone rubber and silicone resin; metal hydroxides; Examples include inorganic flame retardants such as metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. When these flame retardants are used, the content is preferably in the range of 0.1 to 20% by mass in the curable resin composition.

　前記無機質充填材は、例えば、本発明の硬化性樹脂組成物を半導体封止材料用途に用いる場合などに配合される。前記無機質充填材は、例えば、溶融シリカ、結晶シリカ、アルミナ、窒化珪素、水酸化アルミ等が挙げられる。中でも、無機質充填材をより多く配合することが可能となることから、前記溶融シリカが好ましい。前記溶融シリカは破砕状、球状のいずれでも使用可能であるが、溶融シリカの配合量を高め、且つ、硬化性組成物の溶融粘度の上昇を抑制するためには、球状のものを主に用いることが好ましい。更に、球状シリカの配合量を高めるためには、球状シリカの粒度分布を適当に調整することが好ましい。その充填率は硬化性樹脂組成物１００質量部中、０．５～９５質量部の範囲で配合することが好ましい。 The inorganic filler is blended, for example, when the curable resin composition of the present invention is used for semiconductor sealing materials. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Especially, since it becomes possible to mix | blend more inorganic fillers, the said fused silica is preferable. The fused silica can be used in either crushed or spherical shape, but in order to increase the blending amount of the fused silica and to suppress an increase in the melt viscosity of the curable composition, a spherical one is mainly used. It is preferable. Furthermore, in order to increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition.

　この他、本発明の硬化性樹脂組成物を導電ペーストなどの用途に使用する場合は、銀粉や銅粉等の導電性充填剤を用いることができる。 In addition, when the curable resin composition of the present invention is used for applications such as a conductive paste, a conductive filler such as silver powder or copper powder can be used.

　以上詳述した通り、本発明の活性エステル樹脂は、硬化物における耐熱性や耐吸湿性が高く、誘電特性にも優れる特徴を有する。この他、汎用有機溶剤への溶解性や、エポキシ樹脂との硬化性等、樹脂材料に求められる一般的な要求性能も十分に高いものであり、プリント配線基板や半導体封止材料、レジスト材料等の電子材料用途の他、塗料や接着剤、成型品等の用途にも広く利用することができる。 As described in detail above, the active ester resin of the present invention is characterized by high heat resistance and moisture absorption resistance in a cured product and excellent dielectric properties. In addition, the general required performance required for resin materials, such as solubility in general-purpose organic solvents and curability with epoxy resins, is sufficiently high, such as printed wiring boards, semiconductor encapsulation materials, resist materials, etc. In addition to the above electronic material applications, it can be widely used for applications such as paints, adhesives and molded products.

　本発明の硬化性樹脂組成物をプリント配線基板用途やビルドアップ接着フィルム用途に用いる場合、一般には有機溶剤を配合して希釈して用いることが好ましい。前記有機溶剤は、メチルエチルケトン、アセトン、ジメチルホルムアミド、メチルイソブチルケトン、メトキシプロパノール、シクロヘキサノン、メチルセロソルブ、エチルジグリコールアセテート、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。有機溶剤の種類や配合量は硬化性樹脂組成物の使用環境に応じて適宜調整できるが、例えば、プリント配線板用途では、メチルエチルケトン、アセトン、ジメチルホルムアミド等の沸点が１６０℃以下の極性溶剤であることが好ましく、不揮発分が４０～８０質量％となる割合で使用することが好ましい。ビルドアップ接着フィルム用途では、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン溶剤、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル溶剤、セロソルブ、ブチルカルビトール等のカルビトール溶剤、トルエン、キシレン等の芳香族炭化水素溶剤、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン等を用いることが好ましく、不揮発分が３０～６０質量％となる割合で使用することが好ましい。 When the curable resin composition of the present invention is used for printed wiring board applications or build-up adhesive film applications, it is generally preferable to mix and dilute with an organic solvent. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate and the like. The type and blending amount of the organic solvent can be adjusted as appropriate according to the use environment of the curable resin composition. For example, for printed wiring board applications, methyl ethyl ketone, acetone, dimethylformamide and the like are polar solvents having a boiling point of 160 ° C. or lower. The non-volatile content is preferably 40 to 80% by mass. For build-up adhesive film applications, 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, carbitols such as cellosolve, butyl carbitol, etc. It is preferable to use a solvent, an aromatic hydrocarbon solvent such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like, and it is preferable to use them in a proportion that the nonvolatile content is 30 to 60% by mass.

　また、本発明の硬化性樹脂組成物を用いてプリント配線基板を製造する方法は、例えば、硬化性組成物を補強基材に含浸し硬化させてプリプレグを得、これと銅箔とを重ねて加熱圧着させる方法が挙げられる。前記補強基材は、紙、ガラス布、ガラス不織布、アラミド紙、アラミド布、ガラスマット、ガラスロービング布などが挙げられる。硬化性樹脂組成物の含浸量は特に限定されないが、通常、プリプレグ中の樹脂分が２０～６０質量％となるように調製することが好ましい。 Moreover, the method of manufacturing a printed wiring board using the curable resin composition of the present invention includes, for example, impregnating a curable composition into a reinforcing base material and curing it to obtain a prepreg, and stacking this with a copper foil. The method of carrying out thermocompression bonding is mentioned. Examples of the reinforcing substrate include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. The amount of impregnation of the curable resin composition is not particularly limited, but it is usually preferable to prepare so that the resin content in the prepreg is 20 to 60% by mass.

　本発明の硬化性樹脂組成物を半導体封止材料用途に用いる場合、一般には無機質充填材を配合することが好ましい。本発明の活性エステル樹脂と硬化剤、無機質充填剤、及びその他の任意成分を含有する半導体封止材料は、例えば、押出機、ニーダー、ロール等を用いて配合物を混合して調製することができる。得られた半導体封止材料を用いて半導体パッケージを成型する方法は、例えば、該半導体封止材料を注型或いはトランスファー成形機、射出成型機などを用いて成形し、更に５０～２００℃の温度条件下で２～１０時間加熱する方法が挙げられ、このような方法により、成形物である半導体装置を得ることが出来る。 In general, when the curable resin composition of the present invention is used for a semiconductor sealing material, it is preferable to blend an inorganic filler. The semiconductor encapsulating material containing the active ester resin of the present invention, a curing agent, an inorganic filler, and other optional components may be prepared by mixing the compound using, for example, an extruder, a kneader, or a roll. it can. A method for molding a semiconductor package using the obtained semiconductor sealing material includes, for example, molding the semiconductor sealing material using a casting or transfer molding machine, injection molding machine, etc., and further a temperature of 50 to 200 ° C. Examples of the method include heating for 2 to 10 hours under conditions, and by such a method, a semiconductor device which is a molded product can be obtained.

　次に本発明を実施例、比較例により具体的に説明する。実施例中の「部」及び「％」の記載は、特に断わりのない限り質量基準である。なお、本実施例におけるＧＰＣ測定条件は以下の通りである。 Next, the present invention will be specifically described with reference to examples and comparative examples. In the examples, “parts” and “%” are based on mass unless otherwise specified. In addition, the GPC measurement conditions in a present Example are as follows.

◆ＧＰＣの測定条件
　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。
　　（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） ◆ 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 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”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
“A-1000” manufactured by Tosoh Corporation
“A-2500” manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
“F-2” manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids, filtered through a microfilter (50 μl)

実施例１　活性エステル樹脂（１）の製造
　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、パラターシャリブチルフェノール２３４．３質量部、トルエン５２．８部、３７質量％ホルマリン水溶液５２．８質量部、４９％水酸化ナトリウム４．８質量部を仕込み、室温から７５℃まで攪拌しながら７５℃まで昇温し、同温度で１時間撹拌して反応させた。反応終了後、第１リン酸ソーダ７．１質量部を添加して中和し、トルエン３６３．２質量部加え、水１２１．１質量部で３回洗浄した。加熱減圧条件下で乾燥させ、未反応のパラターシャリブチルフェノールとフェノール樹脂（Ｂ－１）とを含む混合物（１）２３４．８質量部を得た。混合物（１）の水酸基当量は１５５ｇ/当量であった。 Example 1 Production of Active Ester Resin (1) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 234.3 parts by mass of paratertiary butylphenol, 52.8 parts of toluene, 37 parts by mass 52.8 parts by weight of a formalin aqueous solution and 4.8 parts by weight of 49% sodium hydroxide were charged, the temperature was raised from room temperature to 75 ° C. with stirring, and the mixture was stirred at the same temperature for 1 hour for reaction. After completion of the reaction, 7.1 parts by mass of first sodium phosphate was added for neutralization, 363.2 parts by mass of toluene was added, and the mixture was washed 3 times with 121.1 parts by mass of water. The mixture was dried under heating and reduced pressure to obtain 234.8 parts by mass of a mixture (1) containing unreacted paratertiary butylphenol and phenol resin (B-1). The hydroxyl equivalent of mixture (1) was 155 g / equivalent.

　　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、イソフタル酸クロリド１４１．４質量部、トルエン１０００質量部を仕込み、系内を減圧窒素置換しながら溶解させた。次いで先で得た混合物（１）２１７．０質量部を仕込み、系内を減圧窒素置換しながら溶解させた。テトラブチルアンモニウムブロマイド０．４質量部を溶解させ、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２８０質量部を３時間かけて滴下した。滴下終了後、そのまま１時間撹拌を続けて反応させた。反応終了後、反応混合物を静置して分液し、水層を取り除いた。残った有機層に水３０７．３質量部を加えて約１５分間撹拌混合した後、混合物を静置して分液し、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後、加熱減圧条件下で乾燥させ、活性エステル樹脂（１）２９８．１質量部を得た。活性エステル樹脂（１）の官能基当量は２２０ｇ/当量、ＪＩＳ　Ｋ７２３４に基づいて測定した軟化点は１３２℃であった。また、ＧＰＣチャート図から算出される活性エステル樹脂（１）中のビス（パラターシャリーブチルフェニル）イソフタレートの含有量は１０．１％であった。 A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was charged with 141.4 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene, and dissolved in the system while substituting with nitrogen under reduced pressure. Next, 217.0 parts by mass of the previously obtained mixture (1) was charged, and the system was dissolved while substituting with nitrogen under reduced pressure. While dissolving 0.4 parts by mass of tetrabutylammonium bromide and applying a nitrogen gas purge, the inside of the system was controlled to 60 ° C. or less, and 280 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of dropping, the reaction was continued for 1 hour with stirring. After completion of the reaction, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. After adding 307.3 parts by mass of water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand and liquid-separated to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7, and then dried under heating and reduced pressure to obtain 298.1 parts by mass of an active ester resin (1). The functional group equivalent of the active ester resin (1) was 220 g / equivalent, and the softening point measured based on JIS K7234 was 132 ° C. In addition, the content of bis (paratertiary butylphenyl) isophthalate in the active ester resin (1) calculated from the GPC chart was 10.1%.

実施例２　活性エステル樹脂（２）の製造
　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、パラターシャリーオクチルフェノール３２１．９質量部、トルエン５２．８質量部、３７質量％ホルマリン水溶液５２．８質量部、４９％水酸化ナトリウム６．６質量部を仕込み、室温から７５℃まで昇温し、同温度で１時間撹拌して反応させた。反応終了後、第１リン酸ソーダ９．７質量部を添加して中和し、トルエン４９４．６質量部加え、水１６４．９質量部で３回洗浄した。加熱減圧条件下で乾燥させ、未反応のパラターシャリオクチルフェノールとフェノール樹脂（Ｂ－２）とを含む混合物（２）３１９．８質量部得た。混合物（２）の水酸基当量は２１１ｇ/当量であった。 Example 2 Production of Active Ester Resin (2) In a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, 321.9 parts by mass of paratertiary octylphenol, 52.8 parts by mass of toluene, 37 52.8 parts by mass of an aqueous formalin solution and 6.6 parts by mass of 49% sodium hydroxide were added, the temperature was raised from room temperature to 75 ° C., and the mixture was stirred at the same temperature for 1 hour for reaction. After completion of the reaction, the mixture was neutralized by adding 9.7 parts by mass of first sodium phosphate, added with 494.6 parts by mass of toluene, and washed with 164.9 parts by mass of water three times. The mixture was dried under heating under reduced pressure to obtain 319.8 parts by mass of a mixture (2) containing unreacted paratertiaryoctylphenol and phenol resin (B-2). The hydroxyl equivalent of the mixture (2) was 211 g / equivalent.

　実施例１において混合物（１）２１７．０質量部の代わりに混合物（２）２９５．４質量部に変更した以外は実施例１と同様にして、活性エステル樹脂（２）３７４．８質量部を得た。活性エステル樹脂（２）の官能基当量は２７６ｇ/当量、ＪＩＳ　Ｋ７２３４に基づいて測定した軟化点は１０１℃であった。また、ＧＰＣチャート図から算出される活性エステル樹脂（２）中のビス（パラターシャリーオクチルフェニル）イソフタレートの含有量は１４．８％であった。 In the same manner as in Example 1 except that instead of 217.0 parts by mass of the mixture (1) 217.0 parts by mass in Example 1, the mixture was changed to 295.4 parts by mass, the active ester resin (2) 374.8 parts by mass. Obtained. The functional group equivalent of the active ester resin (2) was 276 g / equivalent, and the softening point measured based on JIS K7234 was 101 ° C. In addition, the content of bis (paratertiary octylphenyl) isophthalate in the active ester resin (2) calculated from the GPC chart was 14.8%.

比較製造例１　活性エステル樹脂（１’）の製造
　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との付加反応物（水酸基当量１６５ｇ/当量、軟化点８５℃）１６５質量部、１－ナフトール７２質量部、及びトルエン６３０質量部を仕込み、系内を減圧窒素置換しながら溶解させた。次いで、イソフタル酸クロライド１５２質量部を仕込み、系内を減圧窒素置換しながら溶解させた。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２１０ｇを３時間かけて滴下した。滴下終了後、そのまま１時間撹拌を続けて反応させた。反応終了後、反応混合物を静置して分液し、水層を取り除いた。残った有機層に水を加えて約１５分間撹拌混合した後、混合物を静置して分液し、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後、加熱減圧条件下でトルエン等を留去し、活性エステル樹脂（１’）を得た。活性エステル樹脂（１’）の官能基当量は２２３ｇ/当量、ＪＩＳ　Ｋ７２３４に基づいて測定した軟化点は１５０℃であった。 Comparative Production Example 1 Production of Active Ester Resin (1 ′) Addition reaction product of dicyclopentadiene and phenol (hydroxyl equivalent 165 g / equivalent) to a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer , Softening point 85 ° C.), 165 parts by mass, 1-naphthol 72 parts by mass, and toluene 630 parts by mass were charged and the system was dissolved while substituting with nitrogen under reduced pressure. Next, 152 parts by mass of isophthalic acid chloride was charged, and the system was dissolved while substituting with nitrogen under reduced pressure. While performing nitrogen gas purge, the inside of the system was controlled to 60 ° C. or lower, and 210 g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of dropping, the reaction was continued for 1 hour with stirring. After completion of the reaction, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand and liquid-separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer became 7, and then toluene and the like were distilled off under heating and reduced pressure conditions to obtain an active ester resin (1 ′). The functional group equivalent of the active ester resin (1 ′) was 223 g / equivalent, and the softening point measured based on JIS K7234 was 150 ° C.

実施例３、４及び比較例１
　活性エステル樹脂、エポキシ樹脂（＊）、ジメチルアミノピリジンを下記表１に示す割合で配合し、メチルエチルケトンで不揮発分を５８質量％に調整して、硬化性樹脂組成物を得た。得られた硬化性樹脂組成物について、下記要領で各種評価試験を行った。結果を表１に示す。
エポキシ樹脂（＊）：ジシクロペンタジエン変性フェノール型エポキシ樹脂（ＤＩＣ株式会社製「ＥＰＩＣＬＯＮ　ＨＰ－７２００Ｈ」、エポキシ当量２７７ｇ/当量） Examples 3 and 4 and Comparative Example 1
An active ester resin, an epoxy resin (*), and dimethylaminopyridine were blended in the proportions shown in Table 1 below, and the nonvolatile content was adjusted to 58% by mass with methyl ethyl ketone to obtain a curable resin composition. About the obtained curable resin composition, various evaluation tests were done in the following way. The results are shown in Table 1.
Epoxy resin (*): dicyclopentadiene-modified phenol type epoxy resin (“EPICLON HP-7200H” manufactured by DIC Corporation, epoxy equivalent 277 g / equivalent)

積層板の作成
　下記条件で積層板を作成した。
　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 Creation of a laminated board The laminated board was created on condition of the following.
Base material: Nitto Boseki Co., Ltd. glass cloth “# 2116” (210 × 280 mm)
Number of plies: 6
Prepregation conditions: 160 ° C
Curing conditions: 200 ° C., 40 kg / cm 2 for 1.5 hours Molded plate thickness: 0.8 mm

ガラス転移温度の測定
　先で得た積層板を幅５ｍｍ、長さ５４ｍｍのサイズに切り出し、これを試験片として、粘弾性測定装置（レオメトリック社製「固体粘弾性測定装置ＲＳＡＩＩ」）を用い、レクタンギュラーテンション法、周波数１Ｈｚ、昇温速度３℃／分の測定条件で、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。 Measurement of glass transition temperature The laminate obtained above was cut into a size of 5 mm in width and 54 mm in length, and this was used as a test piece, using a viscoelasticity measuring device (“Solid Viscoelasticity Measuring Device RSAII” manufactured by Rheometric), Under the measurement conditions of the rectangular tension method, the frequency of 1 Hz, and the heating rate of 3 ° C./min, the temperature at which the elastic modulus change was maximum (the tan δ change rate was the largest) was evaluated as the glass transition temperature.

誘電率及び誘電正接の測定
　加熱真空乾燥後、２３℃、湿度５０％の室内に２４時間保管した積層板について、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」を用い、１ＧＨｚでの誘電率および誘電正接を測定した。 Measurement of dielectric constant and dielectric loss tangent A laminated board stored for 24 hours in a room at 23 ° C and 50% humidity after being heated and vacuum dried, in accordance with JIS-C-6481, impedance material analyzer manufactured by Agilent Technologies, Inc. HP 4291B "was used to measure the dielectric constant and dielectric loss tangent at 1 GHz.

耐吸湿性の評価
先で得た積層板を幅２５ｍｍ、長さ７５ｍｍのサイズに切り出し、これを試験片として、
８５℃／８５％ＲＨの雰囲気下に１６８時間放置し、吸湿試験を行った。試験前後の試験片の質量を測定し、その重量変化率を吸湿率として評価した。 The laminate obtained at the evaluation destination of moisture absorption resistance was cut into a size of 25 mm in width and 75 mm in length, and this was used as a test piece.
The sample was left for 168 hours in an atmosphere of 85 ° C./85% RH, and a moisture absorption test was performed. The mass of the test piece before and after the test was measured, and the weight change rate was evaluated as the moisture absorption rate.

Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Claims (9)

フェノール性水酸基含有化合物（Ａ）、芳香環上に一つ乃至複数の炭化水素基を有するフェノール化合物（ｂ）がメチレン基で結節された分子構造を有するフェノール樹脂（Ｂ）、及び芳香族ポリカルボン酸又はその酸ハロゲン化物（Ｃ）を必須の反応原料とすることを特徴とする活性エステル樹脂。 A phenolic hydroxyl group-containing compound (A), a phenol resin (B) having a molecular structure in which a phenol compound (b) having one or more hydrocarbon groups on an aromatic ring is knotted by a methylene group, and an aromatic polycarboxylic acid An active ester resin comprising an acid or an acid halide (C) thereof as an essential reaction raw material. 前記フェノール樹脂（Ｂ）が、前記芳香環上に一つ乃至複数の炭化水素基を有するフェノール化合物（ｂ）とホルムアルデヒドとの重縮合物である請求項１記載の活性エステル樹脂。 The active ester resin according to claim 1, wherein the phenol resin (B) is a polycondensate of a phenol compound (b) having one or more hydrocarbon groups on the aromatic ring and formaldehyde. 前記芳香環上に一つ乃至複数の炭化水素基を有するフェノール化合物（ｂ）が有する炭化水素基が、炭素原子数１～１２の脂肪族炭化水素基又はアリール基である請求項１記載の活性エステル樹脂。 2. The activity according to claim 1, wherein the hydrocarbon group of the phenol compound (b) having one or more hydrocarbon groups on the aromatic ring is an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aryl group. Ester resin. 前記芳香環上に一つ乃至複数の炭化水素基を有するフェノール化合物（ｂ）が、フェノール性水酸基のパラ位に炭化水素基を有するものである請求項１記載の活性エステル樹脂。 The active ester resin according to claim 1, wherein the phenol compound (b) having one or more hydrocarbon groups on the aromatic ring has a hydrocarbon group at the para position of the phenolic hydroxyl group. 前記フェノール性水酸基含有化合物（Ａ）と前記芳香環上に一つ乃至複数の炭化水素基を有するフェノール化合物（ｂ）とが同一化合物である請求項１記載の活性エステル樹脂。 The active ester resin according to claim 1, wherein the phenolic hydroxyl group-containing compound (A) and the phenol compound (b) having one or more hydrocarbon groups on the aromatic ring are the same compound. 請求項１～５の何れか一つに記載の活性エステル樹脂と、硬化剤とを含有する硬化性樹脂組成物。 A curable resin composition comprising the active ester resin according to any one of claims 1 to 5 and a curing agent. 請求項６記載の硬化性樹脂組成物の硬化物。 A cured product of the curable resin composition according to claim 6. 請求項６記載の硬化性樹脂組成物を用いてなるプリント配線基板。 A printed wiring board using the curable resin composition according to claim 6. 請求項６記載の硬化性樹脂組成物を用いてなる半導体封止材料。 The semiconductor sealing material which uses the curable resin composition of Claim 6.
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