WO2023089998A1 - 硬化性組成物、その硬化物、プリプレグ、回路基板、ビルドアップフィルム、半導体封止材及び半導体装置 - Google Patents

硬化性組成物、その硬化物、プリプレグ、回路基板、ビルドアップフィルム、半導体封止材及び半導体装置 Download PDF

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WO2023089998A1
WO2023089998A1 PCT/JP2022/038147 JP2022038147W WO2023089998A1 WO 2023089998 A1 WO2023089998 A1 WO 2023089998A1 JP 2022038147 W JP2022038147 W JP 2022038147W WO 2023089998 A1 WO2023089998 A1 WO 2023089998A1
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curable composition
group
resin
mass
cured product
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PCT/JP2022/038147
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English (en)
French (fr)
Japanese (ja)
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ヨンチャン キム
弘司 林
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Dic株式会社
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Priority to CN202280066410.9A priority Critical patent/CN118103425A/zh
Priority to KR1020247014284A priority patent/KR20240070654A/ko
Priority to JP2023511632A priority patent/JP7327706B1/ja
Publication of WO2023089998A1 publication Critical patent/WO2023089998A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—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
    • 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
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • 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
    • C08L67/06—Unsaturated polyesters
    • 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
    • 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
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement

Definitions

  • the present invention relates to a curable composition, a cured product thereof, a prepreg, a circuit board, a build-up film, a semiconductor sealing material, and a semiconductor device.
  • Epoxy resin compositions which contain epoxy resins and their curing agents as essential components, exhibit excellent heat resistance and insulating properties in their cured products, and are therefore widely used in electronic components such as semiconductors and multilayer printed circuit boards. .
  • the speed and frequency of signals in various electronic devices have been increasing in recent years. As the speed and frequency of these signals increase, materials with lower dielectric constants and lower dielectric loss tangents are required. However, it has been difficult to obtain a material with a low dielectric loss tangent while maintaining a sufficiently low dielectric constant.
  • the problem to be solved by the present invention is that even a curable composition containing a hydrocarbon resin (hydrocarbon-based plasticizer) with extremely low polarity has high compatibility, and the curing of the curable composition is
  • An object of the present invention is to provide a curable composition having a low dielectric loss tangent, a cured product thereof, a prepreg, a circuit board, a build-up film, a semiconductor sealing material, and a semiconductor device.
  • a curable composition obtained by blending a specific active ester with a hydrocarbon resin and a curing agent has high compatibility, and the cured product is The present invention was completed by discovering that it has a low dielectric loss tangent.
  • the present invention provides a curable composition containing an active ester resin, a hydrocarbon resin and a curing agent, wherein the active ester resin is a compound (a1 ) and a resin (A) having a phenolic hydroxyl group, which is a reaction product of the divinyl compound (a2), and a curable composition which is a reaction product of an aromatic dicarboxylic acid or its acid halide (B).
  • the active ester resin is a compound (a1 ) and a resin (A) having a phenolic hydroxyl group, which is a reaction product of the divinyl compound (a2)
  • a curable composition which is a reaction product of an aromatic dicarboxylic acid or its acid halide (B).
  • the present invention also relates to a cured product of the curable composition, a prepreg, a circuit board, a build-up film, a semiconductor sealing material, and a semiconductor device using the curable composition.
  • the curable composition of the present invention has high compatibility even when a hydrocarbon resin with extremely low polarity is blended, and the cured product thereof has a low dielectric loss tangent. It can be used for electronic members such as films and semiconductor sealing materials, and can also be used for semiconductor devices using these electronic members.
  • FIG. 1 is a GPC chart of the active ester resin (1) obtained in Production Example 1.
  • FIG. 2 is a GPC chart of the active ester resin (2) obtained in Production Example 2.
  • FIG. 3 is a GPC chart of the active ester resin (1') obtained in Comparative Production Example 1.
  • the active ester resin of the present invention comprises a resin (A) having a phenolic hydroxyl group which is a reaction product of a compound (a1) having an alkyl group having 5 or more carbon atoms and a phenolic hydroxyl group and a divinyl compound (a2), and an aromatic It is a reaction product with a dicarboxylic acid or its acid halide (B).
  • the compound (a1) is not particularly limited as long as it is a compound having an alkyl group with 5 or more carbon atoms and a phenolic hydroxyl group.
  • the alkyl group of the compound (a1) may have 5 or more carbon atoms, and examples thereof include pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, A dodecyl group and the like can be mentioned.
  • the alkyl group may be linear or branched, and may have an alicyclic structure.
  • the alkyl group has 5 or more carbon atoms, preferably 12 or less carbon atoms, more preferably 10 or less carbon atoms, and particularly preferably 8 or less carbon atoms.
  • Examples of the compound (a1) having a phenolic hydroxyl group include phenol and naphthol.
  • Specific examples of the compound (a1) include pentylphenol, hexylphenol, heptylphenol, octylphenol, nonylphenol, decylphenol, undecylphenol, dodecylphenol, pentylnaphthol, hexylnaphthol, heptylnaphthol, octylnaphthol, nonylnaphthol, decylnaphthol, undecylnaphthol, dodecylnaphthol and the like.
  • substitution positions on the aromatic ring of the alkyl group and phenolic hydroxyl group of these compounds (a1) are not particularly limited, but when the compound (a1) is phenol, the alkyl group and the phenolic hydroxyl group are para It is preferably substituted at the position.
  • the compound (a1) can be used alone or in combination of two or more.
  • the divinyl compound (a2) is not particularly limited as long as it is a compound capable of reacting with the compound (a1) and polymerizing the compounds (a1) with each other.
  • the divinyl compound (a2) can be used alone or in combination of two or more.
  • a compound having an aromatic ring or an alicyclic ring in the molecular structure is preferable because it has good compatibility and becomes an active ester resin having excellent dielectric properties in a cured product.
  • More preferable specific examples of the divinyl compound (a2) include compounds represented by the following general formulas (1-1) to (1-4).
  • R 1 is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group or an aralkyl group, and Y has 1 carbon atom; 4 alkylene group, oxygen atom, sulfur atom, carbonyl group, i is 0 or an integer of 1-4, j is an integer of 1-4. ]
  • Each R 1 in the general formulas (1-1) to (1-4) is independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group.
  • Aliphatic hydrocarbon groups such as methyl group, ethyl group, vinyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group; methoxy group, ethoxy group, propyl Alkoxy groups such as oxy group and butoxy group; Halogen atoms such as fluorine atom, chlorine atom and bromine atom; Aryl groups substituted with atoms, etc.; is mentioned.
  • the general formula (1-1) has good compatibility and becomes an active ester resin having excellent dielectric properties in the cured product.
  • ) is preferably a compound represented by
  • the resin (A) having a phenolic hydroxyl group has the compound (a1) It is bound at the structural site represented by the following general formula (2).
  • X is represented by any one of the following general formulas (X-1) to (X-4). ]
  • R 1 is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aralkyl group, and Y has 1 to 4 alkylene group, oxygen atom, sulfur atom, carbonyl group, i is 0 or an integer of 1-4, j is an integer of 1-4.
  • the resin (A) having a phenolic hydroxyl group may use a compound other than the compound (a1) and the divinyl compound (a2) as a reaction raw material.
  • examples of other compounds include, for example, various aldehyde compounds, compounds (a2′) that are compounds other than the divinyl compound (a2) and capable of polymerizing the compound (a1), and resins (A) having a phenolic hydroxyl group.
  • Substituent-introducing agents (a3) for introducing aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, aryl groups, and aralkyl groups can be used as substituents on the aromatic ring of .
  • the divinyl compound (a2) is preferably 50% by mass or more, preferably 80% by mass or more.
  • substituent-introducing agent (a3) examples include aralkyl group-introducing agents such as phenylmethanol compounds, phenylmethyl halide compounds, naphthylmethanol compounds, naphthylmethyl halide compounds, and styrene compounds.
  • the method for producing the resin (A) having phenolic hydroxyl groups is not particularly limited, it is preferable to adjust the ratio of the reaction raw materials so that the number of phenolic hydroxyl groups per molecule is 2 or more.
  • the compound (a1) is used in an amount of 2 to 10 mol with respect to 1 mol of the divinyl compound (a2), and is produced by a method of heating and stirring under acid catalyst conditions at a temperature of about 80 to 180°C. be able to. You may perform reaction in an organic solvent as needed. After completion of the reaction, if desired, the excess amount of the compound (a1) may be distilled off.
  • the acid catalyst examples include p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, oxalic acid, etc., and hydrates thereof can also be used. These can be used alone or in combination of two or more. Moreover, you may use these acid catalysts as aqueous solution.
  • the amount of the acid catalyst to be added is preferably in the range of 0.01 to 20% by mass relative to the compound (a1).
  • organic solvent examples include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; acetic ester 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.
  • Solvents include aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. These can be used alone or in combination of two or more.
  • resin (A) having a phenolic hydroxyl group examples include the following general formula (A -1).
  • the general formula (A-1) below is merely an example of the resin (A) having a phenolic hydroxyl group, and does not exclude other resins.
  • each R 1 is independently an alkyl group having 5 or more carbon atoms
  • each R 2 is independently a hydrogen atom or represented by the following general formula (R-1) is a structural moiety and n is an integer from 1-10.
  • R 1 is an alkyl group having 5 or more carbon atoms, and n is an integer of 1 to 10. ]
  • R-2 a structure represented by the following formula (R-2) may be partially introduced as R 2 in the general formula (B-1).
  • the aromatic dicarboxylic acid or its acid halide (B) is particularly limited as long as it is an aromatic compound capable of forming an ester bond by reacting with the phenolic hydroxyl group of the resin (A) having a phenolic hydroxyl group. isn't it.
  • 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.
  • -dicarboxylic acid naphthalene-2,7-dicarboxylic acid, and other naphthalenedicarboxylic acids; acid halides thereof; mentioned.
  • the acid halides include acid chlorides, acid bromides, acid fluorides, acid iodides and the like. These can 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 provide active ester resins with high reaction activity and excellent curability.
  • the active ester resin of the present invention can be prepared, for example, by combining the resin (A) having a phenolic hydroxyl group and the aromatic polycarboxylic acid or its acid halide (B) in the presence of an alkali catalyst at a temperature of about 40 to 65 ° C. It can be produced by a method of heating and stirring under certain conditions. You may perform reaction in an organic solvent as needed. After completion of the reaction, if desired, the reaction product may be purified by washing with water, reprecipitation, or the like.
  • the alkali catalyst examples include sodium hydroxide, potassium hydroxide, triethylamine, pyridine, and the like. These can be used alone or in combination of two or more. Also, the alkali catalyst may be used as an aqueous solution of about 3 to 30% by mass. Among them, sodium hydroxide or potassium hydroxide with high catalytic ability is preferable.
  • organic solvent examples include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; acetic ester 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, N-methylpyrrolidone and the like. These can be used alone or in combination of two or more.
  • the compound (a1) remaining in the resin (A) having a phenolic hydroxyl group, and the aromatic polycarboxylic acid or its acid halide (B) may contain the reacted ester compound.
  • the weight average molecular weight (Mw) of the active ester resin is preferably in the range of 600 to 50,000, more preferably in the range of 800 to 30,000, because the curing shrinkage of the curable composition of the present invention is lower. preferable.
  • the weight average molecular weight (Mw) of the active ester resin is a value measured by GPC (gel permeation chromatography).
  • the softening point of the active ester resin of the present invention is a value measured based on JIS K7234, preferably in the range of 80 to 180°C, more preferably in the range of 85 to 160°C.
  • the functional group equivalent weight of the active ester resin is preferably in the range of 200 to 350 g/equivalent, and 200 to 300 g/equivalent, since the curable composition of the present invention has good compatibility and excellent curability. A range of equivalents is more preferred.
  • the functional group in the active ester resin means the ester bonding site and the phenolic hydroxyl group in the active ester resin. Further, the functional group equivalent weight of the active ester resin is a value calculated from the charged amount of raw materials.
  • the curable composition of the present invention contains a hydrocarbon resin and a curing agent in addition to the active ester resin.
  • the hydrocarbon resin is not particularly limited as long as it is composed of carbon atoms and hydrogen atoms, and examples thereof include thermoplastic elastomers.
  • the hydrocarbon resins may be used singly or in combination of two or more.
  • thermoplastic elastomer examples include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), polystyrene-based thermoplastic elastomers such as styrene-ethylene/propylene-styrene block copolymer (SEPS); olefin-based thermoplastic elastomers, polybutadiene, and the like.
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • SEPS styrene-ethylene/propylene-
  • thermoplastic elastomers polystyrene-based thermoplastic elastomers are preferred, and styrene-ethylene-butylene-styrene block copolymer (SEBS) is more preferred.
  • SEBS products include “Tuftech” manufactured by Asahi Kasei Chemicals Corporation, “Lavalon” manufactured by Mitsubishi Chemical Corporation, “Actimer” manufactured by Riken Technos Co., Ltd., “Elastomer AR” manufactured by Aron Kasei Co., Ltd., and Kraton Polymer Japan Co., Ltd. "Clayton G” manufactured by Nippon Soda Co., Ltd., “B series” and “BI series” manufactured by Nippon Soda Co., Ltd., and the like.
  • the ratio of the hydrocarbon resin in the curable composition of the present invention is preferably in the range of 5 to 40% by mass, because it has good compatibility and can lower the dielectric loss tangent in the cured product. A range of 10 to 35% by mass is more preferred.
  • the curing agent is not particularly limited as long as it is a compound that can react with the active ester resin, but one example of the curing agent is an epoxy resin.
  • epoxy resin examples include phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthol novolak type epoxy resin, bisphenol novolak type epoxy resin, biphenol novolak 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. These can be used alone or in combination of two or more.
  • epoxy resin When an epoxy resin is used as the curing agent, other epoxy resin curing agents may be used in combination with the active ester resin.
  • Other curing agents for epoxy resins include, for example, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF 3 -amine complexes, amine compounds such as guanidine derivatives; Amide compounds such as polyamide resins synthesized from dimers and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride , hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.; , naphtholaralkyl resins, triphenolmethane type resins
  • the mixing ratio of these is the above-mentioned per 1 mol of the total epoxy groups in the epoxy resin. It is preferable that the total amount of functional groups in the active ester resin and other epoxy resin curing agents is 0.7 to 1.5 mol.
  • the curable composition of the present invention includes, as other resins, cyanate ester resin; bismaleimide resin; benzoxazine resin; styrene-maleic anhydride resin; allyl group-containing resin such as diallyl bisphenol and triallyl isocyanurate; Esters; phosphoric acid ester-carbonate copolymers and the like may be contained. These can be used alone or in combination of two or more.
  • the curable composition of the present invention may contain various additives such as curing accelerators, flame retardants, inorganic fillers, silane coupling agents, release agents, pigments and emulsifiers, if necessary.
  • the curing accelerator examples include phosphorus compounds, tertiary amines, imidazole compounds, pyridine compounds, organic acid metal salts, Lewis acids, and amine complex salts.
  • triphenylphosphine is a phosphorus-based compound and 1,8-diazabicyclo-[5.4.0]-undecene (DBU )
  • the imidazole compound is preferably 2-ethyl-4-methylimidazole
  • the pyridine compound is preferably 4-dimethylaminopyridine.
  • 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 phosphoric acid amide; 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-dihydroxyphenyl )-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic organic phosphorus organic phosphorus compounds such as compounds and derivatives obtained by reacting them with compounds such as epoxy resins and phenolic resins; triazine compounds, cyanuric acid compounds, isocyanuri
  • the inorganic filler is blended, for example, when the curable composition of the present invention is used as a semiconductor sealing material.
  • the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.
  • the fused silica is preferable because it allows a larger amount of inorganic filler to be blended.
  • the fused silica may be crushed or spherical, but spherical fused silica is mainly used in order to increase the amount of fused silica and to suppress the increase in the melt viscosity of the curable composition. is preferred.
  • the filling rate is in the range of 0.5 to 95% by mass in the curable composition.
  • a conductive filler such as silver powder or copper powder can be used.
  • the curable composition of the present invention has excellent properties such as low cure shrinkage and low dielectric loss tangent in the cured product.
  • the curable composition of the present invention can be suitably used for prepregs used in electronic members, circuit boards, semiconductor encapsulants, and semiconductor devices containing cured products of semiconductor encapsulants.
  • it can be widely used for applications such as coatings, adhesives, molded articles, etc., other than electronic member applications.
  • the curable composition of the present invention When the curable composition of the present invention is used for applications such as prepregs, circuit boards, and build-up films, it is generally preferable to mix and dilute an organic solvent.
  • the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate.
  • the type and blending amount of the organic solvent can be appropriately adjusted according to the usage environment of the curable composition. It is preferable that the non-volatile content is 40 to 80% by mass.
  • ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; acetic ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitol solvents such as cellosolve and butyl carbitol.
  • aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like are preferably used, preferably in a proportion that gives a non-volatile content of 30 to 60% by mass.
  • the cured product of the invention can be obtained by curing the curable composition of the invention.
  • a curing method is not particularly limited, and a known method can be adopted.
  • the cured products can be in the form of laminates, castings, adhesive layers, coatings, films and the like.
  • the prepreg of the present invention can have a reinforcing substrate and a semi-cured product of the curable composition of the present invention impregnating the reinforcing substrate.
  • the method of obtaining a prepreg using the curable composition of the present invention is not particularly limited. , aramid paper, aramid cloth, glass mat, glass roving cloth, etc.), and then heated at a heating temperature (preferably 50 to 170 ° C.) according to the type of solvent used to semi-cure the curable composition ( or uncured).
  • the mass ratio of the curable composition and the reinforcing base material to be used is not particularly limited, but it is preferable to adjust the resin content in the prepreg to 20 to 60% by mass.
  • a semi-cured product of the curable composition can be obtained by adjusting the heating temperature and heating time to stop the curing reaction in the middle without completing it.
  • the degree of curing of the semi-cured product can be, for example, 85% or less and 5% or more.
  • the cured product can have a higher degree of cure than the semi-cured product.
  • the degree of curing of the semi-cured product can be calculated from the following formula by measuring the amount of heat generated by curing when the curable composition is heated and the amount of heat generated by curing of the semi-cured product by DSC.
  • Curing degree (%) [1-(curing calorific value of semi-cured product/curing calorific value of curable composition)] ⁇ 100
  • the circuit board of the present invention comprises a laminate containing the prepreg of the present invention and copper foil.
  • the method for obtaining a circuit board is not particularly limited. A method of thermocompression bonding can be used.
  • the build-up film of the present invention contains the curable composition of the present invention.
  • the method for producing a build-up film is not particularly limited, for example, the curable composition of the present disclosure is applied onto a support film to form a curable composition layer and an adhesive film for a multilayer printed wiring board. method.
  • the build-up film softens under the lamination temperature conditions (usually 70 to 140° C.) in the vacuum lamination method, and at the same time as laminating the circuit board, via holes or through holes present in the circuit board can be filled with resin. Since it is required to exhibit fluidity (resin flow), the curable composition preferably contains the aforementioned inorganic filler, organic solvent, and other components so as to exhibit such characteristics.
  • the diameter of the through hole of the circuit board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to allow resin filling within this range.
  • the method for producing the adhesive film described above comprises preparing the varnish-like curable composition, applying the varnish-like composition to the surface of the support film (Y), further heating, Alternatively, it can be produced by drying the organic solvent by blowing hot air or the like to form the composition layer (X) composed of the curable composition.
  • the thickness of the composition layer (X) to be formed is usually preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 ⁇ m, the thickness of the resin composition layer is preferably 10 to 100 ⁇ m.
  • the composition layer (X) may be protected with a protective film to be described later. By protecting the surface of the resin composition layer with a protective film, it is possible to prevent the surface of the resin composition layer from being dusted or scratched.
  • the support film (Y) and protective film described above are polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, Further examples include release paper and metal foils such as copper foil and aluminum foil.
  • the support film and protective film may be subjected to release treatment in addition to mud treatment and corona treatment.
  • the thickness of the support film is not particularly limited, it is usually 10 to 150 ⁇ m, preferably 25 to 50 ⁇ m. Also, the thickness of the protective film is preferably 1 to 40 ⁇ m.
  • the support film (Y) described above is peeled off after lamination on the circuit board or after formation of an insulating layer by heat curing. If the support film (Y) is peeled off after the adhesive film is cured by heating, it is possible to prevent the adhesion of dust and the like during the curing process. When peeling after curing, the support film is normally subjected to a release treatment in advance.
  • the semiconductor sealing material of the present invention contains the curable composition of the present invention.
  • the curable composition of the present invention has excellent properties such as low cure shrinkage and low dielectric loss tangent in the cured product.
  • it since it has excellent compatibility even if a hydrocarbon resin with extremely low polarity is blended, it becomes a uniform curable composition and a uniform cured product can be obtained, so it is also suitable for use as a semiconductor encapsulant. be able to.
  • the semiconductor encapsulant of the present invention is preferably the curable composition of the present invention containing an inorganic filler.
  • various additives may be added to the semiconductor encapsulant of the present invention, and examples of the additives include those described with respect to the above curable composition.
  • the method for producing the semiconductor encapsulating material of the present invention is not particularly limited, and can be obtained by mixing the curable composition of the present invention and, if necessary, various additives.
  • a method of sufficiently melting and mixing using a kneader, a roll, or the like until the mixture becomes uniform can be used.
  • the semiconductor device of the present disclosure contains the cured product of the semiconductor sealing material of the present invention described above.
  • the semiconductor device of the present invention can be obtained by heat-curing the semiconductor encapsulant of the present invention. 20°C) to 250°C, and the like.
  • the cured product obtained from the curable composition of the present invention has high uniformity and low dielectric loss tangent, so it can be suitably used for electronic members.
  • it can be suitably used for prepregs, circuit boards, build-up films, build-up substrates, semiconductor sealing materials, semiconductor devices, conductive pastes and the like.
  • the electronic members thus obtained can be suitably used for various applications, for example, industrial machine parts, general machine parts, automobile/railway/vehicle parts, aerospace-related parts, electronic/electrical parts, building materials, Examples include, but are not limited to, containers/packaging members, daily necessities, sports/leisure goods, housing members for wind power generation, and the like.
  • Measuring device "HLC-8320 GPC” manufactured by Tosoh Corporation, Column: Guard column “HXL-L” manufactured by Tosoh Corporation + “TSK-GEL G4000HXL” manufactured by Tosoh Corporation + “TSK-GEL G3000HXL” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: "GPC Workstation EcoSEC-WorkStation” 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-8320".
  • the mixture was stirred at the same temperature for 1 hour to react. After completion of the reaction, the mixture was cooled to 80°C, neutralized by adding 1.0 parts by mass of a 49% by mass sodium hydroxide aqueous solution, and then cooled to 25°C.
  • active ester resin (1) After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand for liquid separation, and the aqueous layer was removed. After repeating this operation until the pH of the aqueous layer reached 7, toluene and the like were distilled off under heating and reduced pressure conditions to obtain an active ester resin (1).
  • the functional group equivalent weight of active ester resin (1) was 272 g/equivalent calculated from the charged ratio.
  • a GPC chart of the obtained active ester resin (1) is shown in FIG.
  • the mixture was stirred at the same temperature for 1 hour to react. After completion of the reaction, the mixture was cooled to 80°C, neutralized by adding 0.23 parts by mass of a 49% by mass sodium hydroxide aqueous solution, and then cooled to 25°C.
  • active ester resin (2) After repeating this operation until the pH of the aqueous layer reached 7, toluene and the like were distilled off under heating and reduced pressure conditions to obtain an active ester resin (2).
  • the functional group equivalent weight of active ester resin (2) was 314 g/equivalent calculated from the charged ratio.
  • a GPC chart of the obtained active ester resin (2) is shown in FIG.
  • the mixture was stirred at the same temperature for 1 hour to react. After completion of the reaction, the reaction mixture was cooled to 80°C, neutralized by adding 0.1 part by mass of a 49% by mass sodium hydroxide aqueous solution, and then cooled to 25°C.
  • Example 1 Preparation of curable composition (1)
  • the mass parts were uniformly mixed to obtain a curable composition (1).
  • Example 2 Preparation of curable composition (2)
  • the mass parts were uniformly mixed to obtain a curable composition (2).
  • a varnish was prepared by diluting each curable composition with toluene so that the total non-volatile content was 30% by mass. The appearance of the prepared varnishes was visually observed, and the compatibility of the varnishes was evaluated according to the following criteria.
  • ⁇ The solution satisfies both uniformity and transparency.
  • x A solution that does not satisfy at least one of homogeneity and transparency.
  • Table 1 shows the compositions and evaluation results of the curable compositions (1), (2) and (1') obtained in Examples 1 and 2 and Comparative Example 1 above.
  • the composition shown in Table 1 is the blending amount at 100% by mass of non-volatile matter.
  • the curable composition of Comparative Example 1 uses a compound having an alkyl group and a phenolic hydroxyl group, which is a raw material of the active ester resin used in the curable composition, and has an alkyl group having less than 5 carbon atoms. This is an example. It was confirmed that the curable composition of Comparative Example 1 was inferior in compatibility and had a slightly higher dielectric loss tangent than the curable composition of the present invention.

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PCT/JP2022/038147 2021-11-18 2022-10-13 硬化性組成物、その硬化物、プリプレグ、回路基板、ビルドアップフィルム、半導体封止材及び半導体装置 WO2023089998A1 (ja)

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KR1020247014284A KR20240070654A (ko) 2021-11-18 2022-10-13 경화성 조성물, 그 경화물, 프리프레그, 회로 기판, 빌드 업 필름, 반도체 밀봉재 및 반도체 장치
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JPH0770293A (ja) * 1993-09-03 1995-03-14 Sanyo Chem Ind Ltd オキシアルキレンエーテル、帯電防止剤および樹脂組成物
JP2009242560A (ja) * 2008-03-31 2009-10-22 Dic Corp エポキシ樹脂組成物、及びその硬化物
JP2010077344A (ja) * 2008-09-29 2010-04-08 Dic Corp エポキシ樹脂組成物、その硬化物、及びビルドアップフィルム絶縁材料
JP2015174986A (ja) * 2014-03-18 2015-10-05 Dic株式会社 活性エステル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム
JP2018009129A (ja) * 2016-07-15 2018-01-18 Dic株式会社 活性エステル樹脂とその硬化物

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JP2013135032A (ja) 2011-12-26 2013-07-08 Panasonic Corp マスクフィルムおよびそれを用いた回路基板の製造方法
JP6371513B2 (ja) 2013-11-07 2018-08-08 ナミックス株式会社 フレキシブルプリント配線板、およびその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0770293A (ja) * 1993-09-03 1995-03-14 Sanyo Chem Ind Ltd オキシアルキレンエーテル、帯電防止剤および樹脂組成物
JP2009242560A (ja) * 2008-03-31 2009-10-22 Dic Corp エポキシ樹脂組成物、及びその硬化物
JP2010077344A (ja) * 2008-09-29 2010-04-08 Dic Corp エポキシ樹脂組成物、その硬化物、及びビルドアップフィルム絶縁材料
JP2015174986A (ja) * 2014-03-18 2015-10-05 Dic株式会社 活性エステル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム
JP2018009129A (ja) * 2016-07-15 2018-01-18 Dic株式会社 活性エステル樹脂とその硬化物

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