Classifications

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  • 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
  • C08L63/04—Epoxynovolacs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
  • C08L23/30—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by oxidation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
• • 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
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
  • C09K3/1012—Sulfur-containing polymers, e.g. polysulfides
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
  • H10W74/473—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins containing a filler
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
  • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09K2200/0625—Polyacrylic esters or derivatives thereof
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
  • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
  • C09K2200/0657—Polyethers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
  • C09K2200/068—Containing also other elements than carbon, oxygen or nitrogen in the polymer main chain
  • C09K2200/0682—Containing sulfur

Definitions

• This disclosure relates to a molding resin composition and an electronic component device.
• epoxy resin encapsulation In the field of element encapsulation for electronic devices such as transistors, ICs (integrated circuits), and LSIs (large scale integration), resin encapsulation has traditionally been the mainstream due to its productivity and cost advantages, and epoxy resin compositions are widely used as epoxy resin molding materials for encapsulation. This is because epoxy resins have an excellent balance of properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to insert products.
• release agent In order to improve the production efficiency of electronic device components and to provide good continuous moldability, a release agent is generally added to epoxy resin compositions to facilitate smooth release from the mold.
• release agents that have been reported include copolymers of ⁇ -olefins and maleic anhydride (see, for example, Patent Document 1), compounds obtained by esterifying copolymers of ⁇ -olefins and maleic anhydride (see, for example, Patent Documents 2 and 3), and oxidized polyolefins (see, for example, Patent Document 4).
• Patent Document 1 JP-A-10-36486 Patent Document 2: JP-A-2001-247748 Patent Document 3: JP-A-2003-64239 Patent Document 4: JP-A-2006-182913 Patent Document 5: JP-A-2005-255978
• the present disclosure has been made in consideration of the above-mentioned conventional circumstances, and an object of the present disclosure is to provide a molding resin composition having excellent mold releasability, and an electronic component device using the same.
• R 10 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different.
• n represents an average value and is a number from 0 to 10.
• ⁇ 6> The molding resin composition according to any one of ⁇ 3> to ⁇ 5>, wherein the polyethylene oxide has a weight average molecular weight of 2,800 or more.
• ⁇ 7> The molding resin composition according to any one of ⁇ 3> to ⁇ 6>, wherein the acid value of the oxidized polyethylene is 2 mgKOH/g to 50 mgKOH/g.
• ⁇ 8> The molding resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the copolymer contains a structural unit represented by the following general formula (C) and a structural unit represented by the following general formula (D):
• R 11 represents a monovalent aliphatic hydrocarbon group having 3 to 28 carbon atoms
• R 12 and R 13 each independently represent a hydrogen atom, an alkyl group, or an aryl group.
• This disclosure makes it possible to provide a molding resin composition with excellent release properties, and an electronic component device using the same.
• FIG. 1 is a graph showing the transition of shear release strength for Examples 1 to 5 and Comparative Examples 1 to 3.
• FIG. 1 is a graph showing the transition of shear release strength for Example 6 and Comparative Example 4.
• the term "step” includes not only a step that is independent of other steps, but also a step that cannot be clearly distinguished from other steps as long as the purpose of the step is achieved.
• the numerical range indicated using “to” includes the numerical values before and after "to” as the minimum and maximum values, respectively.
• the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages.
• the upper or lower limit value of the numerical range may be replaced with a value shown in the examples.
• each component may contain multiple types of corresponding substances.
• the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified.
• the particles corresponding to each component may include multiple types of particles.
• the particle size of each component means the value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.
• the molding resin composition of the present disclosure contains a sulfur atom-containing epoxy resin, a curing agent, a release agent, an inorganic filler, and a copolymer of an ⁇ -olefin having 5 to 30 carbon atoms and at least one of maleic anhydride and a maleic anhydride derivative (hereinafter, may be referred to as a specific copolymer).
• the molding resin composition of the present disclosure has excellent releasability. The reason for this is not clear, but is presumed to be as follows.
• the specific copolymer has, in its molecule, a hydrophobic structural unit derived from an ⁇ -olefin having 5 to 30 carbon atoms and a hydrophilic structural unit derived from at least one of maleic anhydride and a maleic anhydride derivative. Therefore, by using the specific copolymer, the release agent can be dispersed well in the epoxy resin, and when the molding resin composition is cured to form a cured product, the release agent is likely to be uniformly dispersed in the cured product. Furthermore, by using a sulfur atom-containing epoxy resin, the release agent tends to bleed out onto the surface of the cured product. The release agent uniformly dispersed in the cured product is likely to ooze out uniformly from the surface of the cured product.
• the molding resin composition of the present disclosure has excellent mold releasability.
• the components constituting the molding resin composition are described below.
• the molding resin composition of the present disclosure contains a sulfur atom-containing epoxy resin as an epoxy resin, a curing agent, a release agent, an inorganic filler, and a specific copolymer, and may contain other components as necessary.
• the molding resin composition of the present disclosure contains a sulfur atom-containing epoxy resin as an epoxy resin.
• the molding resin composition of the present disclosure may contain an epoxy resin other than the sulfur atom-containing epoxy resin.
• the ratio of the sulfur atom-containing epoxy resin in the epoxy resins is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and even more preferably 18% by mass to 30% by mass.
• the mass proportion of the epoxy resin in the entire molding resin composition is preferably 0.5% by mass to 30% by mass, more preferably 2% by mass to 20% by mass, and even more preferably 3.5% by mass to 13% by mass, from the viewpoints of strength, flowability, heat resistance, moldability, and the like.
• the structure of the sulfur-containing epoxy resin is not particularly limited as long as it contains a sulfur atom in the molecule.
• the sulfur-containing epoxy resin may contain, for example, an epoxy compound having a diphenyl sulfide structure, or a compound represented by the following general formula (B).
• R 10 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different from each other.
• n represents an average value and is a number from 0 to 10.
• Examples of the monovalent organic group having 1 to 18 carbon atoms represented by R 10 include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclopentyl group, and a cyclohexyl group; aryl groups such as a phenyl group and a tolyl group; and alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
• YSLV - 120TE (trade name, Nippon Steel Chemical & Material Co., Ltd.), in which the 3- and 3-positions are tert-butyl groups, the 6- and 6-positions are methyl groups, and the other R 10 are hydrogen atoms, when the positions at which oxygen atoms are substituted in R 10 are the 4- and 4'-positions, is commercially available.
• epoxy resins include novolac-type epoxy resins (phenol novolac-type epoxy resins, o-cresol novolac-type epoxy resins, etc.) which are obtained by epoxidizing novolac resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, etc., and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol, dihydroxynaphthalene, etc., with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc., under an acid catalyst; and triphenylmethane-type phenolic resins which are obtained by condensing or co-condensing the above-mentioned phenolic compound with an aromatic aldeh
• triphenylmethane type epoxy resins which are obtained by epoxidizing a novolak resin obtained by co-condensing the above-mentioned phenol compounds and naphthol compounds with an aldehyde compound under an acidic catalyst; copolymer type epoxy resins which are obtained by epoxidizing a novolak resin obtained by co-condensing the above-mentioned phenol compounds and naphthol compounds with an aldehyde compound under an acidic catalyst; diphenylmethane type epoxy resins which are diglycidyl ethers of bisphenol A, bisphenol F, etc.; biphenyl type epoxy resins which are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene type epoxy resins which are diglycidyl ethers of stilbene-based phenol compounds; epoxy resins which are glycidyl ethers of alcohols such as butanediol, polyethylene glycol,
• Terpene-modified epoxy resins which are glycidyl ethers of dicyclopentadiene-modified phenolic resins; dicyclopentadiene-modified epoxy resins, which are glycidyl ethers of cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified epoxy resins, which are glycidyl ethers of polycyclic aromatic ring-modified phenolic resins; naphthalene-type epoxy resins, which are glycidyl ethers of naphthalene ring-containing phenolic resins; halogenated phenol novolac-type epoxy resins; hydroquinone-type epoxy resins; trimethylolpropane-type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenol
• the other epoxy resins preferably include at least one of diphenylmethane type epoxy resin, triphenylmethane type epoxy resin, o-cresol novolac type epoxy resin, and biphenylaralkyl type epoxy resin, and more preferably include diphenylmethane type epoxy resin or biphenylaralkyl type epoxy resin.
• the epoxy equivalent (molecular weight/number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of the balance of various properties such as moldability, reflow resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 100 g/eq to 1000 g/eq, and more preferably 150 g/eq to 500 g/eq.
• the epoxy equivalent of the epoxy resin is a value measured by a method in accordance with JIS K 7236:2009.
• the softening point or melting point of the epoxy resin is not particularly limited.
• the softening point or melting point of the epoxy resin is preferably 40° C. to 180° C. from the viewpoints of moldability and reflow resistance, and more preferably 50° C. to 130° C. from the viewpoint of handleability during preparation of the molding resin composition.
• the melting point or softening point of the epoxy resin is a value measured by differential scanning calorimetry (DSC) or a method in accordance with JIS K 7234:1986 (ring and ball method).
• the molding resin composition of the present disclosure contains a curing agent.
• a phenol curing agent is preferred from the viewpoint of moldability and reliability.
• an active ester compound is preferred from the viewpoint of keeping the dielectric constant and dielectric tangent of the cured product low.
• other curing agents other than the phenol curing agent and the active ester compound may be used.
• an acid anhydride curing agent, an amine curing agent, etc. may be used.
• the molding resin composition may contain only one type of curing agent, or may contain two or more types of curing agents.
• the molding resin composition contains two or more types of curing agents
• two or more types of phenolic curing agents may be used
• two or more types of active ester compounds may be used
• a phenolic curing agent and an active ester compound may be used in combination.
• the active ester compound refers to a compound that has one or more ester groups in one molecule that react with an epoxy group and has an epoxy resin curing action.
• the dielectric constant and dielectric loss tangent of the cured product can be kept low compared to when a phenolic curing agent is used alone as the curing agent.
• the reason for this is presumed to be as follows. In the reaction between an epoxy resin and a phenolic curing agent, a secondary hydroxyl group is generated. In contrast, in the reaction between an epoxy resin and an active ester compound, an ester group is generated instead of a secondary hydroxyl group.
• a molding resin composition containing an active ester compound as a curing agent can suppress the dielectric constant and dielectric loss tangent of the cured product to be lower than a molding resin composition containing only a curing agent that generates a secondary hydroxyl group as a curing agent.
• polar groups in a cured product increase the water absorption of the cured product
• the polar group concentration of the cured product can be reduced by using an active ester compound as a curing agent, and the water absorption of the cured product can be reduced. It is presumed that by reducing the water absorption of the cured product, that is, by reducing the content of H2O , which is a polar molecule, the dielectric constant and dielectric loss tangent of the cured product can be further reduced.
• active ester compound is not particularly limited as long as it has at least one ester group in the molecule that reacts with an epoxy group.
• active ester compounds include phenol ester compounds, thiophenol ester compounds, N-hydroxyamine ester compounds, and esters of heterocyclic hydroxy compounds.
• active ester compounds include ester compounds obtained from at least one of an aliphatic carboxylic acid and an aromatic carboxylic acid and at least one of an aliphatic hydroxy compound and an aromatic hydroxy compound.
• Ester compounds that use an aliphatic compound as a polycondensation component tend to have excellent compatibility with epoxy resins due to the presence of an aliphatic chain.
• Ester compounds that use an aromatic compound as a polycondensation component tend to have excellent heat resistance due to the presence of an aromatic ring.
• active ester compounds include aromatic esters obtained by condensation reaction between aromatic carboxylic acids and phenolic hydroxyl groups.
• aromatic esters having a structural unit derived from the aromatic carboxylic acid component, a structural unit derived from the monohydric phenol, and a structural unit derived from the polyhydric phenol are preferred.
• active ester compounds include the active ester resin described in JP 2012-246367 A, which has a structure obtained by reacting a phenolic resin having a molecular structure in which phenolic compounds are bonded via alicyclic hydrocarbon groups with an aromatic dicarboxylic acid or its halide and an aromatic monohydroxy compound.
• the active ester resin is preferably a compound represented by the following structural formula (1).
• R1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group
• X is an unsubstituted benzene ring, an unsubstituted naphthalene ring, a benzene ring or a naphthalene ring substituted with an alkyl group having 1 to 4 carbon atoms, or a biphenyl group
• Y is a benzene ring, a naphthalene ring, or a benzene ring or a naphthalene ring substituted with an alkyl group having 1 to 4 carbon atoms
• k is 0 or 1
• n represents the average number of repetitions and is 0 to 5.
• Specific examples of the compound represented by structural formula (1) include the following exemplary compounds (1-1) to (1-10).
• t-Bu is a tert-butyl group.
• active ester compounds include the compound represented by the following structural formula (2) and the compound represented by the following structural formula (3), which are described in JP 2014-114352 A.
• R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms;
• Z represents an ester-forming structural moiety (z1) selected from the group consisting of an unsubstituted benzoyl group, an unsubstituted naphthoyl group, a benzoyl group or a naphthoyl group substituted with an alkyl group having 1 to 4 carbon atoms, and an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (z2); and at least one of the Z's is an ester-forming structural moiety (z1).
• R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms;
• Z represents an ester-forming structural moiety (z1) selected from the group consisting of an unsubstituted benzoyl group, an unsubstituted naphthoyl group, a benzoyl group or a naphthoyl group substituted with an alkyl group having 1 to 4 carbon atoms, and an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (z2); and at least one of the Z's is an ester-forming structural moiety (z1).
• the active ester compound Commercially available products may be used as the active ester compound.
• Commercially available products of the active ester compound include "EXB9451”, “EXB9460”, “EXB9460S”, and “HPC-8000-65T” (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure; "EXB9416-70BK”, “EXB-8", and “EXB-9425” (manufactured by DIC Corporation) as active ester compounds containing an aromatic structure; “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac; and "YLH1026” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac.
• the ester equivalent (molecular weight/number of ester groups) of the active ester compound is not particularly limited, but from the viewpoint of the balance of various properties such as moldability, reflow resistance, and electrical reliability, it is preferably 150 g/eq to 400 g/eq, more preferably 170 g/eq to 300 g/eq, and even more preferably 200 g/eq to 250 g/eq.
• the ester equivalent of the active ester compound is a value measured by a method in accordance with JIS K 0070:1992.
• the phenolic curing agent include polyhydric phenolic compounds such as resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol; novolak-type phenolic resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol, and dihydroxynaphthalene, with an aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde, under an acidic catalyst; and polyphenolic compounds synthesized from the above phenolic compounds and dimethoxyparaxylene, bis(methoxymethyl)bi
• phenol curing agent examples include aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins, paraxylylene-modified phenolic resins, metaxylylene-modified phenolic resins, melamine-modified phenolic resins, terpene-modified phenolic resins, dicyclopentadiene-type phenolic resins and dicyclopentadiene-type naphthol resins synthesized by copolymerization of the above-mentioned phenolic compounds and dicyclopentadiene, cyclopentadiene-modified phenolic resins, polycyclic aromatic ring-modified phenolic resins, biphenyl-type phenolic resins, triphenylmethane-type phenolic resins obtained by condensing or co-condensing the above-mentioned phenolic compounds with aromatic aldehyde compounds such as benzaldehy
• the hydroxyl equivalent of the phenolic curing agent is not particularly limited. From the viewpoint of the balance of various properties such as moldability, reflow resistance, and electrical reliability, the hydroxyl equivalent of the phenolic curing agent is preferably 70 g/eq to 1000 g/eq, and more preferably 80 g/eq to 500 g/eq.
• the hydroxyl equivalent of the phenol curing agent is a value measured by a method in accordance with JIS K 0070:1992.
• the equivalent ratio of epoxy resin to curing agent i.e., the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (number of functional groups in the curing agent/number of functional groups in the epoxy resin), is not particularly limited. From the viewpoint of keeping the amount of unreacted components low, it is preferably set in the range of 0.5 to 2.0, and more preferably in the range of 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, it is even more preferable to set it in the range of 0.8 to 1.2.
• the molar ratio of the ester groups contained in the active ester compound to the phenolic hydroxyl groups contained in the phenolic hardener is preferably 9/1 to 1/9, more preferably 8/2 to 2/8, and even more preferably 3/7 to 7/3.
• the mass ratio of the active ester compound to the total amount of the active ester compound and the phenolic curing agent is preferably 40% by mass to 90% by mass, more preferably 50% by mass to 80% by mass, and even more preferably 55% by mass to 70% by mass, from the viewpoint of excellent bending strength after curing of the molding resin composition and keeping the dielectric tangent of the cured product low.
• the mass ratio of the phenolic curing agent to the total amount of the active ester compound and the phenolic curing agent is preferably 10% by mass to 60% by mass, more preferably 20% by mass to 50% by mass, and even more preferably 30% by mass to 45% by mass, from the viewpoint of excellent bending strength after curing of the molding resin composition and keeping the dielectric tangent of the cured product low.
• the softening point or melting point of the curing agent is not particularly limited. From the viewpoints of moldability and reflow resistance, the softening point or melting point of the curing agent is preferably 40° C. to 180° C., and from the viewpoint of handleability during production of the molding resin composition, it is more preferably 50° C. to 130° C.
• the melting point or softening point of the curing agent is a value measured in the same manner as the melting point or softening point of the epoxy resin.
• the molding resin composition of the present disclosure contains an inorganic filler.
• the type of inorganic filler is not particularly limited. Specific examples of inorganic fillers include fused silica, crystalline silica, and other silica, glass, alumina, aluminum nitride, boron nitride, talc, clay, mica, calcium titanate, barium titanate, and other inorganic materials.
• An inorganic filler having a flame retardant effect may be used. Examples of inorganic fillers having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, and zinc borate.
• inorganic fillers silica such as fused silica is preferred from the viewpoint of reducing the linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity. From the viewpoint of further reducing the dielectric tangent, boron nitride is preferred.
• One type of inorganic filler may be used alone, or two or more types may be used in combination.
• Inorganic fillers may be in the form of powder, beads formed by spheroidizing powder, fibers, etc.
• the average particle size of the inorganic filler is not particularly limited.
• the volume average particle size is preferably 0.2 ⁇ m to 50 ⁇ m, and more preferably 0.5 ⁇ m to 30 ⁇ m.
• the volume average particle diameter is 0.2 ⁇ m or more, the increase in viscosity of the molding resin composition tends to be further suppressed.
• the volume average particle diameter is 50 ⁇ m or less, the filling ability into narrow gaps tends to be further improved.
• the volume average particle diameter of the inorganic filler refers to a value measured as the volume average particle diameter (D50) by a laser diffraction scattering particle size distribution measuring device.
• the volume average particle diameter of the inorganic filler in the molding resin composition or its cured product can be measured by a known method.
• the inorganic filler is extracted from the molding resin composition or the cured product using an organic solvent, nitric acid, aqua regia, etc., and thoroughly dispersed using an ultrasonic disperser or the like to prepare a dispersion.
• the volume average particle diameter of the inorganic filler can be measured from the volume-based particle size distribution measured using a laser diffraction scattering particle size distribution measuring device.
• the volume average particle diameter of the inorganic filler can be measured from the volume-based particle size distribution obtained by embedding the cured product in a transparent epoxy resin or the like and observing the cross section obtained by polishing it with a scanning electron microscope. Furthermore, the volume average particle diameter of the inorganic filler can be measured by continuously observing the two-dimensional cross section of the cured product using an FIB device (focused ion beam SEM) or the like and performing three-dimensional structural analysis.
• FIB device focused ion beam SEM
• the particle shape of the inorganic filler is preferably spherical rather than angular, and the particle size distribution of the inorganic filler is preferably wide.
• the total content of inorganic fillers contained in the molding resin composition is preferably more than 50% by volume, more preferably more than 55% by volume, even more preferably more than 55% by volume to 90% by volume or less, and particularly preferably 60% by volume to 85% by mass.
• the content (vol %) of the inorganic filler in the molding resin composition can be determined by the following method.
• a thin sample of the cured product of the molding resin composition is photographed with a scanning electron microscope (SEM).
• An arbitrary area S is specified in the SEM image, and the total area A of the inorganic filler contained in the area S is calculated.
• the total area A of the inorganic filler is divided by the area S to convert it into a percentage (%), and this value is the content (volume %) of the inorganic filler in the molding resin composition.
• the area S is set to be sufficiently large relative to the size of the inorganic filler, for example, a size that contains 100 or more inorganic fillers.
• the area S may be the total area of a plurality of cut surfaces.
• the inorganic filler may have a biased presence ratio in the direction of gravity when the molding resin composition is cured.
• an SEM an image of the entire cured product in the direction of gravity is taken, and the area S that includes the entire cured product in the direction of gravity is specified.
• the molding resin composition of the present disclosure contains a mold release agent from the viewpoint of obtaining good releasability from the mold during molding.
• the mold release agent is not particularly limited, and a conventionally known one can be used. Specific examples include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene, etc.
• the mold release agent may be used alone or in combination of two or more kinds.
• the release agent preferably contains a polyolefin wax, and more preferably contains polyethylene oxide.
• the polyethylene oxide may be linear polyethylene oxide or branched polyethylene oxide. Linear polyethylene oxide and branched polyethylene oxide may be used in combination.
• linear oxidized polyethylene refers to oxidized polyethylene in which the number of carbon atoms in the side alkyl chain is about 10% or less of the number of carbon atoms in the main alkyl chain, and generally, oxidized polyethylene with a penetration of 2 or less is classified as linear oxidized polyethylene.
• linear oxidized polyethylene Compared with branched oxidized polyethylene of the same molecular weight and acid value, linear oxidized polyethylene has a high alkyl chain efficiency, tends to bleed out from the base resin easily, and tends to have high releasability. This tendency becomes more pronounced the greater the amount of inorganic filler blended and the greater the weight average molecular weight of the linear oxidized polyethylene.
• the weight average molecular weight of the polyethylene oxide is preferably 2800 or more from the viewpoint of releasability, and is preferably 30000 or less from the viewpoints of adhesion and prevention of mold/package staining, more preferably 2800 to 30000, still more preferably 2900 to 20000, and particularly preferably 3000 to 15000.
• the weight average molecular weight refers to a value measured by high-temperature GPC. The measurement method is as follows.
• Measuring instrument Waters high temperature GPC Column: Polymer Laboratories product name PLgel 10 ⁇ m MIXED-B (7.5 mm ⁇ 300 mm) ⁇ 2 Flow rate: 1.0 ml/min (sample concentration: 0.3 w/vol%) Injection volume: 100 ⁇ l
• the acid value of the oxidized polyolefin is preferably 2 mgKOH/g to 50 mgKOH/g, more preferably 10 mgKOH/g to 40 mgKOH/g, and even more preferably 15 mgKOH/g to 30 mgKOH/g. If the acid value is 5 mgKOH/g or more, package staining tends to be more easily suppressed, and if it is 50 mgKOH/g or less, mold releasability tends to be more improved.
• the acid value of the oxidized polyolefin is a value measured by a method in accordance with JIS K 5902:1969.
• the content of the release agent is preferably 1 part by mass to 30 parts by mass, more preferably 5 parts by mass to 25 parts by mass, and even more preferably 7 parts by mass to 20 parts by mass, per 100 parts by mass of the sulfur atom-containing epoxy resin.
• the content of the release agent is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass, based on 100 parts by mass of the epoxy resin and the curing agent in total.
• the amount of the release agent is 0.01 parts by mass or more based on 100 parts by mass of the epoxy resin and the curing agent in total, sufficient releasability tends to be obtained. When the amount is 10 parts by mass or less, better adhesion tends to be obtained.
• the content of polyethylene oxide is preferably 1 part by mass to 30 parts by mass, more preferably 5 parts by mass to 25 parts by mass, and even more preferably 7 parts by mass to 20 parts by mass, per 100 parts by mass of the sulfur atom-containing epoxy resin.
• the amount of polyethylene oxidized is 1 part by mass or more per 100 parts by mass of the sulfur atom-containing epoxy resin, sufficient releasability tends to be obtained.
• the content of the polyethylene oxide is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the epoxy resin and the curing agent in total.
• the amount of the polyethylene oxide is 0.01 part by mass or more per 100 parts by mass of the epoxy resin and the curing agent in total, sufficient releasability tends to be obtained. When the amount is 10 parts by mass or less, better adhesion tends to be obtained.
• the molding resin composition of the present disclosure contains a specific copolymer.
• the ⁇ -olefin having 5 to 30 carbon atoms used in the specific copolymer is not particularly limited. Specific examples of the ⁇ -olefin having 5 to 30 carbon atoms include 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1- Examples of the ⁇ -olefin include linear ⁇ -olefins such as hexacosene
• linear ⁇ -olefins having 10 to 25 carbon atoms are preferred, and linear ⁇ -olefins having 15 to 25 carbon atoms such as 1-eicosene, 1-docosene, and 1-tricosene are more preferred.
• the maleic anhydride derivative used in the specific copolymer include methylmaleic anhydride and dimethylmaleic anhydride.
• the specific copolymer preferably contains a structural unit represented by the following general formula (C) and a structural unit represented by the following general formula (D).
• R 11 represents a monovalent aliphatic hydrocarbon group having 3 to 28 carbon atoms
• R 12 and R 13 each independently represent a hydrogen atom, an alkyl group, or an aryl group.
• R 11 is preferably a straight-chain hydrocarbon group having 13 to 23 carbon atoms, and more preferably a straight-chain hydrocarbon group having 18 to 21 carbon atoms, such as an n-octadecyl group, an n-eicosyl group, or an n-heneicosyl group.
• the alkyl group represented by R 12 or R 13 includes an alkyl group having 1 to 4 carbon atoms, and a methyl group is preferable.
• the aryl group represented by R 12 or R 13 is preferably a phenyl group.
• R 12 and R 13 are preferably a hydrogen atom.
• the specific copolymer may have any structure, such as a random, block or graft copolymer.
• the specific copolymer may or may not contain other structural units than the structural unit represented by general formula (C) and the structural unit represented by general formula (D).
• the ratio of other structural units to the total structural units of the specific copolymer is preferably 0 mol% to 50 mol%, more preferably 0 mol% to 35 mol%, and even more preferably 0 mol% to 20 mol%.
• the specific copolymer may have a carboxy group as a result of at least a portion of the structural units derived from at least one of maleic anhydride and maleic anhydride derivatives contained in the specific copolymer being hydrolyzed.
• the method for producing the specific copolymer is not particularly limited, and a general copolymerization method such as reacting raw materials can be used.
• an organic solvent capable of dissolving ⁇ -olefin and maleic anhydride may be used.
• the organic solvent is not particularly limited, but toluene is preferred, and alcohol-based solvents, ether-based solvents, amine-based solvents, and the like can also be used.
• the reaction temperature varies depending on the type of organic solvent used, but from the viewpoints of reactivity and productivity, it is preferably 50°C to 200°C, and more preferably 80°C to 120°C.
• the reaction time is not particularly limited as long as the specific copolymer is obtained, but from the viewpoint of productivity, it is preferably 1 hour to 30 hours, more preferably 2 hours to 15 hours, and even more preferably 4 hours to 10 hours.
• the conditions are preferably a temperature of 100°C to 220°C, more preferably 120°C to 180°C, a pressure of 13.3 x 10 3 Pa or less, more preferably 8 x 10 3 Pa or less, and a time of 0.5 hours to 10 hours.
• a reaction catalyst such as an amine catalyst or an acid catalyst may be added to the reaction.
• the pH of the reaction system is preferably about 1 to 10.
• the specific copolymer may be a commercially available product.
• One commercially available product is Nissan Electol WPB-1 (trade name, manufactured by NOF Corporation), which uses 1-eicosene, 1-docosene, and 1-tricosene as raw materials.
• the weight average molecular weight of the specific copolymer is preferably 5000 to 100000, more preferably 10000 to 70000, and even more preferably 15000 to 50000. If the weight average molecular weight is 5000 or more, the effect of preventing mold/package contamination tends to be sufficient, and if it is 100000 or less, the softening point of the specific copolymer does not increase too much, and deterioration of kneadability, etc. tends to be suppressed.
• the weight average molecular weight of the specific copolymer is determined by measuring the molecular weight by gel permeation chromatography (GPC) and converting the molecular weight using a calibration curve of standard polystyrene.
• GPC conditions are as follows: -GPC conditions- Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.) Columns: 3 in total Gelpack GL-R420 Gelpack GL-R430 Gelpack GL-R440 (The above are product names manufactured by Showa Denko Materials Technoservice Co., Ltd.) Eluent: tetrahydrofuran Measurement temperature: 25°C Flow rate: 2.05 mL/min Detector: Hitachi L-3300 RI (manufactured by Hitachi, Ltd.)
• the content of the specific copolymer is preferably 0.01 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 1 to 4 parts by mass, per 100 parts by mass of the sulfur atom-containing epoxy resin.
• the content of the specific copolymer is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the epoxy resin and the curing agent in total.
• the amount of the specific copolymer is 0.01 parts by mass or more based on 100 parts by mass of the epoxy resin and the curing agent in total, sufficient releasability tends to be obtained.
• the amount is 10 parts by mass or less, adhesion and the effect of improving mold and package staining tend to be sufficient.
• the molding resin composition of the present disclosure may contain a curing accelerator as necessary.
• the type of the curing accelerator is not particularly limited and can be selected depending on the type of epoxy resin, the desired properties of the molding resin composition, and the like.
• the curing accelerator examples include diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 2-heptadecylimidazole, derivatives of the cyclic amidine compounds, phenol novolac salts of the cyclic amidine compounds or derivatives thereof, and combinations of these compounds with maleic anhydride, quinone compounds such as 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-
• organic phosphines such as tertiary phosphines, such as tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, and tris(benzyl)phosphine; phosphine compounds such as complexes of the above-mentioned organic phosphines with organic borons; compounds having intramolecular polarization obtained by adding a compound having a ⁇ bond, such as quinone compounds, such as 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1
• halogenated phenol compounds include compounds having intramolecular polarization obtained by reacting a halogenated phenol compound such as bromophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, and 4-bromo-4'-hydroxybiphenyl with the resulting compound and then subjecting the resulting compound to a dehydrohalogenation process; tetra-substituted phosphonium compounds such as tetraphenylphosphonium, tetraphenylborate salts of tetra-substit
• the curing accelerator is preferably an organic phosphine-containing curing accelerator, which may include the organic phosphines, phosphine compounds such as complexes of the organic phosphines and organic borons, and compounds having intramolecular polarization formed by adding a compound having a ⁇ bond to the organic phosphines or the phosphine compounds.
• particularly suitable curing accelerators include triphenylphosphine, an adduct of triphenylphosphine and a quinone compound, an adduct of tributylphosphine and a quinone compound, and an adduct of tri-p-tolylphosphine and a quinone compound.
• the amount is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of the epoxy resin and curing agent combined.
• the amount of the curing accelerator is 0.1 parts by mass or more per 100 parts by mass of the epoxy resin and curing agent combined, it tends to cure well in a short time.
• the amount of the curing accelerator is 30 parts by mass or less per 100 parts by mass of the epoxy resin and curing agent combined, it tends to cure not too quickly and to produce a good molded product.
• the molding resin composition of the present disclosure may contain a stress relaxation agent.
• a stress relaxation agent By containing a stress relaxation agent, it is possible to further reduce the warpage deformation of the package and the occurrence of package cracks.
• the stress relaxation agent include known stress relaxation agents (flexibilizers) that are generally used.
• thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based elastomers, indene-styrene-coumarone copolymers, triphenylphosphine oxide, and organic phosphorus compounds such as phosphoric acid esters, rubber particles such as NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, urethane rubber, and silicone powder, and rubber particles having a core-shell structure such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, and methyl methacrylate-butyl acrylate copolymer.
• MBS methyl methacrylate-styrene-butadiene copolymer
• MBS methyl methacrylate-silicon
• the stress relaxation agent may be used alone or in combination of two or more types.
• silicone-based stress relaxation agent include those having an epoxy group, those having an amino group, and those modified with polyether. More preferred are silicone compounds such as a silicone compound having an epoxy group and a polyether-based silicone compound.
• the stress relaxation agent contains at least one of an indene-styrene-coumarone copolymer and triphenylphosphine oxide.
• the amount thereof is, for example, preferably 1 part by mass to 35 parts by mass, and more preferably 2 parts by mass to 34 parts by mass, per 100 parts by mass of the epoxy resin and the curing agent in total.
• the stress relaxation agent contains at least one of an indene-styrene-coumarone copolymer and triphenylphosphine oxide
• the amount thereof is, for example, preferably 1 part by mass to 30 parts by mass, and more preferably 2 parts by mass to 20 parts by mass, per 100 parts by mass of the epoxy resin and the curing agent in total.
• the content of the silicone-based stress relaxation agent may be, for example, 2 parts by mass or less, or 1 part by mass or less, relative to 100 parts by mass of the epoxy resin and the curing agent in total.
• the molding resin composition may not contain a silicone-based stress relaxation agent.
• the lower limit of the content of the silicone-based stress relaxation agent is not particularly limited, and may be 0 parts by mass or 0.1 parts by mass.
• the content of the silicone-based stress relaxation agent is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 7% by mass or less, particularly preferably 5% by mass or less, and extremely preferably 0.5% by mass or less, relative to the entire molding resin composition.
• the content of the silicone-based stress relaxation agent may be 0% by mass or 0.1% by mass.
• the molding resin composition of the present disclosure may contain various additives such as coupling agents, ion exchangers, flame retardants, colorants, etc., as exemplified below.
• the molding resin composition of the present disclosure may contain various additives known in the art, as necessary, in addition to the additives exemplified below.
• the molding resin composition of the present disclosure may contain a coupling agent.
• the molding resin composition preferably contains a coupling agent.
• the coupling agent include known coupling agents such as silane-based compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane, and disilazane, titanium-based compounds, aluminum chelate-based compounds, and aluminum/zirconium-based compounds.
• the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass, and more preferably 0.1 parts by mass to 2.5 parts by mass, per 100 parts by mass of the inorganic filler.
• the amount of the coupling agent is 0.05 parts by mass or more per 100 parts by mass of the inorganic filler, the adhesiveness tends to be further improved.
• the amount of the coupling agent is 5 parts by mass or less per 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.
• the molding resin composition of the present disclosure may contain an ion exchanger.
• the molding resin composition preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including an electronic component to be sealed.
• the ion exchanger is not particularly limited, and a conventionally known ion exchanger can be used. Specific examples include hydrotalcite compounds and hydrated oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth.
• the ion exchanger may be used alone or in combination of two or more types. Among them, hydrotalcite represented by the following general formula (A) is preferred.
• the molding resin composition contains an ion exchanger
• the content of the ion exchanger is preferably 0.1 to 30 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the epoxy resin and hardener combined.
• the molding resin composition of the present disclosure may contain a flame retardant.
• the flame retardant is not particularly limited, and a conventionally known one may be used. Specific examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, metal hydroxides, etc.
• the flame retardant may be used alone or in combination of two or more kinds.
• the amount is not particularly limited as long as it is an amount sufficient to obtain the desired flame retardant effect.
• the amount of flame retardant is preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 100 parts by mass of the epoxy resin and hardener combined.
• the molding resin composition of the present disclosure may contain a colorant.
• the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and red iron oxide.
• the content of the colorant can be appropriately selected depending on the purpose, etc.
• the colorant may be used alone or in combination of two or more kinds.
• the method for preparing the molding resin composition is not particularly limited.
• a typical method is to thoroughly mix the components in a predetermined amount with a mixer or the like, melt-knead them with a mixing roll, an extruder, or the like, cool them, and pulverize them. More specifically, for example, a method is to stir and mix the predetermined amounts of the above-mentioned components, knead them with a kneader, roll, extruder, or the like that has been heated to 70°C to 140°C in advance, cool them, and pulverize them.
• the molding resin composition of the present disclosure is preferably solid at room temperature and normal pressure (e.g., 25°C, atmospheric pressure).
• the shape is not particularly limited, and examples include powder, granules, and tablets.
• the molding resin composition is in tablet form, it is preferable from the viewpoint of handleability that the dimensions and mass are set to be suitable for the molding conditions of the package.
• the dielectric constant at 5 GHz of the cured product of the molding resin composition of the present disclosure is, for example, 3.3 to 4.0. From the viewpoint of miniaturization of electronic components such as antennas, the dielectric constant at 5 GHz of the cured product is preferably 3.3 to 3.8, more preferably 3.3 to 3.6, and even more preferably 3.3 to 3.5.
• the measurement of the relative dielectric constant is carried out at a temperature of 25 ⁇ 3° C. using a dielectric constant measuring device (for example, a cavity resonator). In order to make the relative dielectric constant of the cured product 3.3 to 3.5 at 5 GHz, it is preferable to use an active ester compound as the curing agent.
• the dielectric loss tangent at 5 GHz of the cured product of the molding resin composition of the present disclosure is, for example, 0.08 or less. From the viewpoint of reducing transmission loss, the dielectric loss tangent at 5 GHz of the cured product is preferably 0.04 or less, more preferably 0.02 or less, and even more preferably 0.01 or less.
• the lower limit of the dielectric loss tangent at 5 GHz of the cured product is not particularly limited, and is, for example, 0.001.
• the dielectric loss tangent is measured at a temperature of 25 ⁇ 3° C. using a dielectric constant measuring device (for example, a cavity resonator). In order to make the dielectric loss tangent of the cured product 0.01 or less at 5 GHz, it is preferable to use an active ester compound as the curing agent.
• the molding resin composition of the present disclosure can be applied to, for example, the manufacture of electronic component devices, particularly high-frequency devices, which will be described later.
• the molding resin composition of the present disclosure may be used to seal electronic components in high-frequency devices.
• an active ester compound As a curing agent.
• semiconductor packages (PKGs) used in electronic component devices have become more functional and smaller.
• the molding resin composition of the present disclosure uses an active ester compound as a curing agent, and thereby a cured product having a low dielectric tangent and dielectric constant can be obtained. Therefore, the molding resin composition is particularly suitable for use in antenna-in-package (AiP) applications in which an antenna disposed on a support member of a high-frequency device is encapsulated with the molding resin composition.
• AlP antenna-in-package
• the molding resin composition used in the manufacture of the electronic component device contains alumina particles as an inorganic filler.
• the electronic component device of the present disclosure includes a support member, an electronic component disposed on the support member, and a cured product of the molding resin composition described above that encapsulates the electronic component.
• electronic component devices include those (e.g., high frequency devices) obtained by mounting electronic components (active elements such as semiconductor chips, transistors, diodes, and thyristors, passive elements such as capacitors, resistors, and coils, antennas, etc.) on a support member such as a lead frame, a pre-wired tape carrier, a wiring board, glass, a silicon wafer, or an organic substrate, and then sealing the resulting electronic component region with a molding resin composition.
• active elements such as semiconductor chips, transistors, diodes, and thyristors, passive elements such as capacitors, resistors, and coils, antennas, etc.
• the type of the support member is not particularly limited, and any support member that is generally used in the manufacture of electronic component devices can be used.
• the electronic component may include an antenna, or may include an antenna and an element other than an antenna.
• the antenna is not limited as long as it functions as an antenna, and may be an antenna element or a wiring.
• other electronic components may be arranged on the surface of the support member opposite to the surface on which the electronic components are arranged, as necessary.
• the other electronic components may be sealed with the molding resin composition described above, may be sealed with another resin composition, or may not be sealed.
• the manufacturing method of the electronic component device of the present disclosure includes a step of placing an electronic component on a support member, and a step of encapsulating the electronic component with the molding resin composition described above.
• the method for carrying out each of the above steps is not particularly limited, and each step can be carried out by a general method. Furthermore, there are no particular limitations on the types of support members and electronic components used in the manufacture of electronic component devices, and support members and electronic components that are generally used in the manufacture of electronic component devices can be used.
• Methods for encapsulating electronic components using the aforementioned molding resin composition include low-pressure transfer molding, injection molding, and compression molding. Of these, low-pressure transfer molding is the most common.
• Molding resin compositions of Examples and Comparative Examples were prepared by mixing the components shown below in the blending ratios (parts by mass) shown in Tables 1 and 2. This molding resin composition was solid at room temperature and normal pressure. Tables 1 and 2 also show the content of the inorganic filler relative to the entire molding resin composition ("Filler amount (volume %)" in the tables).
• Epoxy resin 1 Triphenylmethane type epoxy resin (epoxy equivalent: 167 g/eq)
• Epoxy resin 2 A compound represented by general formula (B), in which, when the positions at which oxygen atoms are substituted in R 10 are the 4 and 4' positions, the 3 and 3' positions are tert-butyl groups, the 6 and 6' positions are methyl groups, and the remaining R 10 are hydrogen atoms (epoxy equivalent: 245 g/eq).
• Epoxy resin 3 bisphenol F type epoxy resin (epoxy equivalent: 193 g/eq)
• Epoxy resin 4 biphenyl aralkyl type epoxy resin (epoxy equivalent 277 g/eq)
• Epoxy resin 5 biphenyl type epoxy resin (epoxy equivalent: 196 g/eq)
• Epoxy resin 6 o-cresol novolac type epoxy resin (epoxy equivalent: 200 g/eq)
• Hardener 1 Triphenylmethane type phenolic resin (hydroxyl equivalent: 106 g/eq)
• Hardener 2 Melamine modified phenolic resin (hydroxyl equivalent: 120 g/eq)
• Hardener 3 Biphenyl aralkyl type phenolic resin (hydroxyl group equivalent: 200 g/eq)
• Hardener 4 Active ester compound, DIC Corporation, product name "EXB-8" Curing accelerator: adduct of tributylphosphine and 1,4-benzoquinone Coupling
• Additive 1 silicone oil with epoxy equivalent of 2900 g/eq and viscosity of 2850 mm 2 /s (25° C.)
• Additive 2 triphenylphosphine oxide
• Additive 3 polysiloxane with epoxy equivalent of 1660 g/eq and softening point of 80° C.
• Inorganic filler 1 silica particles (volume average particle size: 0.6 ⁇ m)
• Inorganic filler 2 Magnesium hydroxide particles (volume average particle size: 1.5 ⁇ m)
• Inorganic filler 3 Silica particles (volume average particle size: 27 ⁇ m)
• Inorganic filler 4 Silica particles (volume average particle size: 16 ⁇ m)
• Inorganic filler 5 silica particles (volume average particle size: 11 ⁇ m)
• Inorganic filler 6 silica particles (volume average particle size: 2.3 ⁇ m)
• Inorganic filler 7 silica particles (volume average particle size: 30 ⁇ m)
• Inorganic filler 8 Silica particles (nanosilica particles with a specific surface area of 190 m 2 /g to 230 m 2 /g)
• Inorganic filler 9 silica particles (volume average particle size: 17 ⁇ m)
• Inorganic filler 10 silica particles (volume average particle size: 1.5 ⁇ m)
• the volume average particle size of each of the inorganic fillers is a value obtained by the following measurement. Specifically, first, the inorganic filler was added to a dispersion medium (water) in a range of 0.01% by mass to 0.1% by mass, and dispersed in a bath-type ultrasonic cleaner for 5 minutes. 5 ml of the obtained dispersion was poured into a cell, and the particle size distribution was measured at 25° C. using a laser diffraction scattering particle size distribution measuring device (LA920, manufactured by Horiba, Ltd.). The particle size at an integrated value of 50% (volume basis) in the obtained particle size distribution was defined as the volume average particle size.
• the specific surface area of the inorganic filler 8 was a value measured from the nitrogen adsorption capacity in accordance with JIS Z 8830:2013.
• thermosetting resin composition was evaluated as follows.
• the thermosetting resin composition was molded into test pieces (disks with a diameter of 50 mm and a thickness of 3 mm) for measuring hot hardness using a transfer molding machine under the conditions of a mold temperature of 175°C to 180°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds.
• the hot hardness (Shore D) of the test pieces was measured using a Shore D hardness tester. The results are shown in Tables 3 and 4.
• Example 6 The molding resin compositions of Example 6 and Comparative Example 4 were molded using a transfer molding machine under conditions of a molding temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 120 seconds to obtain a plate-shaped molded product (length 127 mm, width 12.7 mm, thickness 4 mm). This was designated as Test Piece 1. Test Piece 1 was then post-cured at 175°C for 5 hours to obtain a plate-shaped cured product (length 127 mm, width 12.7 mm, thickness 4 mm). This was designated as Test Piece 2. The bending strength (MPa) of the test pieces 1 and 2 was measured using an autograph (flexural tester AG-500, manufactured by Shimadzu Corporation). The results are shown in Table 4.
• Example 6 The molding resin compositions of Example 6 and Comparative Example 4 were charged into a transfer molding machine and molded under conditions of a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 120 seconds. Post-curing was carried out at 175°C for 6 hours to prepare rectangular parallelepiped test pieces measuring 90 mm x 0.6 mm x 0.8 mm.
• the dielectric constant (Dk) and dielectric loss tangent (Df) of this test piece were measured at a frequency of 5 GHz using a cavity resonator (Kanto Electronics Application Development Co., Ltd.) and a network analyzer (Keysight Technologies, product name "PNA E8364B") in an environment at a temperature of 25 ⁇ 3° C. The results are shown in Table 4.
• the molding resin composition was compression molded into a disk shape on a ferroplate (35 mm x 50 mm x 0.5 mm) with a hard chrome-plated surface to produce a cured product with a disk area of 3.14 cm2.
• the molding of the molding resin composition was performed at a molding temperature of 175°C, a molding time of 90 seconds, and a molding pressure of 10 MPa.
• the cured product was fixed using a surface adsorption machine, and the ferromagnetic plate was pulled out horizontally to the interface between the cured product and the ferromagnetic plate, thereby peeling the cured product from the ferromagnetic plate.
• the shear release force (shear release strength) required to peel the cured product from the ferromagnetic plate was read using a push-pull gauge (manufactured by Imada Co., Ltd., maximum scale 500 (N)). After the measurement of the shear release force was completed, the molding resin composition was compressed again into a disk shape at the site where the cured material was peeled off from the ferroplate, and the shear release force was then measured. This process was repeated 10 times in total. The measurement results are shown in Tables 3 and 4. The progress of the shear release strength at each measurement is shown in Figures 1 and 2. In Figure 2, the solid line shows the results of Example 6, and the dotted line shows the results of Comparative Example 4.
• Example 1 to 5 which used a phenol curing agent, showed a steeper decrease in shear release strength than Comparative Examples 1 to 3, and were found to have excellent release properties.
• Example 6 in which an active ester compound was used as a curing agent, showed a steeper decrease in shear release strength than Comparative Example 4, and was found to have excellent release properties.

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