Classifications

• • 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
  • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • 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
• • C—CHEMISTRY; METALLURGY
  • 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
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01Q—ANTENNAS, i.e. RADIO AERIALS
  • H01Q1/00—Details of, or arrangements associated with, antennas
  • H01Q1/40—Radiating elements coated with or embedded in protective material
• • 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
  • H10W74/473—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins containing a filler

Definitions

• This disclosure relates to a molding resin composition and an electronic component device.
• Patent Documents 1 and 2 disclose a thermosetting resin composition that contains an active ester resin as a curing agent for epoxy resin, which is said to be able to keep the dielectric tangent of the cured product low.
• Patent Document 1 JP 2012-246367 A
• Patent Document 2 JP 2014-114352 A
• a molding resin composition containing an epoxy resin, a curing agent, and an inorganic filler can be mentioned.
• the transmission signal is converted into heat due to dielectric loss, and communication efficiency is likely to decrease.
• the amount of dielectric loss generated by the heat conversion of radio waves transmitted for communication in a dielectric is expressed as the product of the frequency, the square root of the relative dielectric constant, and the dielectric loss tangent.
• the transmission signal is more likely to be converted into heat in proportion to the frequency.
• radio waves used for communication have become higher in frequency to accommodate the increase in the number of channels accompanying the diversification of information. From the viewpoint of reducing dielectric loss, there is a demand for a molding resin composition capable of molding a cured product with a low dielectric loss tangent.
• an active ester resin is used as a curing agent in order to keep the dielectric tangent of the cured product low, the strength of the cured product may decrease.
• 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 capable of forming a cured product that exhibits a low dielectric tangent and excellent strength, and an electronic component device using the same.
• a molding resin composition comprising an epoxy resin including at least one of a phenol novolac type epoxy resin having an epoxy equivalent of 156 g/eq to 250 g/eq and a cresol novolac type epoxy resin having an epoxy equivalent of 156 g/eq to 250 g/eq, an active ester compound, and an inorganic filler.
• ⁇ 3> The molding resin composition according to ⁇ 1> or ⁇ 2>, wherein the total content of the inorganic filler is more than 50 volume % based on the total molding resin composition.
• ⁇ 4> The molding resin composition according to any one of ⁇ 1> to ⁇ 3>, which is used for a high-frequency device.
• ⁇ 5> The molding resin composition according to ⁇ 4>, which is used for sealing electronic parts in a high-frequency device.
• ⁇ 6> The molding resin composition according to ⁇ 4>, which is used for an antenna-in-package.
• a support member an electronic component disposed on the support member;
• An electronic component device comprising: ⁇ 8> The electronic component device according to ⁇ 7>, wherein the electronic component includes an antenna.
• the present disclosure provides a molding resin composition capable of forming a cured product that exhibits a low dielectric tangent and excellent strength, and an electronic component device using the same.
• 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 an epoxy resin including at least one of a phenol novolac type epoxy resin having an epoxy equivalent of 156 g/eq to 250 g/eq and a cresol novolac type epoxy resin having an epoxy equivalent of 156 g/eq to 250 g/eq, an active ester compound, and an inorganic filler.
• an epoxy resin including at least one of a phenol novolac type epoxy resin having an epoxy equivalent of 156 g/eq to 250 g/eq and a cresol novolac type epoxy resin having an epoxy equivalent of 156 g/eq to 250 g/eq, an active ester compound, and an inorganic filler.
• the phenol novolac type epoxy resin having an epoxy equivalent of 156 g/eq to 250 g/eq and the cresol novolac type epoxy resin having an epoxy equivalent of 156 g/eq to 250 g/eq may be referred to as a specific novolac type epoxy resin.
• the molding resin composition of the present disclosure is capable of forming a cured product that exhibits a low dielectric tangent and is excellent in strength.
• the reason for this is not clear, but is presumed to be as follows.
• a phenolic curing agent is used as a curing agent for an epoxy resin
• a secondary hydroxyl group is generated in the reaction between the epoxy resin and the phenolic curing agent.
• an active ester compound is used as a curing agent for an epoxy resin, an ester group is generated instead of a secondary hydroxyl group in the reaction between the epoxy resin and the active ester compound.
• an ester group has a lower polarity than a secondary hydroxyl group
• a molding resin composition containing an active ester compound as a curing agent can suppress the dielectric tangent of the cured product to a lower value 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.
• the dielectric tangent of the cured product can be further reduced.
• the specific novolac type epoxy resin has few molecular structures that can cause steric hindrance in its molecule, so that the crosslink density of the cured product can be improved. Therefore, it is presumed that it is possible to form a cured product with excellent strength.
• the molding resin composition of the present disclosure exhibits a low dielectric tangent and is capable of forming a cured product with excellent strength.
• the components constituting the molding resin composition are described below.
• the molding resin composition of the present disclosure contains at least one specific novolac type epoxy resin as an epoxy resin, an active ester compound as a curing agent, and an inorganic filler, and may contain other components as necessary.
• the molding resin composition of the present disclosure includes at least one specific novolac type epoxy resin as an epoxy resin.
• the molding resin composition of the present disclosure may include an epoxy resin other than the specific novolac type epoxy resin.
• the total proportion of the specific novolac epoxy resins in the epoxy resins is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, and even more preferably 70% by mass to 80% 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 specific novolac type epoxy resin is not particularly limited as long as it is an epoxy resin having an epoxy equivalent of 156 g/eq to 250 g/eq obtained by epoxidizing a phenol novolac resin or a cresol novolac resin using a method such as glycidyl etherification, etc.
• the epoxy equivalent of the specific novolac type epoxy resin is preferably 170 g/eq to 240 g/eq, more preferably 180 g/eq to 230 g/eq, and even more preferably 190 g/eq to 220 g/eq.
• the specific novolac type epoxy resin is more preferably an epoxy resin represented by the following general formula (B):
• B an epoxy resin represented by the following general formula (B):
• ESCN-190 and ESCN-195 (trade names, Sumitomo Chemical Co., Ltd.) in which R A is a methyl group
• N-770 and N-775 (trade names, DIC Corporation) in which R A is a hydrogen atom are commercially available.
• R A represents a hydrogen atom or a methyl group
• n represents an average value and is a number from 0 to 10.
• epoxy resins include novolac-type epoxy resins (excluding specific novolac-type epoxy resins) 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, resorcin, catechol, bisphenol A, bisphenol F, and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol, and dihydroxynaphthalene with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acid catalyst; triphenylmethane-type epoxy resins obtained by epoxidizing triphenylmethane-type phenolic resins obtained by condensing or co-condensing the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehy
• dicyclopentadiene-type epoxy resins in which a co-condensed resin of dicyclopentadiene and a phenol compound is epoxidized
• alicyclic epoxy resins such as vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane in which an olefin bond in a molecule is epoxidized
• paraxylylene-modified epoxy resins which are glycidyl ethers of paraxylylene-modified phenol resins
• metaxylylene-modified epoxy resins which are glycidyl ethers of metaxylylene-modified phenol resins
• the other epoxy resins preferably include biphenyl type epoxy resins.
• the epoxy equivalent (molecular weight/number of epoxy groups) of the other 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 other epoxy resin is preferably 100 g/eq to 1000 g/eq, and more preferably 150 g/eq to 500 g/eq. In the present disclosure, 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 an active ester compound as a curing agent.
• the curing agent may contain other curing agents besides the active ester compound, such as a phenolic curing agent.
• the molding resin composition may contain only one type of active ester compound, or may contain two or more types of active ester compounds.
• 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 a curing action for an epoxy resin.
• 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 a 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 molding resin composition of the present disclosure preferably includes a combination of an epoxy resin and an active ester compound that results in an unreacted epoxy rate of 2% or less, more preferably a combination that results in an unreacted epoxy rate of 1.2% or less, and even more preferably a combination that results in an unreacted epoxy rate of 0.7% or less.
• the molding resin composition of the present disclosure contains two or more types of epoxy resins or two or more types of active ester compounds, it preferably contains at least one combination of an epoxy resin and an active ester compound that results in an unreacted epoxy ratio of 2% or less.
• an epoxy resin having a sterically crowded structure in the molecule such as a triphenylmethane type epoxy resin having a structure in which three aryl groups are bonded to one carbon atom, or an epoxy resin having a benzyl group, tert-butyl group, or other substituent with large steric hindrance as a substituent, tends to leave unreacted epoxy groups in the cured product due to steric hindrance when reacting with an active ester compound.
• the strength of the cured product tends to be reduced by the remaining unreacted epoxy groups in the cured product.
• the epoxy resin and the active ester compound include a combination in which the unreacted epoxy ratio is 2% or less, more preferably a combination in which the unreacted epoxy ratio is 1.2% or less, and even more preferably a combination in which the unreacted epoxy ratio is 0.7% or less.
• the combination of the other epoxy resin and the active ester compound is preferably such that the unreacted epoxy ratio is 2% or less, more preferably such that the unreacted epoxy ratio is 1.2% or less, and even more preferably such that the unreacted epoxy ratio is 0.7% or less.
• the specific novolac type epoxy resin does not contain a sterically crowded structure in the molecule, the unreacted epoxy ratio is likely to be 2% or less, and unreacted epoxy groups are unlikely to be generated during the curing reaction with the active ester compound. Therefore, the specific novolac type epoxy resin is unlikely to cause a decrease in the strength of the cured product due to the generation of unreacted epoxy groups.
• the unreacted epoxy ratio refers to a value measured by the following method.
• Epoxy resin and active ester compound are weighed out in an equivalent ratio of 1:1, mixed, and 1 to 3 parts by mass of phosphorus catalyst is added to 100 parts by mass of the total amount of epoxy resin and active ester compound, and the mixture is melted and mixed while heating at 130°C on a hot plate, cooled to room temperature, and pulverized into powder.
• the phosphorus catalyst is adjusted so that the gel time of the mixture of epoxy resin and active ester compound is about 60 seconds.
• This neat range powder and a cured product sample heated at 175°C for 5.5 hours are placed in an FT-IR (Nicolet iZ10 manufactured by Thermo Fisher scientific) device to obtain an absorption spectrum.
• FT-IR Nicolet iZ10 manufactured by Thermo Fisher scientific
• the area ratio of the epoxy-derived peak (910 cm -1 )/aromatic ring peak (1610 cm -1 ) is calculated, and the unreacted epoxy is quantified from the rate of change in this ratio.
• the gel time is measured by the following method. 0.5 g of the measurement sample is placed on a hot plate heated to 175° C., and the sample is uniformly spread into a circle with a diameter of 2.0 cm to 2.5 cm using a tool at a rotation speed of 20 to 25 revolutions per minute. The time from when the measurement sample is placed on the hot plate until the viscosity of the measurement sample disappears, the sample becomes gelled, and the sample can be peeled off from the hot plate is measured, and this time is regarded as the gel time (seconds).
• the molding resin composition of the present disclosure may contain a phenolic curing agent as another curing agent.
• a 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 phenolic curing agent.
• 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 99% by mass, more preferably 60% by mass to 97% by mass, and even more preferably 80% by mass to 95% 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 active ester compound as the curing agent and the other curing agents such as the phenol curing agent used as necessary are not particularly limited.
• the softening point or melting point of the curing agent is preferably 40° C. to 180° C. from the viewpoint of moldability and reflow resistance, and more preferably 50° C. to 130° C. from the viewpoint of handleability during production of the molding resin composition.
• 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 volume % relative to the total molding resin composition, more preferably more than 55 volume %, even more preferably more than 55 volume % to 90 volume % or less, and particularly preferably 60 volume % to 80 volume %.
• 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 may contain 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 may 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 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 epoxy resin.
• the amount of the release agent is 1 part by mass or more per 100 parts by mass of the epoxy resin, sufficient releasability tends to be obtained.
• the amount is 30 parts by mass or less, better adhesion tends to be obtained.
• 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 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 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 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 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 0.3 to 1 part 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, tablets, etc.
• 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, 2.5 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 2.6 to 3.7, more preferably 2.8 to 3.6, and even more preferably 2.9 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).
• the dielectric loss tangent at 5 GHz of the cured product of the molding resin composition of the present disclosure is, for example, 0.008 or less. From the viewpoint of reducing transmission loss, the dielectric loss tangent at 5 GHz of the cured product is preferably 0.006 or less, more preferably 0.005 or less, and even more preferably 0.004 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).
• the molding resin composition of the present disclosure can be applied to, for example, the manufacture of electronic component devices, particularly high-frequency devices, described below.
• the molding resin composition of the present disclosure may be used to seal electronic components in high-frequency devices.
• semiconductor packages (PKGs) used in electronic component devices have become more functional and smaller.
• AiP radio waves used for communication are becoming higher in frequency to accommodate an increase in the number of channels accompanying the diversification of information, and a low dielectric tangent is required for the sealing material.
• the molding resin composition of the present disclosure can give a cured product having a low dielectric tangent, and is therefore particularly suitable for use in antenna-in-package (AiP) applications in high-frequency devices in which an antenna disposed on a support member is encapsulated with the molding resin composition.
• an electronic component device including an antenna such as an 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 encapsulating 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 can be carried out by a general method.
• the types of the support member and electronic components used in the manufacture of the electronic component device are not particularly limited and support members and electronic components generally used in the manufacture of the electronic component device can be used.
• Methods for encapsulating electronic components using the molding resin composition described above 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 at 110° C. in the blending ratios (parts by mass) shown in Table 1. This molding resin composition was a solid at room temperature and normal pressure. Table 1 also shows the content of the inorganic filler relative to the entire molding resin composition ("Filler amount (volume %)" in the table.
• Epoxy resin 1 ...triphenylmethane type epoxy resin (epoxy equivalent: 169 g/eq)
• Epoxy resin 2 ...triphenylmethane type epoxy resin (epoxy equivalent: 215 g/eq)
• Epoxy resin 3 biphenyl type epoxy resin (epoxy equivalent 192 g/eq)
• Epoxy resin 4 biphenyl aralkyl type epoxy resin (epoxy equivalent 274 g/eq)
• Epoxy resin 5 o-cresol novolac type epoxy resin (epoxy equivalent: 200 g/eq)
• Epoxy resin 6 benzyl group-modified cresol novolac type epoxy resin (epoxy equivalent: 264 g/eq)
• Hardener 1 Active ester compound, DIC Corporation, product name "EXB-8"
• Hardener 2 Melamine modified phenolic resin (hydroxyl equivalent: 120 g/eq)
• Curing accelerator an adduct of tributylphosphine and 1,4
• 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.
• a dispersion medium water
• LA920 laser diffraction scattering particle size distribution measuring device
• the molding resin composition was 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 piece 2 was measured by an autograph (flexural tester AG-500, manufactured by Shimadzu Corporation). The results are shown in Table 1.
• the molding resin composition was charged into a transfer molding machine, molded under the conditions of a mold temperature of 180°C, molding pressure of 6.9 MPa, and curing time of 120 seconds, and post-cured at 175°C for 6 hours to obtain a rod-shaped cured product (length 90 mm, width 0.6 mm, thickness 0.8 mm).
• the cured product was used as a test piece, and the relative dielectric constant (Dk) and dielectric loss tangent (Df) were measured at 25 ⁇ 3°C and 5 GHz (model CP511) using a cavity resonator (Kanto Electronics Application Development Co., Ltd.) and a network analyzer (Keysight Technologies, product name "PNA E8364B"). The results are shown in Table 1.
• Epoxy resins 1 to 6 were used as the epoxy resins, curing agent 1 was used as the curing agent, and the above curing accelerator was used as the phosphorus catalyst. Using these epoxy resins, curing agents, and curing accelerators, the unreacted epoxy ratio was measured according to the above-mentioned procedure. The results are shown in Table 2.
• the cured product of the molding resin composition of Example 1 which used an active ester compound as a curing agent, has a low dielectric tangent equivalent to the cured products of the molding resin compositions of Comparative Examples 1 and 2, and also exhibits a higher bending strength. Furthermore, as is clear from the evaluation results in Table 1, the cured product of the molding resin composition of Example 2, in which an active ester compound and a phenolic resin were used in combination as a curing agent, has a lower dielectric tangent and exhibits higher bending strength than the cured products of the molding resin compositions of Comparative Examples 3 and 4.
• the molding resin compositions of Comparative Examples 5 and 6 have a slightly smaller amount of filler than the molding resin compositions of Example 2 and Comparative Examples 3 and 4, but other components, except for the type of epoxy resin, are roughly the same as those of the molding resin compositions of Example 2 and Comparative Examples 3 and 4.
• the cured product of the molding resin composition of Example 2 which uses an active ester compound and a phenolic resin in combination as a curing agent, has a lower dielectric tangent and exhibits higher bending strength than the cured products of the molding resin compositions of Comparative Examples 5 and 6.
• a specific novolac type epoxy resin as a curing agent, it is possible to form a cured product that exhibits a low dielectric tangent and excellent strength.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Epoxy Resins (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=91195696

Family Applications (1)

Country Status (5)

Citations (9)

Family Cites Families (2)

• 2023
  • 2023-11-21 KR KR1020257016844A patent/KR20250112775A/ko active Pending
  • 2023-11-21 WO PCT/JP2023/041787 patent/WO2024111575A1/ja not_active Ceased
  • 2023-11-21 JP JP2024560158A patent/JPWO2024111575A1/ja active Pending
  • 2023-11-21 TW TW112145000A patent/TW202436504A/zh unknown
  • 2023-11-21 CN CN202380037407.9A patent/CN119677792A/zh active Pending

Patent Citations (10)

Also Published As

Similar Documents

Legal Events