WO2022124405A1

WO2022124405A1 - Resin composition for molding and high frequency device

Info

Publication number: WO2022124405A1
Application number: PCT/JP2021/045636
Authority: WO
Inventors: 格山浦; 道俊荒田; 貴大齋藤
Original assignee: 昭和電工マテリアルズ株式会社
Priority date: 2020-12-11
Filing date: 2021-12-10
Publication date: 2022-06-16
Also published as: JPWO2022124405A1; TW202229394A

Abstract

A resin composition for molding, said resin composition containing an epoxy resin, a curing agent that contains an active ester compound, and a first inorganic filler that has a relative dielectric constant of 8 or more at 10 GHz.

Description

Molding resin compositions and high frequency devices

The present disclosure relates to a molding resin composition and a high frequency device.

In recent years, with the demand for higher functionality, lighter weight, shorter length, and smaller electronic devices, high-density integration of electronic components and high-density mounting have progressed, and semiconductor packages used in these electronic devices have been conventionally used. The size is increasing, and the size is getting smaller and smaller. Furthermore, the frequency of radio waves used for communication of electronic devices is increasing.

A high dielectric constant epoxy resin composition used for encapsulating a semiconductor element has been proposed from the viewpoint of miniaturization of a semiconductor package and compatibility with high frequencies (see, for example, Patent Document 1).

JP-A-2015-36410

By the way, along with the miniaturization and high functionality of the semiconductor package (PKG), the development of the antenna-in-package (AiP), which is a PKG having an antenna function, is also underway. By using a material having a high relative permittivity as the sealing material for sealing the antenna, it is possible to reduce the size of the AiP, while the material having a high relative permittivity generally has a high dielectric loss tangent.

The amount of transmission loss generated by heat conversion of radio waves transmitted for communication in a dielectric is expressed as the product of the square root of frequency and relative permittivity and the dielectric loss tangent. That is, since the transmission signal easily changes to heat in proportion to the frequency, a sealing material having a lower dielectric loss tangent is required in the high frequency band in order to suppress the transmission loss.

For example, in AiP, the radio wave used for communication is increased in frequency in order to cope with the increase in the number of channels due to the diversification of information, and the sealing material has a high relative permittivity and a low dielectric loss tangent. It is required to be compatible with.

The present disclosure provides a molding resin composition capable of producing a cured product capable of achieving both a high relative permittivity and a low dielectric loss tangent, and a high frequency device having a cured product obtained by curing this composition. Make it an issue.

Specific means for solving the above-mentioned problems include the following aspects.
<1> A molding resin composition containing an epoxy resin, a curing agent containing an active ester compound, and a first inorganic filler which is an inorganic filler having a relative permittivity of 8 or more at 10 GHz.
<2> The molding resin composition according to <1>, wherein the first inorganic filler contains a titanium-based inorganic filler containing a titanium element.
<3> The molding resin composition according to <1> or <2>, which further contains a second inorganic filler which is an inorganic filler having a relative permittivity of less than 8 at 10 GHz.
<4> The molding resin according to <3>, wherein the content of the first inorganic filler is 40% by mass or more with respect to the total of the first inorganic filler and the second inorganic filler. Composition.
<5> The ratio of the average particle size of the first inorganic filler to the average particle size of the second inorganic filler (first inorganic filler / second inorganic filler) is 0.5 to 20. The molding resin composition according to <3> or <4>.
<6> The molding resin composition according to any one of <3> to <5>, wherein the second inorganic filler contains at least one selected from the group consisting of silica particles and alumina particles.
<7> The molding resin composition according to any one of <1> to <6>, wherein the average particle size of the first inorganic filler is 0.5 μm to 30 μm.
<8> Any of <1> to <7>, wherein the first inorganic filler contains at least one titanium-based inorganic filler selected from the group consisting of barium titanate, calcium titanate, and strontium titanate. The molding resin composition according to one.
<9> A molding resin composition containing an epoxy resin, a curing agent containing an active ester compound, and a first inorganic filler which is a titanium-based inorganic filler containing a titanium element.
<10> The molding resin composition according to any one of <1> to <9> for use in producing the cured product in a high-frequency device having an antenna and a cured product of the resin composition.
<11> A high frequency device comprising an antenna and a cured product of the molding resin composition according to any one of <1> to <10>.

According to the present disclosure, there are provided a molding resin composition capable of producing a cured product capable of achieving both a high relative permittivity and a low dielectric loss tangent, and a high frequency device having a cured product obtained by curing the composition. be able to.

In the present disclosure, the term "process" includes, in addition to a process independent of other processes, the process as long as the purpose of the process is achieved even if it cannot be clearly distinguished from the other process. ..
In the present disclosure, the numerical range indicated by using "-" includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, each component may contain a plurality of applicable substances. When a plurality of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, a plurality of types of particles corresponding to each component may be contained. When a plurality of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the plurality of particles present in the composition, unless otherwise specified.

<Plastic composition for molding>
The molding resin composition of the present disclosure contains an epoxy resin, a curing agent containing an active ester compound, and a first inorganic filler which is an inorganic filler having a relative permittivity of 8 or more at 10 GHz. The molding resin composition of the present disclosure contains an active ester compound which is a curing agent for an epoxy resin and a first inorganic filler, so that a high specific dielectric constant and a low dielectric loss tangent can be achieved at the same time. Can manufacture things. Further, the molding resin composition of the present disclosure is used for producing a resin molded product by using various molding methods such as a low pressure transfer molding method, an injection molding method, and a compression molding method. The molding resin composition of the present disclosure may be a composition used for sealing a member such as an antenna.

Conventionally, a phenol curing agent, an amine curing agent, or the like is generally used as a curing agent for an epoxy resin, but a secondary hydroxyl group is generated in the reaction between the epoxy resin and the phenol curing agent or the amine curing agent. On the other hand, in the reaction between the epoxy resin and the active ester compound, an ester group is generated instead of the secondary hydroxyl group. Since the ester group has a lower polarity than the secondary hydroxyl group, the molding resin composition of the present disclosure is a cured product as compared with a molding resin composition containing only a curing agent that generates a secondary hydroxyl group as a curing agent. It is considered that the dielectric positive contact of the resin can be kept low.

Hereinafter, each component constituting the molding resin composition will be described. The molding resin composition of the present embodiment contains an epoxy resin, a curing agent containing an active ester compound, and a first inorganic filler, and may contain other components as necessary.

(Epoxy resin)
The type of epoxy resin is not particularly limited as long as it has an epoxy group in the molecule.

Specifically, the epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A and bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene. A novolak type epoxy resin (phenol novolak type) which is an epoxidation of a novolak resin obtained by condensing or cocondensing a kind of phenolic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst. Epoxide resin, orthocresol novolak type epoxy resin, etc.); A triphenylmethane type phenol resin obtained by condensing or cocondensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst. Triphenylmethane type epoxide resin; a copolymerized epoxy resin obtained by epoxidizing a novolak resin obtained by cocondensing the above phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst; bisphenol. Diphenylmethane type epoxy resin which is a diglycidyl ether such as A and bisphenol F; biphenyl type epoxy resin which is an alkyl-substituted or unsubstituted biphenol diglycidyl ether; stillben type epoxy resin which is a diglycidyl ether of a stilben-based phenol compound; bisphenol Sulfur atom-containing epoxy resin that is a diglycidyl ether such as S; epoxy resin that is an alcoholic glycidyl ether such as butanediol, polyethylene glycol, polypropylene glycol; and a polyvalent carboxylic acid compound such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid. Glysidyl ester type epoxy resin, which is a glycidyl ester; glycidylamine type epoxy resin, which is obtained by substituting an active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethane, or isocyanuric acid with a glycidyl group; Dicyclopentadiene-type epoxy resin, which is an epoxide of a condensed resin; vinylcyclohexene epoxide, which is an epoxide of an olefin bond in a molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxide) cyclohexyl-5,5 An alicyclic epoxy resin such as 5-spiro (3,4-epoxy) cyclohexane-m-dioxane; a paraxylylene-modified epoxy resin that is a glycidyl ether of a paraxylylene-modified phenol formaldehyde; a metaxylylene-modified epoxy resin that is a glycidyl ether of a metaxylylene-modified phenol resin. A terpene-modified epoxy resin that is a glycidyl ether of a terpene-modified phenol form; a dicyclopentadiene-modified epoxy resin that is a glycidyl ether of a dicyclopentadiene-modified phenol resin; a cyclopentadiene-modified epoxy resin that is a glycidyl ether of a cyclopentadiene-modified phenol resin; Polycyclic aromatic ring-modified epoxy resin, which is a glycidyl ether of a ring-fragrant ring-modified phenol resin; naphthalene-type epoxy resin, which is a glycidyl ether of a naphthalene ring-containing phenol resin; Type epoxy resin; A linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid; an aralkyl-type phenol resin such as a phenol aralkyl resin, a biphenyl aralkyl resin, or a naphthol aralkyl resin is epoxidized. Phenol formaldehyde resin; etc. may be mentioned. Further, an epoxy resin such as an acrylic resin can also be mentioned as an epoxy resin. These epoxy resins may be used alone or in combination of two or more.
From the viewpoint of heat resistance, the epoxy resin preferably contains a triphenylmethane type epoxy resin.
The epoxy resin may contain a triphenylmethane type epoxy resin and a biphenyl type epoxy resin, and may contain a biphenyl aralkyl type epoxy resin and a biphenyl type epoxy resin.

The epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of balance of various characteristics such as moldability, heat resistance and electrical reliability, it 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 shall be a value measured by a method according to JIS K 7236: 2009.

When the epoxy resin is a solid, its softening point or melting point is not particularly limited. From the viewpoint of moldability and heat resistance, the temperature is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability when preparing the molding resin composition, the temperature is more preferably 50 ° C. to 130 ° C.

The melting point or softening point of the epoxy resin shall be a value measured by differential scanning calorimetry (DSC) or a method according to JIS K 7234: 1986 (ring ball method).

The content of the epoxy resin in the molding resin composition is preferably 0.5% by mass to 30% by mass, preferably 2% by mass to 20% by mass, from the viewpoints of strength, fluidity, heat resistance, moldability, and the like. Is more preferable, and 3% by mass to 10% by mass is further preferable.

(Hardener)
The molding resin composition contains a curing agent containing an active ester compound. The molding resin composition may contain a curing agent other than the active ester compound, and may not contain a curing agent other than the active ester compound. The active ester compound may be used alone or in combination of two or more.

The type of the active ester compound is not particularly limited as long as it is a compound having one or more ester groups in the molecule that react with the epoxy group. A phenol curing agent, an amine curing agent, or the like is generally used as the curing agent for the epoxy resin, but a secondary hydroxyl group is generated in the reaction between the epoxy resin and the phenol curing agent or the amine curing agent. On the other hand, in the reaction between the epoxy resin and the active ester compound, an ester group is generated instead of the secondary hydroxyl group. Since the ester group has a lower polarity than the secondary hydroxyl group, there is a tendency that the dielectric loss tangent of the cured product can be reduced by using the active ester compound as the curing agent.

Examples of the active ester compound include phenol ester compounds, thiophenol ester compounds, N-hydroxyamine ester compounds, and esterified products of heterocyclic hydroxy compounds. The active ester compound may be used alone or in combination of two or more.

Examples of the active ester compound 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 containing an aliphatic compound as a component of polycondensation tend to have excellent compatibility with an epoxy resin due to having an aliphatic chain. Ester compounds containing an aromatic compound as a component of polycondensation tend to have excellent heat resistance due to having an aromatic ring.

Specific examples of the active ester compound include aromatic esters obtained by a condensation reaction between an aromatic carboxylic acid and a phenolic hydroxyl group. Among them, an aromatic carboxylic acid component in which 2 to 4 hydrogen atoms of an aromatic ring such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, and diphenylsulfonic acid are substituted with a carboxy group, and the hydrogen atom of the above-mentioned aromatic ring. Aromatic carboxylic acid and a phenolic hydroxyl group are prepared from a mixture of a monovalent phenol in which one of the above is substituted with a hydroxyl group and a polyhydric phenol in which 2 to 4 hydrogen atoms of the aromatic ring are substituted with a hydroxyl group. Aromatic esters obtained by the condensation reaction are preferred. That is, an aromatic ester having a structural unit derived from the aromatic carboxylic acid component, a structural unit derived from the monovalent phenol, and a structural unit derived from the polyhydric phenol is preferable.

Specific examples of the active ester compound include a phenol resin having a molecular structure in which a phenol compound is knotted via an aliphatic cyclic hydrocarbon group described in JP2012-246367, and an aromatic dicarboxylic acid or Examples thereof include an active ester resin having a structure obtained by reacting the halide with an aromatic monohydroxy compound. As the active ester resin, a compound represented by the following structural formula (1) is preferable.

In the structural formula (1), R ¹ is an alkyl group having 1 to 4 carbon atoms, and X is a benzene ring, a 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, and n represents the average number of repetitions. It is 25 to 1.5.

Specific examples of the compound represented by the structural formula (1) include the following exemplary compounds (1-1) to (1-10). T-Bu in the structural formula is a tert-butyl group.

As another specific example of the active ester compound, the compound represented by the following structural formula (2) and the compound represented by the following structural formula (3) described in JP-A-2014-114352 can be used. Can be mentioned.

In the structural formula (2), R ¹ and R ² are independently hydrogen atoms, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and Z is a benzoyl group, a naphthoyl group, or a carbon. An ester-forming structural site (z1) or hydrogen atom (z2) selected from the group consisting of a benzoyl group or a naphthoyl group substituted with an alkyl group of the number 1 to 4 and an acyl group having 2 to 6 carbon atoms, and Z. At least one of them is an ester-forming structural site (z1).

In the structural formula (3), R ¹ and R ² are independently hydrogen atoms, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and Z is a benzoyl group, a naphthoyl group, or a carbon. An ester-forming structural site (z1) or hydrogen atom (z2) selected from the group consisting of a benzoyl group or a naphthoyl group substituted with an alkyl group of the number 1 to 4 and an acyl group having 2 to 6 carbon atoms, and Z. At least one of them is an ester-forming structural site (z1).

Specific examples of the compound represented by the structural formula (2) include the following exemplary compounds (2-1) to (2-6).

Specific examples of the compound represented by the structural formula (3) include the following exemplary compounds (3-1) to (3-6).

As the active ester compound, a commercially available product may be used. Commercially available active ester compounds include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (manufactured by DIC Co., Ltd.) as active ester compounds containing a dicyclopentadiene-type diphenol structure; aromatics. "EXB9416-70BK", "EXB-8", "EXB-9425" (manufactured by DIC Co., Ltd.) as an active ester compound containing a structure; "DC808" (Mitsubishi Chemical Co., Ltd.) as an active ester compound containing an acetylated product of phenol novolac. (Manufactured); Examples of the active ester compound containing a benzoylated product of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.).

The ester group equivalent of the active ester compound is not particularly limited. From the viewpoint of balance of various characteristics such as moldability, heat resistance, and electrical reliability, 150 g / eq to 400 g / eq is preferable, 170 g / eq to 300 g / eq is more preferable, and 200 g / eq to 250 g / eq is further preferable. preferable.
The ester group equivalent of the active ester compound shall be a value measured by a method according to JIS K 0070: 1992.

When the curing agent contains a curing agent other than the active ester compound (hereinafter, also referred to as "other curing agent"), the other curing agents include a phenol curing agent, an amine curing agent, and an acid anhydride curing agent. , Polymercaptan curing agent, polyaminoamide curing agent, isocyanate curing agent, blocked isocyanate curing agent and the like. These curing agents may be used alone or in combination of two or more.

When the curing agent contains other curing agents, the curing agent may contain a phenol curing agent from the viewpoint of suppressing the dielectric loss tangent of the cured product to a low level and from the viewpoint of moldability.

Specific examples of the phenolic curing agent include polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol. , At least one phenolic compound selected from the group consisting of phenolic compounds such as aminophenol and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene, and aldehyde compounds such as formaldehyde, acetaldehyde and propionaldehyde are acid catalysts. Novorak-type phenolic resin obtained by condensing or co-condensing underneath; Phenolic aralkyl resin synthesized from the above phenolic compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, etc., aralkyl-type phenolic resin such as naphthol aralkyl resin. Paraxylylene-modified phenolic resin, methaxylylene-modified phenolic resin; Melamine-modified phenolic resin; Terpen-modified phenolic resin; Dicyclopentadiene-type phenolic resin and dicyclopentadiene-type naphthol synthesized by copolymerization of the above phenolic compound with dicyclopentadiene. Resin; Cyclopentadiene-modified phenolic resin; Polycyclic aromatic ring-modified phenolic resin; Biphenyl-type phenolic resin; Obtained by condensing or co-condensing the above phenolic compound with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst. Triphenylmethane-type phenolic resins; examples thereof include phenolic resins obtained by copolymerizing two or more of these. These phenol curing agents may be used alone or in combination of two or more.

The functional group equivalents of other curing agents (for example, hydroxyl group equivalents in the case of phenol curing agents) are not particularly limited. From the viewpoint of the balance of various characteristics such as moldability, heat resistance, and electrical reliability, it is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.
The functional group equivalent of other curing agents (for example, the hydroxyl group equivalent in the case of a phenol curing agent) shall be a value measured by a method according to JIS K 0070: 1992.

When the curing agent is a solid, its softening point or melting point is not particularly limited. From the viewpoint of moldability and heat resistance, it is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability at the time of manufacturing the molding resin composition, it is more preferably 50 ° C. to 130 ° C.

The melting point or softening point of the curing agent shall be a value measured in the same manner as the melting point or softening point of the epoxy resin.

The equivalent ratio of the epoxy resin to the curing agent, that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (the number of functional groups in the curing agent / the number of functional groups in the epoxy resin) is not particularly limited. From the viewpoint of suppressing each unreacted component to a small amount, it is preferably set in the range of 0.5 to 2.0, and more preferably set in the range of 0.6 to 1.3. From the viewpoint of moldability and heat resistance, it is more preferable to set it in the range of 0.8 to 1.2.

When the curing agent contains an active ester compound, the content of the active ester compound with respect to the total mass of the curing agent is preferably 80% by mass or more, preferably 85% by mass or more, from the viewpoint of keeping the dielectric adjacency of the cured product low. It is more preferably present, and further preferably 90% by mass or more.

(Curing accelerator)
The molding resin composition may contain a curing accelerator. The type of the curing accelerator is not particularly limited, and can be selected according to the type of the epoxy resin or the curing agent, the desired characteristics of the molding resin composition, and the like.

Examples of the curing accelerator include diazabicycloalkene such as 1,5-diazabicyclo [4.3.0] nonen-5 (DBN) and 1,8-diazabicyclo [5.4.0] undecene-7 (DBU). Cyclic amidin compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidin compound; phenol novolac salts of the cyclic amidin compound or its derivatives; these. Maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1 , 4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and other quinone compounds, and diazophenylmethane and other quinone compounds with π-bonded compounds have an intramolecular polarization. Compounds; Cyclic amidinium compounds such as DBU tetraphenylborate salt, DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N-methylmorpholin tetraphenylborate salt and isocyanate are added. Compounds; DBU isocyanate adduct, DBN isocyanate adduct, 2-ethyl-4-methylimidazole isocyanate adduct, N-methylmorpholin isocyanate adduct; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanol Tertiary amine compounds such as amines, dimethylaminoethanol, tris (dimethylaminomethyl) phenols; derivatives of the tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, benzo Ammonium salt compounds such as tetra-n-hexylammonium acid and tetrapropylammonium hydroxide; first phosphine such as ethylphosphine and phenylphosphine, second phosphine such as dimethylphosphine and diphenylphosphine, triphenylphosphine, diphenyl (p-tolyl). ) Phosphin, Tris (alkylphenyl) phosphin, Tris (alkoxyphenyl) phosphin, Tris (alkyl / alkoxyphenyl) phosphin, Tris (dialkylphenyl) phosphin, Tris (trialkylphenyl) phosphin, Tris (Tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, tris (benzyl) ) Organic phosphine such as tertiary phosphine such as phosphine; phosphine compound such as a complex of the organic phosphine and organic borons; the organic phosphine or the phosphine compound and maleic anhydride, 1,4-benzoquinone, 2,5-. Truquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, A quinone compound such as phenyl-1,4-benzoquinone or anthraquinone, a compound having intramolecular polarization by adding a compound having a π bond such as diazophenylmethane; the organic phosphine or the phosphine compound and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodide phenol, 3-iodide phenol, 2-iodide phenol, 4-bromo-2-methyl Phenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro After reacting with a halogenated phenol compound such as -1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl, the process of dehalogenation is performed. Obtained compounds having intramolecular polarization; tetra-substituted phosphoniums such as tetraphenylphosphonium, tetra-phenylborate salts of tetra-substituted phosphoniums such as tetra-p-tolylbolate, salts of tetra-substituted phosphoniums and phenolic compounds, etc. , Tetra-substituted phosphonium compounds; salts of tetraalkylphosphoniums and partial hydrolysates of aromatic carboxylic acid anhydrides; phosphobetaine compounds; adducts of phosphonium compounds and silane compounds; and the like.
The curing accelerator may be used alone or in combination of two or more.
Among these, 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. Things etc. can be mentioned.

When the molding resin composition contains a curing accelerator, the amount thereof is preferably 0.1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin component (total amount of the epoxy resin and the curing agent). It is more preferably 1 part by mass to 15 parts by mass. When the amount of the curing accelerator is 0.1 part by mass or more with respect to 100 parts by mass of the resin component, it tends to cure well in a short time. When the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, the curing rate is not too fast and a good molded product tends to be obtained.

(First inorganic filler)
The molding resin composition contains a first inorganic filler which is an inorganic filler having a relative permittivity of 8 or more at 10 GHz. The first inorganic filler may be used alone or in combination of two or more. The first inorganic filler preferably has a relative permittivity of 8 to 100 at 10 GHz, and more preferably 10 to 100.

The first inorganic filler preferably contains a titanium-based inorganic filler containing a titanium element from the viewpoint of high dielectric constant. Examples of the titanium-based inorganic filler include barium titanate, calcium titanate, strontium titanate, zinc zirconate titanate, and titanium oxide. Of these, barium titanate, calcium titanate and strontium titanate are preferred. Of these, barium titanate is preferable from the viewpoint of high sphericity and high fluidity.

The average particle size of the first inorganic filler is preferably 0.1 m to 100 μm, more preferably 0.5 μm to 30 μm, further preferably 1.0 μm to 20 μm, and even more preferably 3.0 μm to 3.0 μm. It is particularly preferably 10 μm.

The average particle size of the first inorganic filler can be measured as follows. The molding resin composition is placed in a crucible and left at 800 ° C. for 4 hours to incinerate. The particle size distribution of ash obtained by using a laser diffraction / scattering type particle size distribution measuring device (for example, Horiba Seisakusho Co., Ltd., LA920) was obtained, and the average particle size of the inorganic filler was used as the volume average particle size (D50) from the particle size distribution. The particle size can be determined.

The shape of the first inorganic filler is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, and an amorphous shape. Further, the first inorganic filler may be crushed.

In the present disclosure, the relative permittivity of the inorganic filler at 10 GHz is a value measured by the following method.
100 parts by mass of epoxy resin (biphenyl aralkyl type epoxy resin, epoxy equivalent 274 g / eq), 74.8 parts by mass of phenol curing agent (phenol aralkyl resin, hydroxyl group equivalent 205 g / eq) and 1,4-benzoquinone adduct of triphenylphosphine Two parts by mass of the resin composition, the inorganic filler, and the methyl ethyl ketone (MEK) are mixed, and the above-mentioned resin composition is dissolved in MEK to prepare a varnish (75% by mass of the total of the resin composition and the inorganic filler). .. At this time, varnishes having an inorganic filler content of 10% by volume, 20% by volume, and 30% by volume with respect to the solid content excluding the solvent are prepared, respectively.
The obtained varnish was applied onto the substrate, the substrate was dried under the conditions of 100 ° C. for 10 minutes, and then the resin film was peeled off from the substrate. The obtained resin film is molded by compression molding under the conditions of a mold temperature of 175 ° C., a molding pressure of 6.9 MPa, and a curing time of 600 seconds to obtain a cured product for measurement. The relative permittivity at 10 GHz in each of the obtained cured products for measurement is measured, and a graph is created in which the content of the inorganic filler is plotted on the horizontal axis and the measured value of the relative permittivity is plotted on the vertical axis. From the obtained graph, a linear approximation is performed by the least squares method, and the relative permittivity when the content of the inorganic filler is 100% by volume is obtained by extrapolation and used as "the relative permittivity of the entire inorganic filler".

(Second inorganic filler)
The molding resin composition may further contain a second inorganic filler, which is an inorganic filler having a relative permittivity of less than 8 at 10 GHz. The second inorganic filler may have a relative permittivity of 4 or less at 10 GHz.
In the second inorganic filler, the lower limit of the relative permittivity at 10 GHz is not particularly limited, and may be, for example, 2 or more, or 6 or more.

The type of the second inorganic filler is not particularly limited. Specific examples thereof include inorganic materials such as fused silica, crystalline silica, glass, alumina, talc, clay and mica. As the second inorganic filler, an inorganic filler having a flame-retardant effect may be used. Examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, a composite metal hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate.

Among the second inorganic fillers, silica such as molten silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity. The second inorganic filler may be used alone or in combination of two or more. Examples of the form of the second inorganic filler include powder, beads obtained by spheroidizing the powder, fibers and the like.

The average particle size of the second inorganic filler is preferably 0.1 μm to 50 μm, more preferably 0.5 μm to 30 μm.
The average particle size of the second inorganic filler can be measured by the same method as that of the first inorganic filler described above.

The second inorganic filler may contain two or more kinds of inorganic fillers having different average particle sizes from the viewpoint of fluidity. For example, the second inorganic filler may contain an inorganic filler having an average particle size of 0.1 μm to 5 μm and an inorganic filler having an average particle size of 10 μm to 50 μm.

The content of the inorganic filler contained in the molding resin composition is not particularly limited, and is preferably 50% by mass to 95% by mass of the entire molding resin composition from the viewpoint of fluidity and strength. It is more preferably 60% by mass to 95% by mass, and even more preferably 70% by mass to 90% by mass. When the content of the inorganic filler is 50% by mass or more of the entire molding resin composition, the properties such as the relative permittivity, the coefficient of thermal expansion, the thermal conductivity, and the elastic modulus of the cured product tend to be further improved. When the content of the inorganic filler is 95% by mass or less of the entire molding resin composition, an increase in the viscosity of the molding resin composition is suppressed, the fluidity is further improved, and the moldability tends to be better. It is in.
The "inorganic filler" in the content of the inorganic filler contained in the molding resin composition and the inorganic filler described below mean the total of the first inorganic filler and the second inorganic filler. However, when the molding resin composition does not contain the second inorganic filler, the "inorganic filler" means the first inorganic filler.

In the molding resin composition, the content of the first inorganic filler is 40 mass by mass with respect to the total of the first inorganic filler and the second inorganic filler from the viewpoint of the relative permittivity of the cured product. % Or more, more preferably 55% by mass or more, and even more preferably 70% by mass or more. The content of the first inorganic filler may be 95% by mass or less with respect to the total of the first inorganic filler and the second inorganic filler.

In the molding resin composition, the ratio of the average particle size of the first inorganic filler to the average particle size of the second inorganic filler (first inorganic filler / second inorganic filler) is fluidity. From the viewpoint of moldability, the content is preferably 0.5 to 20, and more preferably 1 to 10.

In addition to the above-mentioned components, the molding resin composition may contain various additives such as a coupling agent, an ion exchanger, a mold release agent, a flame retardant, a colorant, and a stress relaxation agent exemplified below. The molding resin composition may contain various additives well known in the art, if necessary, in addition to the additives exemplified below.

(Coupling agent)
The molding resin composition may contain a coupling agent. From the viewpoint of enhancing the adhesiveness between the resin component and the inorganic filler, the molding resin composition preferably contains a coupling agent. Examples of the coupling agent include known coupling agents such as silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane and disilazane, titanium compounds, aluminum chelate compounds and aluminum / zirconium compounds. Can be mentioned.

When the molding resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass, and 0.1 parts by mass to 5 parts by mass with respect to 100 parts by mass of the inorganic filler. More preferably, it is 2.5 parts by mass. When the amount of the coupling agent is 0.05 parts by mass or more with respect to 100 parts by mass of the inorganic filler, the adhesiveness with the frame tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.

(Ion exchanger)
The molding resin composition may contain an ion exchanger. From the viewpoint of improving the moisture resistance and high temperature standing characteristics of the high frequency device including the cured product of the molding resin composition, it is preferable to include an ion exchanger. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples thereof include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. As the ion exchanger, one type may be used alone or two or more types may be used in combination. Of these, hydrotalcite represented by the following general formula (A) is preferable.

Mg _(1-X) Al _X (OH) ₂ (CO ₃ ) _{X / 2}・ mH ₂ O …… (A)
(0 <X≤0.5, m is a positive number)

When the molding resin composition contains an ion exchanger, the content thereof is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions. For example, it is preferably 0.1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).

(Release agent)
The molding resin composition may contain a mold release agent from the viewpoint of obtaining good mold release property from the mold at the time of molding. The release agent is not particularly limited, and conventionally known release agents can be used. Specific examples thereof include higher fatty acids such as carnauba wax, montanic acid and stearic acid, ester waxes such as higher fatty acid metal salts and montanic acid esters, and polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene. As the release agent, one type may be used alone or two or more types may be used in combination.

When the molding resin composition contains a mold release agent, the amount thereof is preferably 0.01 part by mass to 10 parts by mass, preferably 0.1 part by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent). 5 parts by mass is more preferable. When the amount of the mold release agent is 0.01 part by mass or more with respect to 100 parts by mass of the resin component, the mold release property tends to be sufficiently obtained. When it is 10 parts by mass or less, better adhesiveness tends to be obtained.

(Flame retardants)
The molding resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known flame retardants can be used. Specific examples thereof include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides and the like. The flame retardant may be used alone or in combination of two or more.

When the molding resin composition contains a flame retardant, the amount thereof is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect. For example, it is preferably 1 part by mass to 30 parts by mass, and more preferably 2 parts by mass to 20 parts by mass with respect to 100 parts by mass (total amount of epoxy resin and curing agent) of the resin component.

(Colorant)
The molding resin composition may contain a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, lead tan, and red iron oxide. The content of the colorant can be appropriately selected according to the purpose and the like. As the colorant, one type may be used alone or two or more types may be used in combination.

(Stress relaxation agent)
The molding resin composition may contain 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. Examples of the stress relaxation agent include commonly used known stress relaxation agents (flexible agents). Specifically, thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), and acrylic. Rubber particles such as rubber, urethane rubber, silicone powder, core-shell such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer, etc. Examples include rubber particles having a structure. As the stress relaxation agent, one type may be used alone or two or more types may be used in combination.

Among the stress relaxation agents, silicone-based stress relaxation agents are preferable. Examples of the silicone-based stress relieving agent include those having an epoxy group, those having an amino group, those obtained by modifying these with a polyether, and the like, and silicone compounds such as a silicone compound having an epoxy group and a polyether silicone compound are more suitable. preferable. Of these, a polyether silicone compound is preferable from the viewpoint of reducing the dielectric loss tangent of the cured product and suppressing the appearance deterioration of the cured product.

The polyether-based silicone compound is not particularly limited as long as it is a compound in which a polyether group is introduced into silicone, which is a polymer compound having a main skeleton due to a siloxane bond. As the polyether silicone compound, one type may be used alone or two or more types may be used in combination.
The polyether-based silicone compound may be a side chain-modified type polyether-based silicone compound or a terminal-modified type polyether-based silicone compound. Among these, the polyether-based silicone compound is preferably a side chain-modified type polyether-based silicone compound from the viewpoint of suppressing the appearance deterioration of the cured product.

An example of a polyether-based silicone compound is an epoxy-polyester-based silicone compound. The epoxy-polyether-based silicone compound is not particularly limited as long as it is a compound in which a polyether group and an epoxy group are introduced into silicone, which is a polymer compound having a main skeleton due to a siloxane bond.
The epoxy / polyether silicone compound may be a side chain modified epoxy / polyether silicone compound, a terminal modified epoxy / polyether silicone compound, and a side chain and a terminal modified epoxy. It may be a polyether silicone compound. Polydimethylsiloxane is preferable as the main skeleton of the epoxy / polyether silicone compound. As the polyether group, a polyether group obtained by polymerizing one or both of ethylene oxide and propylene oxide is preferable.
The epoxy-polyether-based silicone compound is a side in which a polyether group (preferably a polyether group in which one or both of ethylene oxide and propylene oxide are polymerized) and an epoxy group are present in the side chain of silicone (preferably polydimethylsiloxane). It is preferably a chain-modified epoxy / polyether silicone compound.

When the molding resin composition contains a stress relieving agent, the amount thereof is preferably, for example, 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin component (total amount of the epoxy resin and the curing agent). It is more preferably 2 parts by mass to 20 parts by mass.

<Modification example of resin composition for molding>
Modifications of the molding resin composition of the present disclosure include an epoxy resin, a curing agent containing an active ester compound, and a first inorganic filler which is a titanium-based inorganic filler containing a titanium element. In this modification, a cured product having both a high relative permittivity and a low dielectric loss tangent is obtained by containing an active ester compound which is a curing agent for an epoxy resin and a titanium-based inorganic filler containing a titanium element. Can be manufactured.
The preferred forms of the epoxy resin and the active ester compound used in this modification are the same as the preferred forms of the epoxy resin and the active ester compound used in the above-mentioned molding resin composition of the present disclosure. Further, the preferred form of the modified example of the molding resin composition of the present disclosure is the same as that of the above-mentioned molding resin composition of the present disclosure.

The titanium-based inorganic filler containing the titanium element used in this modification preferably has a relative permittivity of 8 or more at 10 GHz, and more preferably has a relative permittivity of 8 to 100 at 10 GHz. It is more preferable that the relative permittivity at 10 GHz is 10 to 100. A preferred form of the first inorganic filler, which is a titanium-based inorganic filler containing a titanium element used in the present modification, is the first inorganic filler used in the above-mentioned molding resin composition of the present disclosure. This is similar to the preferred form of the material.

(Preparation method of resin composition for molding)
The method for preparing the molding resin composition is not particularly limited. As a general method, a method of sufficiently mixing a predetermined blending amount of components with a mixer or the like, then melt-kneading with a mixing roll, an extruder or the like, cooling and pulverizing can be mentioned. More specifically, for example, a method in which a predetermined amount of the above-mentioned components is uniformly stirred and mixed, kneaded with a kneader, roll, extruder or the like preheated to 70 ° C. to 140 ° C., cooled and pulverized. Can be mentioned.

The molding resin composition is preferably solid at normal temperature and pressure (for example, 25 ° C. and atmospheric pressure). When the molding resin composition is a solid, the shape is not particularly limited, and examples thereof include powder, granules, and tablets. When the molding resin composition is in the shape of a tablet, it is preferable that the dimensions and mass are suitable for the molding conditions of the package from the viewpoint of handleability.

The molding resin composition is preferably used for producing the cured product in a high frequency device having an antenna and a cured product of the resin composition. The molding resin composition may be used for sealing electronic components in high frequency devices. The molding resin composition is preferably used for semiconductor package applications where both high relative permittivity and low dielectric loss tangent are required, and more preferably used for antenna-in-package, for example.

<High frequency device>
The high frequency device of the present disclosure comprises an antenna and a cured product of the molding resin composition of the present disclosure.

The high frequency device of the present disclosure is used, for example, when transmitting and receiving radio waves of 1 GHz or higher, and preferably used when transmitting and receiving radio waves of 3 GHz or higher. The high-frequency device of the present disclosure may have a structure in which the cured product of the molding resin composition of the present disclosure seals the antenna, and the antenna is arranged on the cured product of the molding resin composition of the present disclosure. It may have a structure that has been modified.

Hereinafter, the present invention will be specifically described with reference to Examples, but the scope of the present invention is not limited to these Examples.

<Preparation of resin composition for molding>
The components shown below were mixed in the blending ratio (unit: parts by mass) shown in Table 1 to prepare the molding resin compositions of Examples and Comparative Examples. This molding resin composition was a solid under normal temperature and pressure. Further, the blanks in Table 1 mean that they have not been mixed. The relative permittivity of the inorganic fillers 1 to 5 at 10 GHz is a value measured by the above-mentioned method.

Epoxy resin 1: Triphenylmethane type epoxy resin, epoxy equivalent 167 g / eq
-Epoxy resin 2: Biphenyl aralkyl type epoxy resin, epoxy equivalent 274 g / eq
-Epoxy resin 3: Biphenyl type epoxy resin, epoxy equivalent 192 g / eq
-Active ester compound: Active ester compound containing aromatic structure-Phenol curing agent: Phenolic aralkyl resin, hydroxyl group equivalent 205 g / eq
・ Curing accelerator: 1,4-benzoquinone adduct of triphenylphosphine ・ Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane ・ Release agent: montanic acid ester wax ・ Coloring agent: carbon black ・ Additive : Side chain modified epoxy / polyether modified silicone, viscosity (25 ° C): 1.50 Pa · s
Inorganic filler 1: Spherical barium titanate with a volume average particle size of 6.5 μm (relative permittivity at 10 GHz: 46.29)
Inorganic filler 2: Spherical alumina particles with a volume average particle size of 0.8 μm (relative permittivity at 10 GHz: 7.79)
Inorganic filler 3: Spherical alumina particles with a volume average particle size of 30 μm (relative permittivity at 10 GHz: 7.79)
Inorganic filler 4: Spherical silica particles with a volume average particle size of 0.7 μm (relative permittivity at 10 GHz: 3.61)
Inorganic filler 5: Spherical silica particles having a volume average particle size of 30 μm (relative permittivity at 10 GHz: 3.61)

(Liquidity: Spiral flow)
Using a mold for measuring spiral flow according to EMMI-1-66, the molding resin composition was molded under the conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and a flow distance (cm). ) Was asked. The results are shown in Table 1.

(Gel time)
The gel time of the molding resin composition at 175 ° C. was measured as follows. Specifically, 0.5 g of a sample of the resin composition for molding is placed on a hot plate heated to 175 ° C., and the sample is placed at a rotation speed of 20 rotations / minute to 25 rotations / minute using a jig. It was spread evenly in a circle of 0 cm to 2.5 cm. The time from when the sample was placed on the hot plate until the sample became less viscous and became a gel state and peeled off from the hot plate was measured, and this was measured as the gel time (seconds). The results are shown in Table 1.

(Relative permittivity and dielectric loss tangent)
The molding resin composition is molded with a hand press machine under the conditions of a mold temperature of 175 ° C., a molding pressure of 6.9 MPa, and a curing time of 600 seconds, and post-curing is performed at 175 ° C. for 6 hours to cut the plate-shaped cured product. (Length 50 mm, width 1 mm, thickness about 0.5 mm) were obtained. Using a plate-shaped cured product as a test piece, a permittivity measuring device (Agilent, product name "Network Analyzer N5227A") was used to measure the relative permittivity and dielectric loss tangent at 10 GHz at a temperature of 25 ± 3 ° C. ..
The results are shown in Table 1.

As shown in Table 1, when Example 1 and Comparative Example 1 in which the same epoxy resin is used and the composition of the inorganic filler is similar are compared, in Example 1, a high relative permittivity and a low dielectric loss tangent are compatible. It was found that a cured product was obtained.

The disclosure of Japanese patent application 2020-206092 filed December 11, 2020 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated by reference herein.

Claims

Epoxy resin and
A curing agent containing an active ester compound and
The first inorganic filler, which is an inorganic filler having a relative permittivity of 8 or more at 10 GHz,
A resin composition for molding containing.
The molding resin composition according to claim 1, wherein the first inorganic filler contains a titanium-based inorganic filler containing a titanium element.
The molding resin composition according to claim 1 or 2, further comprising a second inorganic filler which is an inorganic filler having a relative permittivity of less than 8 at 10 GHz.
The molding resin composition according to claim 3, wherein the content of the first inorganic filler is 40% by mass or more with respect to the total of the first inorganic filler and the second inorganic filler.
The ratio of the average particle size of the first inorganic filler to the average particle size of the second inorganic filler (first inorganic filler / second inorganic filler) is 0.5 to 20. Item 3. The molding resin composition according to claim 4.
The molding resin composition according to any one of claims 3 to 5, wherein the second inorganic filler contains at least one selected from the group consisting of silica particles and alumina particles.
The molding resin composition according to any one of claims 1 to 6, wherein the average particle size of the first inorganic filler is 0.5 μm to 30 μm.
The first inorganic filler is any one of claims 1 to 7, which contains at least one titanium-based inorganic filler selected from the group consisting of barium titanate, calcium titanate and strontium titanate. The molding resin composition according to.
Epoxy resin and
A curing agent containing an active ester compound and
The first inorganic filler, which is a titanium-based inorganic filler containing a titanium element,
A resin composition for molding containing.
The molding resin composition according to any one of claims 1 to 9, which is used for producing the cured product in a high-frequency device having an antenna and a cured product of the resin composition.
A high-frequency device having an antenna and a cured product of the molding resin composition according to any one of claims 1 to 10.