JP6766360B2 - Resin composition - Google Patents

Description

The present invention relates to resin compositions.

So far, various techniques have been studied as a sealing resin composition for sealing a semiconductor element. A curing agent is blended in the epoxy resin for the purpose of improving the adhesion to the lead frame. Examples of such a technique include those described in Patent Document 1. In this document, a chain polycarbodiimide compound having a cyanol group is used as a curing agent (crosslinking agent). It is described that this polycarbodiimide compound binds to an epoxy resin and is incorporated into a three-dimensional structure, and the isourea bond generated by the reaction improves the adhesion to the lead frame.

Further, in Patent Document 2, a chain-shaped polycarbodiimide compound having monocyanate introduced at the terminal is used as a curing agent. The document describes that a polycarbodiimide compound having an average molecular weight of 3 to 300,000 is used in order to improve the moisture resistance reliability of the protective film covering the semiconductor element.

Japanese Unexamined Patent Publication No. 2006-176549 JP-A-9-8181

As a result of the present inventor examining a resin composition containing a thermosetting resin, the following has been found.
(1) The chain-like polycarbodiimide compound described in the above document may compete with other curing agents. Therefore, it is difficult to stably obtain a cured product of a resin composition having low shrinkage.
(2) From the viewpoint of suppressing low shrinkage, if the crosslinked structure is made too dense, the elastic modulus of the cured product of the resin composition becomes high. That is, the present inventor has found that in a resin composition containing a thermosetting resin, low shrinkage and low elasticity are problems that have a trade-off relationship with each other.

As a result of further diligent research based on the above-mentioned new findings, the cyclic carbodiimide compound can be used as a curing accelerator, and by using the cyclic carbodiimide compound, low shrinkage can be stably obtained, and the above-mentioned It turned out that the trade-off relationship between the two could be improved.
As described above, the present inventor has found that a resin composition excellent in low shrinkage and low elasticity can be stably obtained, and has completed the present invention.

According to the present invention
Thermosetting resin and
Cyclic carbodiimide compounds and
Inorganic filler and
A resin composition containing a curing agent .
The thermosetting resin contains an epoxy resin and contains
The inorganic filler contains silica, and the content of the inorganic filler is 80% by mass or more and 95% by mass or less with respect to the entire resin composition.
The curing agent is one or more selected from the group consisting of a polyfunctional phenol resin, a modified phenol resin, a phenol aralkyl type phenol resin, and a bisphenol compound .
Provided is a resin composition used for electronic components, wherein the cured product obtained by heat-treating the resin composition at 175 ° C. for 120 seconds and then heat-treating at 175 ° C. for 4 hours has a glass transition temperature of 100 ° C. or higher.

According to the present invention, there is provided a resin composition used for an electronic component having excellent low shrinkage and low elasticity.

It is sectional drawing which shows an example of the electronic component which concerns on this embodiment. It is sectional drawing which shows an example of the manufacturing method of the electronic component which concerns on this embodiment. It is a figure which shows the relationship between the molding shrinkage rate (%) and the thermal elastic modulus (MPa) in the resin composition of Examples and Comparative Examples.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all drawings, similar components are designated by the same reference numerals, and description thereof will be omitted as appropriate.

The resin composition according to the present embodiment contains a thermosetting resin and a cyclic carbodiimide compound. The resin composition can be widely used for various electronic components.
Further, the cyclic carbodiimide compound according to the present embodiment has a cyclic structure having one carbodiimide group in one cyclic. Further, the cyclic carbodiimide compound means a monomer of a carbodiimide compound that does not contain a polycarbodiimide compound containing 3 or more structural units having a carbodiimide group in one molecule.

From various experimental results, the present inventor has found a novel function that the cyclic carbodiimide compound of the present embodiment acts as a curing accelerator. Although the detailed mechanism is not clear, the cyclic carbodiimide compound of the present embodiment has a crosslink density during post-cure because the glass transition temperature (Tg) increases without lowering the flow characteristics such as gel time and melt viscosity. It is thought that it works to increase the temperature. In addition, it is possible to suppress competition with other curing agents. Therefore, by using the cyclic carbodiimide compound as a curing accelerator, it has become possible to stably obtain the low shrinkage characteristics of the resin composition of the present embodiment.
Further, as a result of further study by the present inventor, it has been newly found that the trade-off relationship between low shrinkage and low elasticity can be improved in the resin composition of the present embodiment by using the cyclic carbodiimide compound. Found.

Hereinafter, each component constituting the resin composition according to the present embodiment will be described in detail.

(Thermosetting resin (A))
The resin composition according to this embodiment has a thermosetting resin (A).
The thermosetting resin (A) is one or two types selected from the group consisting of, for example, epoxy resin, phenol resin, oxetane resin, (meth) acrylate resin, unsaturated polyester resin, diallyl phthalate resin, and maleimide resin. Including the above. Among these, it is particularly preferable to contain an epoxy resin from the viewpoint of improving curability, storage stability, heat resistance, moisture resistance, and chemical resistance.

In the present embodiment, as the epoxy resin contained in the thermosetting resin (A), a monomer, an oligomer, or a polymer having two or more epoxy groups in one molecule can be used in general, and the molecular weight and molecular structure thereof are particularly high. Not limited. In the present embodiment, the epoxy resin is, for example, a biphenyl type epoxy resin; a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol type epoxy resin such as a tetramethyl bisphenol F type epoxy resin; a stillben type epoxy resin; a phenol novolac type epoxy. Novolak type epoxy resin such as resin, cresol novolac type epoxy resin; polyfunctional epoxy resin such as triphenol methane type epoxy resin exemplified by triphenol methane type epoxy resin, alkyl modified triphenol methane type epoxy resin; having a phenylene skeleton Phenol aralkyl type epoxy resin such as phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin having a phenylene skeleton, phenol aralkyl type epoxy resin having a biphenylene skeleton, naphthol aralkyl type epoxy resin having a biphenylene skeleton; dihydroxynaphthalene type epoxy resin, dihydroxy Naftor-type epoxy resins such as epoxy resins obtained by glycidyl etherification of naphthalene dimer; triazine nuclei-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; dicyclopentadiene-modified phenol-type epoxy resins and the like Arihashi Cyclic hydrocarbon compound Includes one or more selected from the group consisting of modified phenolic epoxy resins. From the viewpoint of suppressing warpage of the molded body and improving the balance of various properties such as filling property, heat resistance, and moisture resistance, it is selected from among these, biphenyl type epoxy resin, polyfunctional epoxy resin, and phenol aralkyl type epoxy resin. It is more preferable to contain one or more of them, and it is particularly preferable to contain at least one polyfunctional epoxy resin.

In the present embodiment, the content of the thermosetting resin (A) is preferably 1% by mass or more, more preferably 2% by mass or more, and 2.5% by mass, based on the entire resin composition. The above is particularly preferable. Thereby, the fluidity at the time of molding can be improved. Therefore, it is possible to improve the filling property and the molding stability. On the other hand, the content of the thermosetting resin (A) is preferably 15% by mass or less, more preferably 14% by mass or less, and 13% by mass or less with respect to the entire resin composition. Is particularly preferable. As a result, the moisture resistance reliability and reflow resistance of the electronic component can be improved. Further, by controlling the content of the thermosetting resin (A) within such a range, it is possible to contribute to the suppression of warpage of the molded product obtained by sealing the electronic element or the like with the resin composition. ..

(Curing agent (B))
The resin composition of the present embodiment can contain, for example, a curing agent (B). The curing agent (B) contained in the resin composition can be roughly classified into three types, for example, a heavy addition type curing agent, a catalytic type curing agent, and a condensation type curing agent.

The heavy addition type curing agent used as the curing agent (B) includes, for example, aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylerylene diamine (MXDA), diaminodiphenylmethane (DDM), and the like. Polyamine compounds containing aromatic polyamines such as m-phenylenediamine (MPDA) and diaminodiphenylsulfone (DDS), as well as dicyandiamide (DICY) and organic acid dihydralide; hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (HHPA) Acid anhydrides containing alicyclic acid anhydrides such as MTHPA), aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), and benzophenone tetracarboxylic acid (BTDA); novolak type Phenolic resin-based curing agents such as phenol resin, polyvinylphenol and aralkyl type phenol resin; Polymercaptan compounds such as polysulfide, thioester and thioether; Isocyanate compounds such as isocyanate prepolymer and blocked isocyanate; Organic acids such as carboxylic acid-containing polyester resin Includes one or more selected from the group consisting of.

The catalytic curing agent used as the curing agent (B) is a tertiary amine compound such as benzyldimethylamine (BDMA), 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methyl. Includes one or more selected from the group consisting of imidazole compounds such as imidazole, 2-ethyl-4-methylimidazole (EMI24); Lewis acids such as the BF3 complex.

The condensation type curing agent used as the curing agent (B) is one kind selected from the group consisting of, for example, a resole type phenol resin; a urea resin such as a methylol group-containing urea resin; and a melamine resin such as a methylol group-containing melamine resin. Or include two or more types.

Among these, it is more preferable to contain a phenolic resin-based curing agent from the viewpoint of improving the balance of flame resistance, moisture resistance, electrical properties, curability, storage stability and the like. As the phenolic resin-based curing agent, a monomer, an oligomer, or a polymer having two or more phenolic hydroxyl groups in one molecule can be used in general, and the molecular weight and molecular structure thereof are not particularly limited. The phenolic resin-based curing agent used as the curing agent (B) is, for example, a novolac-type phenolic resin such as phenol novolac resin, cresol novolac resin, or bisphenol novolak; a polyfunctional phenolic resin such as polyvinylphenol or triphenolmethane-type phenolic resin; Modified phenolic resins such as terpene-modified phenolic resins and dicyclopentadiene-modified phenolic resins; phenolal aralkyl resins having a phenylene skeleton and / or biphenylene skeleton, phenolal aralkyl resins such as naphthol aralkyl resins having phenylene and / or biphenylene skeletons; bisphenols Includes one or more selected from the group consisting of bisphenol compounds such as A and bisphenol F. Among these, from the viewpoint of suppressing the warp of the molded product obtained by sealing the electronic element or the like with the resin composition, it is more likely that at least one of the polyfunctional phenol resin and the phenol aralkyl type phenol resin is contained. preferable. In the present embodiment, the resin composition contains one or both of a polyfunctional epoxy resin as a thermosetting resin (A) and a polyfunctional phenol resin as a curing agent (B). An example of a preferred embodiment can be given.

In the present embodiment, the content of the curing agent (B) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and 1.5% by mass, based on the entire resin composition. The above is particularly preferable. As a result, excellent fluidity can be realized at the time of molding, and the filling property and moldability can be improved. On the other hand, the content of the curing agent (B) is preferably 9% by mass or less, more preferably 8% by mass or less, and particularly preferably 7% by mass or less, based on the entire resin composition. preferable. As a result, the moisture resistance reliability and reflow resistance of the electronic component can be improved. Further, by controlling the content of the curing agent (B) within such a range, it is possible to contribute to the suppression of warpage of the molded product obtained by sealing the electronic element or the like with the resin composition.

(Curing accelerator (C))
The resin composition according to the present embodiment may contain, for example, a curing accelerator (C). The curing accelerator (C) may be any one that promotes the cross-linking reaction between the thermosetting resin (A) (for example, epoxy resin) and the curing agent (B) (for example, phenol resin-based curing agent).

In the present embodiment, the curing accelerator (C) contains a phosphorus atom such as an organic phosphine, a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound. Compounds; 1,8-diazabicyclo [5,4,0] undecene-7, benzyldimethylamine, 2-methylimidazole and the like, such as amidine and tertiary amine, containing nitrogen atoms such as the quaternary salt of amidine and amine. It can contain one or more selected from the compounds. Among these, it is more preferable to contain a phosphorus atom-containing compound from the viewpoint of improving curability.

Examples of the organic phosphine that can be used in the above resin composition include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine and the like. The third phosphine of.

Examples of the tetra-substituted phosphonium compound that can be used in the above resin composition include compounds represented by the following general formula (6).

（上記一般式（６）において、Ｐはリン原子を表す。Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７は芳香族基またはアルキル基を表す。Ａはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸のアニオンを表す。ＡＨはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸を表す。ｘ、ｙは１〜３の数、ｚは０〜３の数であり、かつｘ＝ｙである。）

In (the general formula (6), P is selected ^.R 4 representing the phosphorus ^atom, R 5, .A ^{R 6} and ^{R 7} representing an aromatic group or alkyl group is a hydroxyl group, a carboxyl group, a thiol group Represents an anion of an aromatic organic acid having at least one functional group on the aromatic ring. AH is an aromatic having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group on the aromatic ring. Represents an organic acid. X and y are numbers 1 to 3, z is a number 0 to 3, and x = y.)

The compound represented by the general formula (6) is obtained, for example, as follows, but is not limited thereto. First, tetra-substituted phosphonium halide, aromatic organic acid and base are mixed with an organic solvent and uniformly mixed to generate an aromatic organic acid anion in the solution system. Then, water can be added to precipitate the compound represented by the general formula (6). In the compound represented by the general formula (6), R ⁴ , R ⁵ , R ⁶ and R ⁷ bonded to the phosphorus atom are phenyl groups, and AH is a compound having a hydroxyl group in the aromatic ring, that is, phenols. Yes, and A is preferably an anion of the phenols. Examples of the phenols include monocyclic phenols such as phenol, cresol, resorcin and catechol, condensed polycyclic phenols such as naphthol, dihydroxynaphthalene and anthraquinol, and bisphenols such as bisphenol A, bisphenol F and bisphenol S. Examples thereof include polycyclic phenols such as phenylphenol and biphenol.

Examples of the phosphobetaine compound that can be used in the above resin composition include compounds represented by the following general formula (7).

（上記一般式（７）において、Ｒ^８は炭素数１〜３のアルキル基、Ｒ^９はヒドロキシル基を表す。ｆは０〜５の数であり、ｇは０〜３の数である。）

(In the above general formula (7), R ⁸ represents an alkyl group having 1 to 3 carbon atoms and R ⁹ represents a hydroxyl group. F is a number from 0 to 5, and g is a number from 0 to 3.)

The compound represented by the general formula (7) can be obtained, for example, as follows. First, it is obtained through a step of contacting a tri-aromatic substituted phosphine, which is a tertiary phosphine, with a diazonium salt to replace the tri-aromatic substituted phosphine with the diazonium group of the diazonium salt. However, it is not limited to this.

Examples of the adduct of the phosphine compound and the quinone compound that can be used in the above resin composition include compounds represented by the following general formula (8).

（上記一般式（８）において、Ｐはリン原子を表す。Ｒ^１０、Ｒ^１１およびＲ^１２は炭素数１〜１２のアルキル基または炭素数６〜１２のアリール基を表し、互いに同一であっても異なっていてもよい。Ｒ^１３、Ｒ^１４およびＲ^１５は水素原子または炭素数１〜１２の炭化水素基を表し、互いに同一であっても異なっていてもよく、Ｒ^１４とＲ^１５が結合して環状構造となっていてもよい。）

(In the above general formula (8), P represents a phosphorus atom. R ¹⁰ , R ¹¹ and R ¹² represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and are identical to each other. R ¹³ , R ¹⁴ and R ¹⁵ represent hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, which may be the same or different from each other, and R ¹⁴ and R ¹⁵ are bonded to each other. It may have a ring structure.)

Examples of the phosphine compound used as an adjunct to the phosphine compound and the quinone compound include triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, tris (benzyl) phosphine and the like. Substituents or those having a substituent such as an alkyl group or an alkoxyl group are preferable, and examples of the substituent such as an alkyl group and an alkoxyl group include those having 1 to 6 carbon atoms. From the viewpoint of availability, triphenylphosphine is preferable.

Examples of the quinone compound used as an adduct of the phosphine compound and the quinone compound include benzoquinone and anthraquinones, and among them, p-benzoquinone is preferable from the viewpoint of storage stability.

As a method for producing an adduct of a phosphine compound and a quinone compound, the adduct can be obtained by contacting and mixing in a solvent in which both organic tertiary phosphine and benzoquinones can be dissolved. As the solvent, ketones such as acetone and methyl ethyl ketone, which have low solubility in adducts, are preferable. However, it is not limited to this.

In the compound represented by the general formula (8), the compounds in which R ¹⁰ , R ¹¹ and R ¹² bonded to the phosphorus atom are phenyl groups and R ¹³ , R ¹⁴ and R ¹⁵ are hydrogen atoms, that is, 1, A compound to which 4-benzoquinone and triphenylphosphine are added is preferable because it reduces the thermal elastic modulus of the cured product of the resin composition.

Examples of the adduct of the phosphonium compound and the silane compound that can be used in the above resin composition include compounds represented by the following general formula (9).

（上記一般式（９）において、Ｐはリン原子を表し、Ｓｉは珪素原子を表す。Ｒ^１６、Ｒ^１７、Ｒ^１８およびＲ^１９は、それぞれ、芳香環または複素環を有する有機基、あるいは脂肪族基を表し、互いに同一であっても異なっていてもよい。式中Ｒ^２０は、基Ｙ^２およびＹ^３と結合する有機基である。式中Ｒ^２１は、基Ｙ^４およびＹ^５と結合する有機基である。Ｙ^２およびＹ^３は、プロトン供与性基がプロトンを放出してなる基を表し、同一分子内の基Ｙ^２およびＹ^３が珪素原子と結合してキレート構造を形成するものである。Ｙ^４およびＹ^５はプロトン供与性基がプロトンを放出してなる基を表し、同一分子内の基Ｙ^４およびＹ^５が珪素原子と結合してキレート構造を形成するものである。Ｒ^２０、およびＲ^２１は互いに同一であっても異なっていてもよく、Ｙ^２、Ｙ^３、Ｙ^４およびＹ^５は互いに同一であっても異なっていてもよい。Ｚ^１は芳香環または複素環を有する有機基、あるいは脂肪族基である。）

(In the above general formula (9), P represents a phosphorus atom and Si represents a silicon atom. R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are organic groups having an aromatic ring or a heterocycle, or an aliphatic compound, respectively. Represents a group group and may be the same or different from each other. In the formula, R ²⁰ is an organic group bonded to the groups Y ² and Y ^{3. In the} formula, R ²¹ is a group Y ⁴ and Y ⁵ . The organic groups to be bonded. Y ² and Y ³ represent a group formed by a proton donating group releasing a proton, and the groups Y ² and Y ³ in the same molecule are bonded to a silicon atom to form a chelate structure. Y ⁴ and Y ⁵ represent groups formed by a proton donating group releasing a proton, and groups Y ⁴ and Y ⁵ in the same molecule combine with a silicon atom to form a chelate structure. There, R ²⁰ and R ²¹ may be the same or different from each other, and Y ² , Y ³ , Y ⁴ and Y ⁵ may be the same or different from each other. Z ¹ is an aromatic ring. Or an organic group having a heterocycle or an aliphatic group.)

In the general formula (9), R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ include, for example, a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, a naphthyl group, a hydroxynaphthyl group, a benzyl group and a methyl group. , Ethyl group, n-butyl group, n-octyl group, cyclohexyl group and the like. Among these, alkyl group such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group and hydroxynaphthyl group, alkoxy group and the like. , An aromatic group having a substituent such as a hydroxyl group or an unsubstituted aromatic group is more preferable.

Further, in the general formula (9), R ²⁰ is an organic group bonded to groups Y ² and Y ³ . Similarly, R ²¹ is an organic group that binds to groups Y ⁴ and Y ⁵ . Y ² and Y ³ are groups formed by a proton donating group releasing a proton, and the groups Y ² and Y ³ in the same molecule combine with a silicon atom to form a chelate structure. Similarly, Y ⁴ and Y ⁵ are groups formed by a proton donating group releasing a proton, and the groups Y ⁴ and Y ⁵ in the same molecule combine with a silicon atom to form a chelate structure. The groups R ²⁰ and R ²¹ may be the same or different from each other, and the groups Y ² , Y ³ , Y ⁴ and Y ⁵ may be the same or different from each other. In such a group represented by −Y ^2- R ²⁰ −Y ³ − and Y ⁴ −R ²¹ −Y ⁵ − in the general formula (9), the proton donor releases two protons. As the proton donor, an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule is preferable, and further, a carboxyl group or a hydroxyl group is added to the adjacent carbon constituting the aromatic ring. An aromatic compound having at least two is preferable, and an aromatic compound having at least two hydroxyl groups on adjacent carbons constituting the aromatic ring is more preferable, for example, catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxy. Naphthalene, 2,2'-biphenol, 1,1'-bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl Alcohol, 1,2-cyclohexanediol, 1,2-propanediol, glycerin and the like can be mentioned, but among these, catechol, 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene are more preferable.

Further, Z ¹ in the general formula (9) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring, and specific examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. An aliphatic hydrocarbon group such as a hexyl group and an octyl group, an aromatic hydrocarbon group such as a phenyl group, a benzyl group, a naphthyl group and a biphenyl group, a glycidyloxy group such as a glycidyloxypropyl group, a mercaptopropyl group and an aminopropyl group. , Reactive substituents such as mercapto group, alkyl group having amino group and vinyl group, etc. Among these, methyl group, ethyl group, phenyl group, naphthyl group and biphenyl group are used from the viewpoint of thermal stability. , More preferred.

As a method for producing an adduct of a phosphonium compound and a silane compound, a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol and dissolved, and then at room temperature. The sodium methoxide-methanol solution is added dropwise with stirring. Further, when a solution prepared in advance in which a tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide is dissolved in methanol is added dropwise to the solution under stirring at room temperature, crystals are precipitated. When the precipitated crystals are filtered, washed with water and vacuum dried, an adduct of a phosphonium compound and a silane compound is obtained. However, it is not limited to this.

In the present embodiment, the content of the curing accelerator (C) is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, and 0. It is particularly preferable that it is 15% by mass or more. Thereby, the curability at the time of sealing molding can be effectively improved. On the other hand, the content of the curing accelerator (C) is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, and 3.5% by mass, based on the entire resin composition. It is particularly preferable that it is% or less. This makes it possible to improve the fluidity during sealing molding.

The cyclic carbodiimide compound according to the present embodiment may be a cyclic carbodiimide compound represented by the following general formula (i). The cyclic carbodiimide compound represented by the following general formula (i) may have two carbodiimide groups in one molecule or one carbodiimide group.

（一般式（ｉ）中、Ｘは、下記一般式（ｉ−１）〜（ｉ−３）で表される２価の基または下記式（ｉ−４）で表される４価の基である。Ｘが２価のときｑは０で、Ｘが４価のときｑは１である。Ａｒ^１〜Ａｒ^４は各々独立に芳香族基である。これらの芳香族基は炭素数１〜６のアルキル基またはフェニル基で置換されていてもよい。）

(In the general formula (i), X is a divalent group represented by the following general formulas (i-1) to (i-3) or a tetravalent group represented by the following formula (i-4). When X is divalent, q is 0, and when X is tetravalent, q is ^1. Ar ^{1 to} Ar ⁴ are independently aromatic groups. These aromatic groups have 1 to 1 carbon atoms. It may be substituted with an alkyl group or a phenyl group of 6).

（上記式（ｉ−１）中、ｎは１〜６の整数である。）

(In the above formula (i-1), n is an integer of 1 to 6).

（上記式（ｉ−２）中、ｍおよびｎは各々独立に０〜３の整数である。）

(In the above formula (i-2), m and n are each independently an integer of 0 to 3.)

（上記式（ｉ−３）中、Ｒ^１およびＲ^２は各々独立に、炭素数１〜６のアルキル基、フェニル基を表す。）

(In the above formula (i-3), R ¹ and R ² independently represent an alkyl group and a phenyl group having 1 to 6 carbon atoms, respectively.)

Further, as the cyclic carbodiimide compound represented by the general formula (i), some compounds having the following structural formulas are exemplified.

As a method for producing the cyclic carbodiimide compound according to the present embodiment, for example, the following method can be used.
(I) The monocyclic cyclic carbodiimide compound can be produced, for example, by a production process including the following steps (1) to (3). First, a nitro compound containing Ar ¹ and Ar ² is prepared (step (1)). Subsequently, an amine compound is produced from the nitro compound (step (2)). Then, a monocyclic cyclic carbodiimide compound can be produced from the amine compound via the triphenylphosphine compound or the urea compound (step (3)).
(Ii) The compound ring cyclic carbodiimide compound can be produced in the same manner as in (i), except that, for example, in the above step (1), a nitro compound containing the above Ar ^{1 to} Ar ⁴ is prepared. it can.

Further, the cyclic carbodiimide compound according to the present embodiment can be produced by a conventionally known method. Examples thereof include a method of producing from an amine substance via an isocyanate body, a method of producing from an amine substance via an isothiocyanate compound, a method of producing from a carboxylic acid compound via an isocyanate compound, and the like.

In the present embodiment, the lower limit of the content of the cyclic carbodiimide compound is not particularly limited, but is preferably 0.1% by mass or more, preferably 0.15% by mass or more, based on the whole resin composition according to the present embodiment. More preferably, 0.2% by mass or more is particularly preferable. On the other hand, the upper limit of the content of the cyclic carbodiimide compound is not particularly limited, but is preferably 2.0% by mass or less, more preferably 1.8% by mass or less, and particularly preferably 1.5% by mass or less. By setting the content of the cyclic carbodiimide compound within the above range, not only low shrinkage characteristics can be obtained, but also a resin composition having an excellent balance between low elasticity and flow characteristics can be obtained.

In the present embodiment, by using the cyclic carbodiimide compound in combination with the curing accelerator (C), it is possible to more easily control the resin design of the resin composition. Therefore, for example, the balance between low shrinkage and low elasticity can be improved.

(Filler (D))
The resin composition of the present embodiment may contain a filler (D). The filler (D) is one or two selected from the group consisting of fused silica such as molten crushed silica and fused spherical silica, silica such as crystalline silica, alumina, aluminum hydroxide, silicon nitride, and aluminum nitride. More than one kind of inorganic filler can be included. Among these, silica such as molten crushed silica, molten spherical silica, and crystalline silica is preferable, and fused spherical silica can be used more preferably.

In the present embodiment, the average particle size (D ₅₀ ) of the filler (D) is preferably 0.01 μm or more and 1 μm or less, and more preferably larger than 1 μm and 50 μm or less. By setting the average particle size to the above lower limit value or more, the fluidity of the resin composition can be improved and the moldability can be improved more effectively. Further, by setting the average particle size to the above upper limit value or less, it is possible to reliably suppress the occurrence of gate clogging and the like. In the present embodiment, the average particle size (D ₅₀ ) of the filler (D) is the particle size distribution of the particles using a commercially available laser diffraction type particle size distribution measuring device (for example, SALD-7000 manufactured by Shimadzu Corporation). Can be measured on a volume basis, and its median diameter (D ₅₀ ) can be used as the average particle size.

The content of the filler (D) is preferably 80% by mass or more, more preferably 83% by mass or more, and particularly preferably 85% by mass or more with respect to the entire resin composition. As a result, low hygroscopicity and low thermal expansion can be improved, and the moisture resistance reliability and reflow resistance of electronic components can be more effectively improved. On the other hand, the content of the filler (D) is preferably 95% by mass or less, more preferably 93% by mass or less, and particularly preferably 90% by mass or less, based on the entire resin composition. preferable. This makes it possible to more effectively improve the fluidity and filling property of the resin composition during molding. Further, by controlling the content of the filler (D) within such a range, it is possible to contribute to the suppression of warpage of the molded product obtained by sealing the electronic element or the like with the resin composition.

Further, as the filler (D), for example, two or more kinds of fillers having different average particle diameters (D50) can be used in combination. Thereby, the filling property of the filler (D) with respect to the entire resin composition can be more effectively enhanced. Therefore, it is possible to contribute to the suppression of warpage of the molded product. Further, in the present embodiment, the filling property of the resin composition is improved by including the first filler having an average particle diameter of 0.01 μm or more and 1 μm or less and the second filler having an average particle diameter of more than 1 μm and 50 μm or less. It is mentioned as one of the preferable aspects from the viewpoint of improving and suppressing the warp of the molded product.

In the present embodiment, when the first filler having an average particle size of 0.01 μm or more and 1 μm or less and the second filler having an average particle size of more than 1 μm and 50 μm or less are included, the average particle size of the entire filler (D) is 1 μm. The content of the second filler, which is larger and 50 μm or less, is preferably, for example, 70% by mass or more, and more preferably 75% by mass or more. This makes it possible to more effectively suppress the warpage of the molded product. On the other hand, the upper limit of the content of the second filler having an average particle size of more than 1 μm and 50 μm or less with respect to the entire filler (D) is not particularly limited and may be, for example, 99% by mass or less.

(Other ingredients)
The resin composition of the present embodiment is, if necessary, one of various additives such as a coupling agent, a mold release agent, a flame retardant, an ion scavenger, a colorant, a low stress agent and an antioxidant. Alternatively, two or more kinds can be appropriately blended.

In the resin composition of the present embodiment, a coupling agent such as a silane coupling agent can be added in order to improve the adhesion between the epoxy resin and the inorganic filler. The coupling agent may be any one that reacts between the epoxy resin and the inorganic filler to improve the interfacial strength between the epoxy resin and the inorganic filler, and is not particularly limited, but for example, epoxysilane. Examples thereof include aminosilane, epoxysilane, and mercaptosilane.

Examples of the epoxysilane include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and β- (3,4 epoxycyclohexyl) ethyltrimethoxy. Examples include silane. Examples of aminosilane include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) γ-aminopropyl. Methyldimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N- (6-aminohexyl) ) 3-Aminopropyltrimethoxysilane, N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethanan and the like. Examples of the ureidosilane include γ-ureidopropyltriethoxysilane. , Hexamethyldisilazane and the like. A primary amino moiety of aminosilane may be used as a latent aminosilane coupling agent protected by reacting with ketone or aldehyde. Further, the aminosilane has a secondary amino group. As the mercaptosilane, for example, γ-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, and bis (3-triethoxy) may be used. Examples thereof include silane coupling agents that exhibit the same functions as mercaptosilane coupling agents by thermal decomposition such as silylpropyl) disulfide. These silane coupling agents are those that have been hydrolyzed in advance. These silane coupling agents may be blended alone or in combination of two or more.

From the viewpoint of continuous moldability, mercaptosilane is preferable, from the viewpoint of fluidity, aminosilane is preferable, and from the viewpoint of adhesion, epoxysilane is preferable.

The lower limit of the content of the coupling agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more, based on the entire resin composition. is there. When the content of the coupling agent is at least the above lower limit value, the interface strength between the epoxy resin and the inorganic filler does not decrease, and good vibration resistance can be obtained. The upper limit of the content of the coupling agent is preferably 1% by mass or less, more preferably 0.8% by mass or less, and particularly preferably 0.6% by mass or less, based on the entire resin composition. .. When the content of the coupling agent is not more than the above upper limit value, the interface strength between the epoxy resin and the inorganic filler does not decrease, and good vibration resistance can be obtained. Further, when the content of the coupling agent such as the silane coupling agent is within the above range, the water absorption of the cured product of the fixing resin composition does not increase, and good rust prevention can be obtained. ..

The release agent may be one or two selected from natural waxes such as carnauba wax, synthetic waxes such as montanic acid ester wax and polyethylene oxide wax, higher fatty acids such as zinc stearate and their metal salts, and paraffin. The above can be included.
The flame retardant may contain, for example, one or more selected from magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene. The colorant can include, for example, carbon black.
The ion scavenger may contain one or more selected from hydrotalcites or hydrous oxides of elements selected from magnesium, aluminum, bismuth, titanium and zirconium.
The colorant may contain one or more selected from carbon black, red iron oxide, and titanium oxide.
The low stress agent may contain one or more selected from silicone compounds such as polybutadiene compounds, acrylonitrile butadiene copolymer compounds, silicone oils, and silicone rubbers.

In the present embodiment, the upper limit of the content of halogen ions (ionic impurities) in the cured product of the resin composition is preferably 20 ppm or less, more preferably 15 ppm or less, based on the entire resin composition. , More preferably 10 ppm or less. The lower limit of the halogen ion content is not particularly limited, but is, for example, 0 ppb or more, more preferably 10 ppb or more, and more preferably 100 ppb or more with respect to the entire resin composition. In the present embodiment, halogen ions can be reduced by using, for example, a high-purity epoxy resin or the carbodiimide compound of the present embodiment. By setting the halogen ion content to the upper limit or less, a cured product of a resin composition having excellent durability can be obtained.
It is generally known that chlorine increases when imidazole is used as a curing accelerator. Although the detailed mechanism is not clear, it is considered that the carbodiimide compound of the present embodiment has a reaction mechanism different from that of imidazole, for example, so that the binding chlorine in the epoxy resin is not eliminated.

The concentration of the halogen ion can be obtained as follows. First, the resin composition of the present embodiment is molded and cured at 175 ° C. for 180 seconds, and then pulverized with a pulverizer to obtain a powder of the cured product. The obtained cured product powder is treated in pure water at 120 ° C. for 24 hours, ions are extracted in pure water, and then measurement can be performed using ICP-MS (inductively coupled plasma ion source mass spectrometer). In the present embodiment, the halogen atom contains a binding halogen component contained in the epoxy resin of the resin composition and a halogen component freed from the epoxy resin. The halogen ion whose concentration is measured refers to the derivative of the free halogen component of the two.

Hereinafter, a method for evaluating the characteristics of the sealing resin composition will be described.

In the present embodiment, the glass transition temperature of the cured product obtained by heat-treating the resin composition at, for example, 175 ° C. for 120 seconds and then heat-treating at 175 ° C. for 4 hours is preferably 100 ° C. or higher, preferably 120 ° C. The above is more preferable, and 135 ° C. or higher is particularly preferable. Thereby, the heat resistance of the electronic component can be improved more effectively. On the other hand, the upper limit of the glass transition temperature is not particularly limited, but can be, for example, 250 ° C. or lower. In the present embodiment, the glass transition temperature (Tg) can be increased by increasing the softening point of the epoxy resin or the curing agent, for example.

In the present embodiment, the linear expansion coefficient (CTE1) of the cured product obtained by heat-treating the resin composition at, for example, 175 ° C. for 120 seconds and then heat-treating at 175 ° C. for 4 hours at a glass transition temperature or lower is 15 ppm. It is preferably / ° C. or lower, and more preferably 12 ppm / ° C. or lower. The coefficient of linear expansion (CTE1) below the glass transition temperature is preferably 1 ppm / ° C. or higher, for example. By controlling CTE1 in this way, it is possible to more reliably suppress the warp of the molded product due to the difference in the linear expansion coefficient between the electronic element and the sealing resin. In the present embodiment, for example, the coefficient of linear expansion (CTE1) can be reduced by increasing the blending amount of the filler.

In the present embodiment, the linear expansion coefficient (CTE2) of the cured product obtained by heat-treating the resin composition at, for example, 175 ° C. for 120 seconds and then heat-treating at 175 ° C. for 4 hours when the glass transition temperature is exceeded is 40 ppm. It is preferably / ° C. or lower, and more preferably 38 ppm / ° C. or lower. Further, the coefficient of linear expansion (CTE2) when the glass transition temperature is exceeded is preferably 5 ppm / ° C. or higher, for example. By controlling CTE2 in this way, warpage of the molded product due to the difference in linear expansion coefficient between the electronic element and the sealing resin can be more reliably suppressed, particularly in a high temperature environment. In the present embodiment, for example, the coefficient of linear expansion (CTE2) can be reduced by increasing the blending amount of the filler.

The glass transition temperature and the coefficient of linear expansion (CTE1, CTE2) of the resin composition of the present embodiment can be measured, for example, as follows. First, the resin composition was injection-molded using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.) at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds, and 10 mm × 4 mm. Obtain a x4 mm test piece. Then, after the obtained test piece was post-cured at 175 ° C. for 4 hours, a thermomechanical analyzer (TMA100 manufactured by Seiko Electronics Co., Ltd.) was used to measure the temperature range from 0 ° C. to 320 ° C. and the heating rate. The measurement is performed under the condition of 5 ° C./min. From this measurement result, the glass transition temperature, the coefficient of linear expansion below the glass transition temperature (CTE1), and the coefficient of linear expansion above the glass transition temperature (CTE2) are calculated.

In the present embodiment, the upper limit of the molding shrinkage of the resin composition is preferably 0.12% or less, more preferably 0.125% or less, and particularly preferably 0.11% or less. preferable. By keeping the upper limit of the molding shrinkage rate low, it is possible to suppress the warpage of the molded product. On the other hand, the lower limit of the molding shrinkage of the resin composition is preferably, for example, −0.5% or more, and more preferably −0.3% or more. By setting the shrinkage rate of the molding shrinkage within the above range, it is possible to more easily demold the molded body. The molding shrinkage is measured by using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.) using, for example, a resin composition, with a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds. It can be carried out according to JIS K 6911 for the test piece prepared under the above conditions. In the present embodiment, for example, the molding shrinkage ratio can be suppressed to a desired value by adjusting the addition amount of the carbodiimide compound according to the blending composition of the thermosetting resin in the resin composition.

In the present embodiment, the storage elastic modulus (E') of the cured product obtained by heat-treating the resin composition at, for example, 175 ° C. for 120 seconds and then heat-treating at 175 ° C. for 4 hours, as measured at 260 ° C. The lower limit value of is not particularly limited, but for example, 500 MPa or more is preferable, 600 MPa or more is more preferable, and 700 MPa or more is further preferable. On the other hand, the upper limit of the storage elastic modulus (E') is not particularly limited, but is preferably 1500 MPa or less, more preferably 1200 MPa or less, still more preferably 1100 MPa or less. By setting the thermal elastic modulus (storage elastic modulus (E') at 260 ° C.) of the resin composition of the present embodiment within the above range, the warpage of the substrate can be suppressed and the semiconductor has excellent reliability. The structure of the device can be realized.

Examples of the method for measuring the thermal elastic modulus of the present embodiment include the following methods. Transfer molding was performed using the resin composition of the present embodiment to obtain a test piece having a width of 4 mm, a length of 20 mm, and a thickness of 0.1 mm. The conditions for transfer molding were a molding temperature of 125 ° C. and a curing time of 7 minutes. The storage elastic modulus at 260 ° C. when the obtained test piece was measured using a DMA (Dynamic mechanical analysis / dynamic viscoelasticity measuring instrument) under the conditions of a three-point bending mode, a frequency of 10 Hz, and a measurement temperature of 260 ° C. Find (E'). The unit is MPa.

Further, in the resin composition of the present embodiment, the following condition (1) is preferably satisfied, and (2) is more preferably satisfied.
(1) The molding shrinkage ratio is not more than the above upper limit value, and the thermal elastic modulus is not more than the above upper limit value.
(2) Satisfy (1) and satisfy that "Y (%) + αX (MPa)", which is a relational expression between the molding shrinkage rate and the thermal elastic modulus, is 0.15% or less.
In the relational expression of (2) above, Y indicates a molding shrinkage rate, and X indicates a thermal elastic modulus. The proportionality constant α (% / Mpa) is, for example, 3.5 × ^10-5 , preferably 4.0 × ^10-5 , and more preferably 4.5 × ^10-5 .

Here, the technical meaning of the relational expression (2) above will be described.
As a result of examination by the present inventor, a certain relationship was found between the molding shrinkage rate and the thermal elastic modulus.
Specifically, as shown in FIG. 3, it was found that a calibration curve showing the relationship between the molding shrinkage and the thermal elastic modulus can be obtained from a comparative example of a normal resin composition containing no cyclic carbodiimide compound. .. When the molding shrinkage is smaller and the thermal elastic modulus is smaller than this calibration curve, it can be seen that a resin composition having excellent low shrinkage and low elasticity was obtained. That is, the calibration curve shown in FIG. 3 is an index showing both low shrinkage and low elasticity.
As a result of concretely examining this index, a relational expression that "Y (%) + αX (MPa)" is 0.15% or less is derived.
0.15% indicates, for example, the general technical level of shrinkage required for a cured product of a sealing resin composition in the semiconductor field.
The proportionality constant α indicates the proportional relationship between the molding shrinkage and the thermal elastic modulus in a normal resin composition containing no cyclic carbodiimide compound, and is a numerical value calculated from experimental data. The larger the proportionality constant α, the better the balance between low shrinkage and low elasticity.
Therefore, satisfying the relational expression (2) above satisfies the low shrinkage property required in a predetermined technical field, and has lower shrinkage property and lower elasticity than a normal resin composition containing no cyclic carbodiimide compound. It can be seen that an excellent resin composition was obtained.

In the present embodiment, the flow length of the spiral flow of the resin composition is preferably 90 cm or more, more preferably 100 cm or more, and particularly preferably 110 cm or more. Thereby, the filling property at the time of molding the resin composition can be improved more effectively. The upper limit of the flow length of the spiral flow is not particularly limited, but can be, for example, 200 cm or less. For the measurement of the spiral flow, for example, a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.) is used, and the mold temperature is 175 ° C. for a mold for measuring the spiral flow according to EMMI-1-66. The resin composition can be injected under the conditions of an injection pressure of 6.9 MPa and a curing time of 120 seconds, and the flow length can be measured. In the present embodiment, the spiral flow can be increased by, for example, using molten spherical silica as a filler, lowering the softening point of the epoxy resin and the curing agent, and reducing the amount of the curing accelerator.

In the present embodiment, the resin composition preferably has, for example, a gel time of 10 seconds or more and 50 seconds or less, and more preferably 15 seconds or more and 45 seconds or less. As a result, the molding cycle can be speeded up while improving the moldability of the resin composition. The gel time can be measured by measuring the time (gel time) from melting the resin composition on a hot plate heated to 175 ° C. to curing while kneading with a spatula. In the present embodiment, the gel time can be reduced, for example, by increasing the amount of the curing accelerator or the carbodiimide compound.

In the present embodiment, the glass transition temperature, molding shrinkage rate, spiral flow, gel time, and thermal elastic modulus are appropriately adjusted, for example, by appropriately adjusting the type and blending ratio of each component of the resin composition, the method of preparing the resin composition, and the like. Can be controlled by Among these, for example, by using a cyclic carbodiimide compound, it can be mentioned as an element for setting the spiral flow and gel time in a desired numerical range. Further, the use and blending amount of the cyclic carbodiimide compound, the combined use of other curing accelerators, the selection of the resin, and the like are mentioned as factors for lowering the molding shrinkage rate and the thermal elastic modulus.

Hereinafter, a method for producing the resin composition according to the present embodiment will be described.

The method for producing the resin composition of the present embodiment is not particularly limited, but for example, after each of the above-mentioned components is mixed by a known means, further melt-kneaded by a kneader such as a roll, a kneader or an extruder, and cooled. Crushed granules, tablet-shaped after crushing, and if necessary, the crushed ones can be sieved, and the dispersibility and fluidity can be appropriately determined by centrifugal milling or hot-cutting. Granules or the like produced by a condyle-building method in which the above are adjusted can be used as the resin composition.

In the resin composition according to this embodiment, it can be used for various electronic components. As an example of the use of the resin composition used for such electronic parts, a sealing material for sealing electronic parts such as semiconductor elements and electronic elements (sealing resin composition), a substrate material (core layer, A build-up layer, a solder resist layer on the outermost layer, etc.), an insulating layer used for a light receiving element such as a white diode, and the like.

Hereinafter, the configuration of the electronic device according to the present embodiment will be described with reference to FIG. FIG. 1 is a cross-sectional view showing an example of the electronic component 100 according to the present embodiment.
The electronic device of the present embodiment includes a cured product of the above-mentioned resin composition.

The outline of the electronic device (electronic component 100) according to the present embodiment will be described.
The electronic component 100 according to the present embodiment includes a sealing resin 20 that seals the electronic element 10 or the metal member. The sealing resin 20 is composed of a cured product of the resin composition according to the present embodiment. Further, as the electronic element 10 and the metal member, for example, those exemplified above can be used.

The resin composition according to the present embodiment is preferably used as a sealing resin constituting a wafer level package obtained by resin-sealing the circuit surface of a wafer, but is used for a pseudo wafer described below. It is also applicable to sealing resins.

Next, the details of the electronic component 100 according to the present embodiment will be described. The electronic component 100 exemplified in FIG. 1 is a semiconductor package including an electronic element 10 which is a semiconductor element and a sealing resin 20 for sealing the electronic element 10. In FIG. 1, an electronic component 100, which is a wafer level package, is shown in particular. The electronic component 100 according to the present embodiment is not limited to the one shown in FIG. The electronic component 100 may be, for example, a semiconductor package obtained by sealing an electronic element 10 (semiconductor element) mounted on an organic substrate or a lead frame with a resin composition. Further, the electronic component 100 may be an in-vehicle electronic control unit obtained by sealing, for example, a wiring board and a plurality of electronic elements 10 mounted on the wiring board together with a resin composition.
Further, the electronic component 100 may include a metal member and a sealing resin 20 for sealing the metal member. Examples of such an electronic component 100 include a resin substrate formed by sealing a metal wiring with a resin composition.
From the above, the resin composition according to the present embodiment is not limited to general electronic devices, but is the semiconductor encapsulating resin composition used for the semiconductor package and the ECU encapsulation used for the in-vehicle electronic control unit (ECU). It can be applied to a resin composition or a sealing resin composition for a resin substrate used for the above resin substrate.

The electronic component 100 shown in FIG. 1 includes an electronic element 10 provided with an electrode 12 on one surface thereof, and a sealing resin 20 provided so as to cover other than one surface of the electronic element 10. On one surface of the electronic element 10, for example, an insulating layer 30 in which a via 40 connected to the electrode 12 is embedded is provided. A wiring 42 forming a rewiring layer is provided on the insulating layer 30 so as to connect to the via 40. Further, an insulating layer 32, which is a solder resist layer, is provided on the insulating layer 30 and the wiring 42. Further, the insulating layer 32 is provided with an opening for connecting to the wiring 42, and a solder ball 44 is provided in the opening. The electronic component 100 shown in FIG. 1 is electrically connected to the outside via a solder ball 44.

Next, a method of manufacturing the electronic component 100 will be described.
The method for manufacturing the electronic component 100 includes a step of sealing and molding the electronic element 10 or the metal member using the above-mentioned resin composition. As a result, it is possible to suppress the occurrence of warpage in the molded product obtained by sealing the electronic element 10 or the metal member.

FIG. 2 is a cross-sectional view showing an example of a method for manufacturing the electronic component 100 according to the present embodiment. In FIG. 2, a method of forming a wafer level package by using a pseudo wafer formed by mounting a plurality of electronic elements 10 which are semiconductor elements on a carrier 50 is illustrated. According to the manufacturing method shown in FIG. 2, it is possible to reduce the thickness of the electronic component 100. The method for manufacturing the electronic component 100 according to the present embodiment is not limited to that shown in FIG. The electronic component 100 may be manufactured, for example, by sealing the electronic element 10 mounted on an organic substrate or a lead frame with a resin composition. Further, the electronic component 100 may be manufactured by, for example, MAP (Mold Array Package) molding or the like.
Hereinafter, an example of a method for manufacturing the electronic component 100 shown in FIG. 2 will be described in detail.

First, as shown in FIG. 2A, a plurality of electronic elements 10 are arranged on the mount film 52 formed on the carrier 50. As a result, a pseudo wafer is formed. The carrier 50 has, for example, a plate shape. The mount film 52 is a heat-removable film whose adhesiveness to the electronic element 10 is lowered by heating, for example. In the present embodiment, for example, the electronic element 10 can be arranged on the mount film 52 so that one side of the electronic element 10 provided with the external electrode faces the mount film 52.

Next, as shown in FIG. 2B, the electronic element 10 is hermetically sealed and molded using the resin composition. The step of sealing and molding is performed, for example, on the electronic element 10 at the wafer level. In addition, performing sealing molding at the wafer level means that a plurality of electronic elements 10 constituting the pseudo wafer are collectively sealed with a resin composition as shown in FIG. 2 (b), or a circuit surface on the wafer is performed. Is a concept including encapsulating the wafers collectively with a resin composition. As a result, the molded body 200 composed of the plurality of electronic elements 10 and the sealing resin 20 for sealing the plurality of electronic elements 10 is formed. In the present embodiment, the molded body 200 is formed by using the above-mentioned resin composition. Therefore, it is possible to suppress warpage even in the molded body 200 having a large area and a thin film thickness.

The sealing molding with the resin composition of the present embodiment is not particularly limited, but can be performed by, for example, compression molding. In this case, compression molding is more preferably performed under temperature conditions of, for example, 120 ° C. or higher and 160 ° C. or lower. Thereby, the resin composition can be sufficiently cured. Further, when the molded body 200 is cooled, it is possible to prevent the molded body 200 from being warped due to the shrinkage of the sealing resin 20.

Next, as shown in FIG. 2C, the molded body 200 is peeled off from the mount film 52.

Next, as shown in FIG. 2D, a rewiring layer is formed on one surface of the molded body 200 where the electronic element 10 is exposed. The rewiring layer includes, for example, the above-mentioned insulating layer 30, the via 40 embedded in the insulating layer 30, the wiring 42 provided on the insulating layer 30, and the insulating layer provided on the insulating layer 30 and the wiring 42. 32 and. Next, a plurality of solder balls 44 connected to the wiring 42 are formed on the rewiring layer. After that, the molded body 200 is diced and individualized into each electronic component 100.
In the present embodiment, for example, the electronic component 100 is formed in this way.

The present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the range in which the object of the present invention can be achieved are included in the present invention.
Hereinafter, an example of the reference embodiment of the present invention will be shown.
<1>
Thermosetting resin and
Cyclic carbodiimide compounds and
A resin composition containing an inorganic filler.
The inorganic filler contains silica, and the content of the inorganic filler is 80% by mass or more and 95% by mass or less with respect to the entire resin composition.
A resin composition used for electronic parts, wherein the glass transition temperature of the cured product obtained by heat-treating the resin composition at 175 ° C. for 120 seconds and then heat-treating at 175 ° C. for 4 hours is 100 ° C. or higher.
<2>
The resin composition according to <1>.
A resin composition further comprising a curing agent.
<3>
The resin composition according to <1> or <2>.
A resin composition further comprising an inorganic filler.
<4>
The resin composition according to <3>.
A resin composition in which the inorganic filler contains silica.
<5>
The resin composition according to any one of <1> to <4>.
A resin composition further comprising a curing accelerator.
<6>
The resin composition according to any one of <1> to <5>.
A resin composition in which the content of the cyclic carbodiimide compound is 0.1% by mass or more and 2.0% by mass or less with respect to the entire resin composition.
<7>
The resin composition according to any one of <1> to <6>.
A resin composition in which the thermosetting resin contains an epoxy resin.

Next, examples of the present invention will be described.

(Preparation of resin composition)
For each example, a resin composition was prepared as follows. First, according to the formulation shown in Table 1, a mixer is used to mix a thermosetting resin (A), a curing agent (B), a cyclic carbodiimide compound, a curing accelerator (C), a silane coupling agent, a mold release agent, and a coloring agent. Used to mix to give a mixture. Next, the filler (D) was added to the above mixture according to the formulation shown in Table 1, and then the mixture was mixed using a mixer. The resulting mixture was then roll-kneaded at 70-100 ° C. Then, the mixture after kneading was cooled and pulverized to obtain a powdery resin composition.

For each comparative example, a resin composition was prepared as follows. First, according to the formulation shown in Table 1, the thermosetting resin (A), the curing agent (B), the curing accelerator (C), the silane coupling agent, the mold release agent, and the coloring agent are mixed using a mixer. Obtained a mixture. Next, the filler (D) was added to the above mixture according to the formulation shown in Table 1, and then the mixture was mixed using a mixer. The resulting mixture was then roll-kneaded at 70-100 ° C. Then, the mixture after kneading was cooled and pulverized to obtain a powdery resin composition.

The unit of the blending ratio of each component in Table 1 is mass%. The details of each component in Table 1 are as follows.

(A) Thermosetting resin Thermosetting resin 1: Phenolic aralkyl type epoxy resin having a biphenylene skeleton (NC-3000, manufactured by Nippon Kayaku Co., Ltd.)
Thermosetting resin 2: Biphenyl type epoxy resin (YX-4000H, manufactured by Mitsubishi Chemical Corporation)

(B) Hardener Hardener 1: Phenolic aralkyl resin having a biphenylene skeleton (MEH-7851SS, manufactured by Meiwa Kasei Co., Ltd.)
Hardener 2: Phenolic aralkyl resin having a phenylene skeleton (XLC-3L, manufactured by Mitsui Chemicals, Inc.)

Cyclic carbodiimide compound: Cyclic carbodiimide compound (TCC, manufactured by Teijin Limited)

(C) Curing accelerator triphenylphosphine (PP360, manufactured by Keiai Kasei Co., Ltd.)

(D) Filler Inorganic filler 1: Spherical fused silica (manufactured by Electrochemical Industry Co., Ltd., FB-950FC, average particle size D ₅₀ : 24 μm)
Inorganic filler 2: Spherical fused silica (manufactured by Admatex Co., Ltd., SO-25R, average particle size D ₅₀ : 0.5 μm)
The average particle size (D ₅₀ ) of the filler (D) is measured by measuring the particle size distribution of the particles using a laser diffraction type particle size distribution measuring device (SALD-7000, manufactured by Shimadzu Corporation) on a volume basis, and the median thereof. The diameter (D ₅₀ ) was taken as the average particle size.

Silane coupling agent: N-phenylγ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-573)

Release agent: Carnauba wax (Nikko Fine Co., Ltd., Nikko Carnauba)
Colorant: Carbon black (manufactured by Mitsubishi Chemical Corporation, MA600)

(Spiral flow)
Spiral flow measurement was performed on the obtained resin composition for each Example and each Comparative Example. Spiral flow measurement uses a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.) to mold for spiral flow measurement according to EMMI-1-66 at a mold temperature of 175 ° C and injection pressure. The resin composition was injected under the conditions of 6.9 MPa and a curing time of 120 seconds, and the flow length was measured. The results are shown in Table 1.

(Glass transition temperature, coefficient of linear expansion)
For each Example and each Comparative Example, the glass transition temperature (Tg) and the coefficient of linear expansion (CTE1, CTE2) of the cured product of the obtained resin composition were measured as follows. First, the resin composition was injection-molded using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.) at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds, and 10 mm × 4 mm. A test piece of × 4 mm was obtained. Then, after the obtained test piece was post-cured at 175 ° C. for 4 hours, a thermomechanical analyzer (TMA100 manufactured by Seiko Electronics Co., Ltd.) was used to measure the temperature range from 0 ° C. to 320 ° C. and the heating rate. The measurement was carried out under the condition of 5 ° C./min. From this measurement result, the glass transition temperature (Tg), the coefficient of linear expansion below the glass transition temperature (CTE1), and the coefficient of linear expansion above the glass transition temperature (CTE2) were calculated. The results are shown in Table 1.

(Molding shrinkage rate)
For each Example and each Comparative Example, the molding shrinkage of the obtained resin composition was measured. The measurement was performed on a test piece prepared using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.) under the conditions of a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds. The procedure was performed according to JIS K 6911. The results are shown in Table 1.

For each Example and each Comparative Example, the thermal elastic modulus of the obtained resin composition was measured. Transfer molding was performed using the above resin composition to obtain a test piece having a width of 4 mm, a length of 20 mm, and a thickness of 0.1 mm. The conditions for transfer molding were a molding temperature of 125 ° C. and a curing time of 7 minutes. This is the thermal elastic modulus when the obtained test piece was measured using a DMA (Dynamic mechanical analysis / dynamic viscoelasticity measuring instrument) under the conditions of a three-point bending mode, a frequency of 10 Hz, and a measurement temperature of 260 ° C. The "storage elastic modulus (E') at 260 ° C." was determined. The unit is MPa.
Further, FIG. 3 shows the relationship between the molding shrinkage (%) and the thermal elastic modulus (MPa) in the resin compositions of each Example and each Comparative Example. In FIG. 3, diamonds show examples and squares show comparative examples.

Although the present invention has been described more specifically based on the above examples, these are examples of the present invention, and various configurations other than the above can be adopted.

10 Electronic element 12 Electrode 20 Encapsulating resin 30, 32 Insulation layer 40 Via 42 Wiring 44 Solder ball 50 Carrier 52 Mount film 100 Electronic component 200 Molded body

Claims (5)

Thermosetting resin and
Cyclic carbodiimide compounds and
Inorganic filler and
A resin composition containing a curing agent .
The thermosetting resin contains an epoxy resin and contains
The inorganic filler contains silica, and the content of the inorganic filler is 80% by mass or more and 95% by mass or less with respect to the entire resin composition.
The curing agent is one or more selected from the group consisting of a polyfunctional phenol resin, a modified phenol resin, a phenol aralkyl type phenol resin, and a bisphenol compound.
A resin composition used for electronic parts, wherein the glass transition temperature of the cured product obtained by heat-treating the resin composition at 175 ° C. for 120 seconds and then heat-treating at 175 ° C. for 4 hours is 100 ° C. or higher. The resin composition according to claim 1 .
A resin composition further comprising a curing accelerator. The resin composition according to claim 1 or 2 .
A resin composition in which the content of the cyclic carbodiimide compound is 0.1% by mass or more and 2.0% by mass or less with respect to the entire resin composition. The resin composition according to any one of claims 1 to 3 .
A resin composition which is a resin composition for sealing. The resin composition according to any one of claims 1 to 4 .
A resin composition in which the epoxy resin comprises one or more selected from a biphenyl type epoxy resin, a polyfunctional epoxy resin, and a phenol aralkyl type epoxy resin.

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