JP2017125150A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition, a cured product of which is excellent in low contractility and low elasticity.SOLUTION: A curable resin composition is for use in an electronic component and comprises a thermosetting resin, a curing agent, a curing accelerator, a cyclic carbodiimide compound represented by formula (i) and an inorganic filler (X is a divalent or tetravalent organic group; if X is divalent, q is 0, and if X is tetravalent, q is 1; Ar1-Ar4 independently represent a C1-6 aromatic group substituted/unsubstituted with alkyl or phenyl).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin composition.

  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 with the lead frame. As such a technique, the thing of patent document 1 is mentioned. 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 is bonded to an epoxy resin and taken into the three-dimensional structure, and the isourea bond generated by the reaction improves the adhesion to the lead frame.

  Moreover, in patent document 2, the chain | strand-shaped polycarbodiimide compound by which the monocyanate was introduce | transduced into the terminal is used as a hardening | curing agent. This document describes the use of a polycarbodiimide compound having an average molecular weight of 300 to 300,000 in order to improve the moisture resistance reliability of the protective film covering the semiconductor element.

JP 2006-176549 A Japanese Patent Laid-Open No. 9-8181

As a result of studying a resin composition containing a thermosetting resin by the present inventor, the following has been found.
(1) The chain polycarbodiimide compound described in the above document may compete with other curing agents. For this reason, it is difficult to stably obtain a cured product of a low-shrinkage resin composition.
(2) From the viewpoint of suppressing low shrinkage, when the crosslinked structure is too dense, the elastic modulus of the cured product of the resin composition is increased. 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 was found that the trade-off relationship can be improved.
Thus, the present inventors have found that a resin composition excellent in low shrinkage and low elasticity can be stably obtained, and have completed the present invention.

According to the present invention,
A thermosetting resin;
There is provided a resin composition for use in electronic components, comprising a cyclic carbodiimide compound.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition used for the electronic component excellent in low shrinkage and low elasticity is provided.

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 elastic modulus (MPa) at the time of the resin composition of an Example and a comparative example.

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

The resin composition according to the present embodiment has a thermosetting resin and a cyclic carbodiimide compound. The resin composition can be widely used for various electronic components.
Moreover, the cyclic carbodiimide compound according to the present embodiment has a cyclic structure having one carbodiimide group in one ring. Moreover, the said cyclic carbodiimide compound means the monomer of the carbodiimide compound which does not contain the polycarbodiimide compound which contains the structural unit which has a carbodiimide group 3 or more in 1 molecule.

The present inventor found a novel function that the cyclic carbodiimide compound of the present embodiment acts as a curing accelerator from various experimental results. Although the detailed mechanism is not clear, the flow characteristics such as gel time and melt viscosity are not lowered, and the glass transition temperature (Tg) is increased. Therefore, the cyclic carbodiimide compound of this embodiment has a crosslinking density during post-cure. It is thought to work to increase Moreover, it can suppress competing with other hardening | curing agents. For this reason, it became possible to obtain stably the low shrinkage | contraction characteristic of the resin composition of this embodiment by utilizing a cyclic carbodiimide compound as a hardening accelerator.
Further, as a result of further investigation by the present inventors, it is newly possible to improve the trade-off relationship between low shrinkage and low elasticity in the resin composition of the present embodiment by using the cyclic carbodiimide compound. It was found.

  Hereinafter, each component which comprises the resin composition which concerns on this embodiment is explained in full detail.

(Thermosetting resin (A))
The resin composition according to the present embodiment has a thermosetting resin (A).
The thermosetting resin (A) is, for example, one or two selected from the group consisting of epoxy resins, phenol resins, oxetane resins, (meth) acrylate resins, unsaturated polyester resins, diallyl phthalate resins, and maleimide resins. Including the above. Among these, it is particularly preferable to include 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), monomers, oligomers and polymers generally having two or more epoxy groups in one molecule can be used, and the molecular weight and molecular structure thereof are particularly It is not limited. In this embodiment, the epoxy resin is, for example, a biphenyl type epoxy resin; a bisphenol type epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a tetramethylbisphenol F type epoxy resin; a stilbene type epoxy resin; a phenol novolac type epoxy. Resin, novolak type epoxy resin such as cresol novolak type epoxy resin; polyfunctional epoxy resin such as trisphenol type epoxy resin exemplified by triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, etc .; having phenylene skeleton Phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin having phenylene skeleton, phenol aralkyl type epoxy resin having biphenylene skeleton, bif Phenol aralkyl type epoxy resins such as naphthol aralkyl type epoxy resins having a nylene skeleton; naphthol type epoxy resins such as dihydroxynaphthalene type epoxy resins and epoxy resins obtained by glycidyl etherification of dihydroxynaphthalene dimers; triglycidyl isocyanurate; Triazine nucleus-containing epoxy resins such as monoallyl diglycidyl isocyanurate; including one or more selected from the group consisting of bridged cyclic hydrocarbon compound-modified phenolic epoxy resins such as dicyclopentadiene-modified phenolic epoxy resins . From the viewpoint of suppressing the warpage of the molded body and improving the balance of various properties such as filling property, heat resistance, and moisture resistance, among these, biphenyl type epoxy resin, polyfunctional epoxy resin, and phenol aralkyl type epoxy resin are selected. It is more preferable to include one or more types, and it is particularly preferable to include at least a 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 with respect to the entire resin composition. The above is particularly preferable. Thereby, the fluidity | liquidity at the time of shaping | molding can be improved. For this reason, it is possible to improve filling properties and molding stability. On the other hand, it is preferable that content of a thermosetting resin (A) is 15 mass% or less with respect to the whole resin composition, it is more preferable that it is 14 mass% or less, and it is 13 mass% or less. Is particularly preferred. Thereby, the moisture resistance reliability and reflow resistance of an electronic component can be improved. In addition, by controlling the content of the thermosetting resin (A) in such a range, it is possible to contribute to suppressing warpage of a molded body obtained by sealing an electronic element or the like with a resin composition. .

(Curing agent (B))
The resin composition of this embodiment can contain a hardening | curing agent (B), for example. The curing agent (B) contained in the resin composition can be roughly classified into three types, for example, a polyaddition type curing agent, a catalyst type curing agent, and a condensation type curing agent.

  Examples of the polyaddition type curing agent used as the curing agent (B) include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA), diaminodiphenylmethane (DDM), In addition to aromatic polyamines such as m-phenylenediamine (MPDA) and diaminodiphenylsulfone (DDS), polyamine compounds including dicyandiamide (DICY) and organic acid dihydrazide; hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride ( Acid anhydrides including alicyclic acid anhydrides such as MTHPA), trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA), etc .; novolac type Phenol resin curing agents such as enol resin, polyvinyl phenol 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 One type or two or more types selected from the group consisting of:

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

  The condensation type curing agent used as the curing agent (B) is, for example, one type selected from the group consisting of a resol 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 two or more types are included.

  Among these, it is more preferable to include a phenol resin-based curing agent from the viewpoint of improving the balance of flame resistance, moisture resistance, electrical characteristics, curability, storage stability, and the like. As the phenol resin-based curing agent, monomers, oligomers, and polymers in general having two or more phenolic hydroxyl groups in one molecule can be used, and the molecular weight and molecular structure are not particularly limited. The phenol resin-based curing agent used as the curing agent (B) is, for example, a novolac type phenol resin such as a phenol novolac resin, a cresol novolac resin, or a bisphenol novolac; a polyfunctional type phenol resin such as a polyvinyl phenol or a triphenolmethane type phenol resin; Modified phenol resins such as terpene-modified phenol resin and dicyclopentadiene-modified phenol resin; phenol aralkyl resins having a phenylene skeleton and / or biphenylene skeleton, phenol aralkyl type phenol resins such as naphthol aralkyl resin having phenylene and / or biphenylene skeleton; bisphenol One type or two or more types selected from the group consisting of bisphenol compounds such as A and bisphenol F are included. Among these, from the viewpoint of suppressing warpage of a molded article obtained by sealing an electronic element or the like with a resin composition, it preferably contains at least one of a polyfunctional phenol resin and a phenol aralkyl type phenol resin. preferable. In the present embodiment, the case where one or both of the polyfunctional epoxy resin as the thermosetting resin (A) and the polyfunctional phenol resin as the curing agent (B) is included in the resin composition, It can mention as an example of a desirable mode.

  In this embodiment, it is preferable that content of a hardening | curing agent (B) is 0.5 mass% or more with respect to the whole resin composition, It is more preferable that it is 1 mass% or more, 1.5 mass% The above is particularly preferable. Thereby, the excellent fluidity | liquidity can be implement | achieved at the time of shaping | molding, and the improvement of a filling property or a moldability can be aimed at. 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 with respect to the entire resin composition. preferable. Thereby, the moisture resistance reliability and reflow resistance of an electronic component can be improved. Further, by controlling the content of the curing agent (B) in such a range, it is possible to contribute to the suppression of warpage of a molded product obtained by sealing an electronic element or the like with a resin composition.

(Curing accelerator (C))
The resin composition according to this embodiment can contain, for example, a curing accelerator (C). The curing accelerator (C) may be anything that promotes the crosslinking 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, for example, an organic phosphine, a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, an adduct of a phosphonium compound and a silane compound, or the like. Compound: Amidine or tertiary amine exemplified by 1,8-diazabicyclo [5,4,0] undecene-7, benzyldimethylamine, 2-methylimidazole, etc. Nitrogen atom content such as quaternary salt of the amidine or amine One type or two or more types selected from compounds can be included. Among these, it is more preferable that a phosphorus atom containing compound is included from a viewpoint of improving curability.

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

  Examples of the tetra-substituted phosphonium compound that can be used in the resin composition include a compound 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 represents a phosphorus atom. R ⁴ , R ⁵ , R ⁶ and R ⁷ represent an aromatic group or an alkyl group. A is selected from a hydroxyl group, a carboxyl group, and a thiol group. An anion of an aromatic organic acid having at least one functional group in 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 in the aromatic ring. Represents an organic acid, where x and y are numbers 1 to 3, z is a number 0 to 3, and x = y.

Although the compound represented by General formula (6) is obtained as follows, for example, it is not limited to this. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed in an organic solvent and mixed uniformly to generate an aromatic organic acid anion in the solution system. Then, when water is added, the compound represented by the general formula (6) can be precipitated. 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 an aromatic ring, that is, phenols. And A is preferably an anion of the phenol. Examples of the phenols include monocyclic phenols such as phenol, cresol, resorcin, and catechol, condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and anthraquinol, bisphenols such as bisphenol A, bisphenol F, and bisphenol S, Examples include polycyclic phenols such as phenylphenol and biphenol.

  Examples of the phosphobetaine compound that can be used in the 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, 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) is obtained, for example, as follows. First, it is obtained through a step of bringing a triaromatic substituted phosphine, which is a third phosphine, into contact with a diazonium salt and replacing the triaromatic substituted phosphine with a diazonium group of the diazonium salt. However, the present invention is not limited to this.

  Examples of the adduct of a phosphine compound and a quinone compound that can be used in the resin composition include a compound 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 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 the same as each other. R ¹³ , R ¹⁴ and R ¹⁵ each represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different from each other, and R ¹⁴ and R ¹⁵ are bonded to each other. And may have a circular structure.)

  Examples of the phosphine compound used as an adduct of a phosphine compound and a quinone compound include an aromatic ring such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine. Those having a substituent or a substituent such as an alkyl group and an alkoxyl group are preferred, 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.

  Moreover, as a quinone compound used for the adduct of a phosphine compound and a quinone compound, a benzoquinone and anthraquinones are mentioned, Especially, p-benzoquinone is preferable from the point 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 capable of dissolving both organic tertiary phosphine and benzoquinone. The solvent is preferably a ketone such as acetone or methyl ethyl ketone, which has low solubility in the adduct. However, the present invention is not limited to this.

In the compound represented by the general formula (8), 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, ie, 1, A compound in which 4-benzoquinone and triphenylphosphine are added is preferred in that the thermal modulus of the cured product of the resin composition is lowered.

  Examples of the adduct of a phosphonium compound and a silane compound that can be used in the resin composition include a compound 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 each an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group. Represents a group, which may be the same or different from each other, wherein R ²⁰ is an organic group bonded to the groups Y ² and Y ^{3. In the} formula, R ²¹ represents the groups Y ⁴ and Y ⁵ ; Y ² and Y ³ represent a group formed by releasing a proton from a proton donating group, and 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 a group formed by releasing a proton from a proton donating group, and groups Y ⁴ and Y ⁵ in the same molecule are combined with a silicon atom to form a chelate structure. there ^{.R 20,} and ^{R 21} are mutually Or different ^{mere, Y 2, Y 3, Y} 4 and Y ⁵ may .Z ¹ also being the same or different organic group having an aromatic ring or a heterocyclic ring or fat, A group.)

In the general formula (9), examples of R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ include 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 groups such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group, and alkoxy groups An aromatic group having a substituent such as a hydroxyl group or an unsubstituted aromatic group is more preferable.

In the general formula ^{(9), R 20} is an organic group bonded to group ^{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 proton-donating groups releasing protons, and groups Y ² and Y ³ in the same molecule are combined with a silicon atom to form a chelate structure. Similarly, Y ⁴ and Y ⁵ are groups formed by proton-donating groups releasing protons, and groups Y ⁴ and Y ⁵ in the same molecule are combined 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. The proton donor is preferably an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule, and further has a carboxyl group or hydroxyl group on 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 Roxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, glycerin, and the like, among these, catechol, 1,2- Dihydroxynaphthalene and 2,3-dihydroxynaphthalene are more preferable.

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, a butyl group, Aliphatic hydrocarbon groups such as hexyl group and octyl group, aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group and biphenyl group, glycidyloxy groups such as glycidyloxypropyl group, mercaptopropyl group and aminopropyl group Reactive groups such as mercapto groups, alkyl groups having amino groups, and vinyl groups. Among these, methyl groups, ethyl groups, phenyl groups, naphthyl groups, and biphenyl groups are preferred from the viewpoint of thermal stability. More preferable.

  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 room temperature. Sodium methoxide-methanol solution is added dropwise with stirring. Furthermore, when a solution prepared by dissolving a tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide in methanol in methanol is added dropwise with stirring at room temperature, crystals are precipitated. The precipitated crystals are filtered, washed with water, and vacuum dried to obtain an adduct of a phosphonium compound and a silane compound. However, it is not limited to this.

  In this embodiment, the content of the curing accelerator (C) is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, based on the entire resin composition. It is particularly preferably 15% by mass or more. Thereby, the sclerosis | hardenability at the time of sealing molding can be improved effectively. 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 with respect to the entire resin composition. % Or less is particularly preferable. Thereby, the fluidity | liquidity at the time of sealing molding can be aimed at.

  The cyclic carbodiimide compound according to the present embodiment may be a cyclic carbodiimide compound represented by the following general formula (i). In addition, the cyclic carbodiimide compound shown by the following general formula (i) may have two carbodiimide groups in one molecule, and may have 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 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 each independently an aromatic group, and these aromatic groups each have 1 to 1 carbon atoms. 6 may be substituted with an alkyl group or a phenyl group.)

（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 each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.)

Examples of the cyclic carbodiimide compound represented by the general formula (i) include several compounds having the following structural formula.

As a manufacturing method of the cyclic carbodiimide compound which concerns on this embodiment, the following methods can be used, for example.
(I) A monocyclic carbodiimide compound can be produced, for example, by a production process including the following steps (1) to (3). First, a nitro body containing Ar ¹ and Ar ² is prepared (step (1)). Subsequently, an amine body is produced from the nitro body (step (2)). Then, a monocyclic carbodiimide compound can be manufactured from an amine body via a triphenylphosphine body or a urea body (process (3)).
(Ii) A bicyclic cyclic carbodiimide compound can be produced in the same manner as (i), except that, in the step (1), a nitro compound containing Ar ^{1 to} Ar ⁴ is prepared. it can.

  Moreover, the cyclic carbodiimide compound which concerns on this embodiment can be manufactured by a conventionally well-known method. Examples include a method of producing from an amine body via an isocyanate body, a method of producing from an amine body via an isothiocyanate body, a method of producing from a carboxylic acid body via an isocyanate body, and the like.

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

  In this embodiment, control of the resin design of the resin composition can be more easily realized by using the cyclic carbodiimide compound in combination with the curing accelerator (C). For this reason, for example, the balance between low shrinkage and low elasticity can be increased.

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

In the present embodiment, the average particle diameter (D ₅₀ ) of the filler (D) is preferably 0.01 μm or more and 1 μm or less, and more preferably greater than 1 μm and ₅₀ μm or less. By setting the average particle size to be equal to or greater than the above lower limit value, the fluidity of the resin composition can be improved, and the moldability can be improved more effectively. Moreover, it can suppress reliably that gate clogging etc. arise by making an average particle diameter below the said upper limit. In the present embodiment, the average particle diameter (D ₅₀ ) of the filler (D) is determined by using a commercially available laser diffraction particle size distribution measuring device (for example, SALD-7000, manufactured by Shimadzu Corporation). Can be measured on a volume basis, and the median diameter (D ₅₀ ) can be defined as the average particle diameter.

  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. Thereby, low moisture absorption and low thermal expansibility can be improved, and the moisture resistance reliability and reflow resistance of an electronic component can be improved more effectively. 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. Thereby, it becomes possible to improve the fluidity | liquidity and filling property at the time of shaping | molding of a resin composition more effectively. In addition, by controlling the content of the filler (D) within such a range, it is possible to contribute to suppressing warpage of a molded body obtained by sealing an electronic element or the like with a resin composition.

  In addition, as the filler (D), for example, two or more fillers having different average particle diameters (D50) can be used in combination. Thereby, the filling property of the filler (D) with respect to the whole resin composition can be improved more effectively. For this reason, it also becomes possible to contribute to suppression of the curvature of a molded object. Further, in the present embodiment, 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 greater than 1 μm and 50 μm or less improves the filling property of the resin composition. It is mentioned as one of the preferable aspects from a viewpoint of improving and suppressing the curvature of a molded object.

  In the present embodiment, when a first filler having an average particle diameter of 0.01 μm or more and 1 μm or less and a second filler having an average particle diameter of greater than 1 μm and 50 μm or less, the average particle diameter of 1 μm with respect to the entire filler (D) is included. For example, the content of the second filler of 50 μm or less is preferably 70% by mass or more, and more preferably 75% by mass or more. Thereby, it becomes possible to suppress the curvature of a molded object more effectively. On the other hand, the upper limit value of the content of the second filler having an average particle size larger than 1 μm and 50 μm or less with respect to the entire filler (D) is not particularly limited, and can be, for example, 99% by mass or less.

(Other ingredients)
In the resin composition of the present embodiment, for example, one kind of various additives such as a coupling agent, a release agent, a flame retardant, an ion scavenger, a colorant, a low stress agent, and an antioxidant, as necessary. Or 2 or more types can be mix | blended suitably.

  In the resin composition of this 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 is not particularly limited as long as it reacts between the epoxy resin and the inorganic filler and improves the interface strength between the epoxy resin and the inorganic filler. For example, epoxy silane, Aminosilane, ureidosilane, mercaptosilane, etc. are mentioned.

  Examples of the epoxy silane include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and β- (3,4 epoxycyclohexyl) ethyltrimethoxy. Silane etc. are mentioned. Examples of the 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-benzenedimethanane, etc. Examples of ureidosilane include γ-ureidopropyltriethoxysilane. , Hexamethyldisilazane, etc. Aminosila It may be used as a latent aminosilane coupling agent in which the primary amino moiety of the amine is protected by reacting with a ketone or aldehyde, and the aminosilane may have a secondary amino group, or as a mercaptosilane. For example, γ-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, and bis (3-triethoxysilylpropyl) disulfide are thermally decomposed. The silane coupling agent which expresses the function similar to a mercapto silane coupling agent by these etc. is mentioned etc. Moreover, these silane coupling agents may mix | blend what hydrolyzed beforehand. Two types of ring agents can be used alone It may be used in combination with the above.

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

  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 with respect to the entire resin composition. is there. If content of a coupling agent is more than the said lower limit, the interface strength of an epoxy resin and an inorganic filler will not fall, and favorable vibration resistance can be obtained. Moreover, as an upper limit of content of a coupling agent, 1 mass% or less is preferable with respect to the whole resin composition, More preferably, it is 0.8 mass% or less, Most preferably, it is 0.6 mass% or less. . If content of a coupling agent is below the said upper limit, the interface strength of an epoxy resin and an inorganic filler will not fall, and favorable vibration resistance can be obtained. Moreover, if content of coupling agents, such as a silane coupling agent, exists in the said range, the water absorption of the hardened | cured material of the resin composition for fixation will not increase, and favorable rust prevention property can be acquired. .

The mold release agent is, for example, one or two kinds selected from natural waxes such as carnauba wax, synthetic waxes such as montanic ester wax and polyethylene oxide wax, higher fatty acids such as zinc stearate and metal salts thereof, and paraffin. The above can be included.
The flame retardant can include one or more selected from, for example, 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 a hydrous oxide of an element selected from magnesium, aluminum, bismuth, titanium, and zirconium.
The colorant may include one or more selected from carbon black, bengara, and titanium oxide.
The low stress agent may include 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, it is 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, for example, halogen ions can be reduced by using a highly pure epoxy resin or the carbodiimide compound of the present embodiment. By setting the content of halogen ions to the upper limit value or less, a cured product of the resin composition having excellent durability can be obtained.
It is known that chlorine is generally increased when imidazole is used as a curing accelerator. Although the detailed mechanism is not clear, since the carbodiimide compound of this embodiment has a reaction mechanism different from imidazole, for example, it is considered that the binding chlorine in the epoxy resin does not desorb.

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

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

  In this embodiment, 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 preferably 100 ° C. or higher. More preferably, it is more preferably 135 ° C. or higher. Thereby, the heat resistance of an electronic component can be improved more effectively. On the other hand, the upper limit value of the glass transition temperature is not particularly limited, but can be, for example, 250 ° C. or lower. In the present embodiment, for example, the glass transition temperature (Tg) can be increased by increasing the softening point of the epoxy resin and the curing agent.

  In this embodiment, the linear expansion coefficient (CTE1) below the glass transition temperature of a 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 15 ppm. / ° C. or less is preferable, and 12 ppm / ° C. or less is more preferable. Moreover, it is preferable that the linear expansion coefficient (CTE1) in below glass transition temperature is 1 ppm / degrees C or more, for example. By controlling the CTE 1 in this way, it is possible to more reliably suppress the warpage of the molded body due to the difference in the linear expansion coefficient between the electronic element and the sealing resin. In the present embodiment, for example, the linear expansion coefficient (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 175 ° C. for 120 seconds and then heat treating at 175 ° C. for 4 hours is 40 ppm. / ° C. or less is preferable, and 38 ppm / ° C. or less is more preferable. Moreover, it is preferable that the linear expansion coefficient (CTE2) in excess of a glass transition temperature is 5 ppm / degrees C or more, for example. By controlling the CTE 2 in this manner, it is possible to more reliably suppress the warpage of the molded body due to the difference in the linear expansion coefficient between the electronic element and the sealing resin, particularly in a high temperature environment. In the present embodiment, for example, the linear expansion coefficient (CTE2) can be reduced by increasing the blending amount of the filler.

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

  In the present embodiment, the upper limit value 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 curbing the upper limit of the molding shrinkage rate, warping of the molded body can be suppressed. On the other hand, the lower limit value of the molding shrinkage rate 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 rate within the above range, it is possible to make the molded body easier to remove. The molding shrinkage is measured, for example, using a resin composition, using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.), a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds. It can carry out according to JISK6911 with respect to the test piece produced on condition of this. In the present embodiment, for example, the molding shrinkage can be suppressed to a desired numerical value by adjusting the amount of the carbodiimide compound added according to the composition of the thermosetting resin in the resin composition.

  In this embodiment, the storage elastic modulus (E ′) of a 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, measured at 260 ° C. Although the lower limit of is not specifically limited, For example, 500 MPa or more is preferable, 600 MPa or more is more preferable, and 700 MPa or more is more preferable. On the other hand, the upper limit value of the storage elastic modulus (E ′) is not particularly limited, but is preferably, for example, 1500 MPa or less, more preferably 1200 MPa or less, and further 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 method. 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. Storage elastic modulus at 260 ° C. when the obtained test piece was measured using DMA (Dynamic mechanical analysis / dynamic viscoelasticity measuring device) under the conditions of a three-point bending mode, a frequency of 10 Hz, and a measurement temperature of 260 ° C. (E ') is obtained. The unit is MPa.

Moreover, in the resin composition of this embodiment, it is preferable to satisfy the following condition (1), and it is more preferable to satisfy (2).
(1) The mold shrinkage is not more than the above upper limit, and the thermal elastic modulus is not more than the above upper limit.
(2) Satisfying (1) and satisfying that “Y (%) + αX (MPa)”, which is a relational expression between the mold shrinkage rate and the thermal elastic modulus, is 0.15% or less.
In the relational expression (2) above, Y represents the molding shrinkage rate and X represents the thermal elastic modulus. Further, 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) will be described.
As a result of studies by the present inventors, a certain relationship has been 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 rate and the elastic modulus during heating was obtained from a comparative example of a normal resin composition not containing a cyclic carbodiimide compound. . From this calibration curve, it can be seen that when the molding shrinkage is small and the thermal elastic modulus is small, a resin composition excellent in low shrinkage and low elasticity is obtained. That is, the calibration curve shown in FIG. 3 is an index indicating both low shrinkage and low elasticity.
As a result of concrete examination of this index, a relational expression that “Y (%) + αX (MPa)” is 0.15% or less is derived.
For example, 0.15% indicates a 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 not containing a 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 required in a predetermined technical field, and has lower shrinkage 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 resin composition preferably has a spiral flow length of 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 shape | molding a resin composition can be improved more effectively. The upper limit value of the flow length of the spiral flow is not particularly limited, but can be, for example, 200 cm or less. The spiral flow is measured by using, for example, a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.) and a mold temperature of 175 ° C. for a spiral flow measurement mold according to EMMI-1-66. The resin composition is injected under conditions of an injection pressure of 6.9 MPa and a curing time of 120 seconds, and the flow length is measured. In the present embodiment, the spiral flow can be increased by using, for example, fused spherical silica as a filler, lowering the softening point of an epoxy resin or a curing agent, or reducing the amount of a curing accelerator.

  In the present embodiment, the resin composition preferably has a gel time of, for example, 10 seconds to 50 seconds, and more preferably 15 seconds to 45 seconds. Thereby, a mold cycle can be made quick, improving the moldability of a resin composition. The gel time can be measured by measuring the time (gel time) until the resin composition is melted on a hot plate heated to 175 ° C. and then cured while being kneaded with a spatula. In this Embodiment, the said gel time can be reduced by increasing the quantity of a hardening accelerator and a carbodiimide compound, for example.

  In the present embodiment, the glass transition temperature, molding shrinkage rate, spiral flow, gel time, and thermal elastic modulus are appropriately adjusted, for example, the types and blending ratios of the components of the resin composition, the resin composition preparation method, and the like. Can be controlled. Among these, for example, by using a cyclic carbodiimide compound, the spiral flow and the gel time can be mentioned as elements for obtaining a desired numerical range. In addition, the use and blending amount of a cyclic carbodiimide compound, the combined use of other curing accelerators, the selection of a resin, and the like can be cited as factors for lowering the molding shrinkage rate and lowering the thermal modulus.

  Hereinafter, the manufacturing method of the resin composition which concerns on this embodiment is demonstrated.

  The method for producing the resin composition of the present embodiment is not particularly limited. For example, after mixing the above-described components by a known means, further melt-kneading with a kneader such as a roll, kneader or extruder, and cooling. Dispersed or fluidized as appropriate by pulverized granules, tablets that have been compressed into tablets after pulverization, and if necessary, sieving the above-mentioned pulverized products, centrifugal milling methods, hot cut methods, etc. Granules and the like produced by the condylar method with adjusted etc. can be used as the resin composition.

  The resin composition according to the present embodiment can be used for various electronic components. As an example of the application of the resin composition used for such an electronic component, a sealing material (sealing resin composition) for sealing an electronic component such as a semiconductor element or an electronic element, a substrate material (core layer, Build-up layer, outermost solder resist layer, etc.), insulating layers used for light receiving elements such as white diodes, and the like.

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

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

  The resin composition according to this embodiment is preferably used for a sealing resin constituting a wafer level package obtained by resin-sealing a circuit surface of a wafer, but is used for a pseudo wafer described below. It can also be applied to a sealing resin.

Next, details of the electronic component 100 according to the present embodiment will be described. An electronic component 100 illustrated in FIG. 1 is a semiconductor package including an electronic element 10 that is a semiconductor element and a sealing resin 20 that seals the electronic element 10. In FIG. 1, an electronic component 100, particularly a wafer level package, is shown. The electronic component 100 according to the present embodiment is not limited to that shown in FIG. The electronic component 100 may be 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, for example. Further, the electronic component 100 may be an in-vehicle electronic control unit obtained by sealing together a wiring board and a plurality of electronic elements 10 mounted on the wiring board with a resin composition, for example.
The electronic component 100 may include a metal member and a sealing resin 20 that seals 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 a general electronic device, but a semiconductor sealing resin composition used for the semiconductor package and an ECU sealing used for the vehicle-mounted electronic control unit (ECU). The present invention can be applied to a resin composition or a sealing resin composition for a resin substrate used for the resin substrate.

  An electronic component 100 shown in FIG. 1 includes an electronic element 10 provided with an electrode 12 on one surface, 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. On the insulating layer 30, a wiring 42 constituting a rewiring layer is provided so as to be connected to the via 40. An insulating layer 32 that is a solder resist layer is provided on the insulating layer 30 and the wiring 42. The insulating layer 32 has an opening connected 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 through the solder balls 44.

Next, a method for manufacturing the electronic component 100 will be described.
The manufacturing method of the electronic component 100 includes a step of sealing and molding the electronic element 10 or the metal member using the above-described resin composition. Thereby, it can suppress that curvature generate | occur | produces in the molded object obtained by sealing the electronic element 10 or a metal member.

FIG. 2 is a cross-sectional view illustrating 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 using a pseudo wafer formed by mounting a plurality of electronic elements 10 as semiconductor elements on a carrier 50 is illustrated. According to the manufacturing method shown in FIG. 2, the electronic component 100 can be thinned. In addition, the manufacturing method of the electronic component 100 which concerns on this embodiment is not limited to what is 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. Moreover, the electronic component 100 may be manufactured by, for example, MAP (Mold Array Package) molding.
Hereinafter, an example of the manufacturing method of 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 a mount film 52 formed on a carrier 50. As a result, a pseudo wafer is formed. The carrier 50 has a plate shape, for example. The mount film 52 is a heat peelable 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 disposed on the mount film 52 such that one surface of the electronic element 10 on which the external electrode is provided faces the mount film 52.

  Next, as shown in FIG. 2B, the electronic element 10 is encapsulated using the resin composition. The process of sealing and molding is performed on the electronic element 10 at the wafer level, for example. Note that sealing molding at the wafer level means that a plurality of electronic elements 10 constituting a pseudo wafer are collectively sealed with a resin composition as shown in FIG. This is a concept including collectively sealing with a resin composition. Thereby, the molded object 200 comprised by the some electronic element 10 and the sealing resin 20 which seals the some electronic element 10 will be formed. In the present embodiment, the molded body 200 is formed using the above-described resin composition. For this reason, even if it is the molded object 200 with a large area and a thin film thickness, it becomes possible to suppress curvature.

  Although the sealing molding by the resin composition of this embodiment is not specifically limited, For example, it can carry out by compression molding. In this case, the compression molding is more preferably performed, for example, under a temperature condition of 120 ° C. or higher and 160 ° C. or lower. Thereby, a resin composition can fully be hardened. Further, when the molded body 200 is cooled, the molded body 200 can be prevented from warping due to the shrinkage of the sealing resin 20.

  Next, as shown in FIG. 2C, the molded body 200 is peeled 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 insulating layer 30 described above, 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 on the wiring 42. 32. Next, a plurality of solder balls 44 connected to the wiring 42 are formed on the rewiring layer. Thereafter, the molded body 200 is diced into individual electronic components 100.
In the present embodiment, for example, the electronic component 100 is formed in this way.

  It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  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 composition shown in Table 1, a thermosetting resin (A), a curing agent (B), a cyclic carbodiimide compound, a curing accelerator (C), a silane coupling agent, a release agent, and a colorant are mixed with a mixer. And mixed to give a mixture. Next, the filler (D) was added to the mixture according to the formulation shown in Table 1, and then mixed using a mixer. Next, the obtained mixture was roll kneaded at 70 to 100 ° C. Next, the kneaded mixture was cooled and pulverized to obtain a granular resin composition.

  About each comparative example, the resin composition was prepared as follows. First, according to the composition shown in Table 1, the thermosetting resin (A), the curing agent (B), the curing accelerator (C), the silane coupling agent, the release agent, and the colorant are mixed using a mixer. To obtain a mixture. Next, the filler (D) was added to the mixture according to the formulation shown in Table 1, and then mixed using a mixer. Next, the obtained mixture was roll kneaded at 70 to 100 ° C. Next, the kneaded mixture was cooled and pulverized to obtain a granular resin composition.

  In addition, the unit of the mixture ratio of each component in Table 1 is mass%. Moreover, the detail of each component in Table 1 is as follows.

(A) Thermosetting resin Thermosetting resin 1: Phenol 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) Curing agent Curing agent 1: Phenol aralkyl resin having a biphenylene skeleton (MEH-7851SS, manufactured by Meiwa Kasei Co., Ltd.)
Curing agent 2: Phenol 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 Kay Kasei Co., Ltd.)

(D) Filler inorganic filler 1: Spherical fused silica (manufactured by Denki Kagaku Kogyo Co., Ltd., FB-950FC, average particle diameter D ₅₀ : 24 μm)
Inorganic filler 2: Spherical fused silica (manufactured by Admatechs Co., Ltd., SO-25R, average particle diameter D ₅₀ : 0.5 μm)
The average particle size (D ₅₀ ) of the filler (D) was measured by measuring the particle size distribution on a volume basis using a laser diffraction particle size distribution analyzer (SALD-7000, manufactured by Shimadzu Corporation). The diameter (D ₅₀ ) was defined as the average particle diameter.

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

Mold release agent: Carnauba wax (Nikko Fine Co., Ltd., Nikko Carnauba)
Colorant: Carbon black (Mitsubishi Chemical Corporation MA600)

(Spiral flow)
About each Example and each comparative example, spiral flow measurement was performed with respect to the obtained resin composition. Spiral flow measurement was performed using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.) in a 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 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, linear expansion coefficient)
About each Example and each comparative example, the glass transition temperature (Tg) and the linear expansion coefficient (CTE1, CTE2) of the hardened | cured material of the obtained resin composition were measured as follows. First, using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.), the resin composition was injected and molded at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds. A test piece of × 4 mm was obtained. Then, after the obtained test piece was post-cured at 175 ° C. for 4 hours, using a thermomechanical analyzer (manufactured by Seiko Denshi Kogyo Co., Ltd., TMA100), a measurement temperature range of 0 ° C. to 320 ° C., a rate of temperature increase The measurement was performed under the condition of 5 ° C./min. From this measurement result, the glass transition temperature (Tg), the linear expansion coefficient (CTE1) below the glass transition temperature, and the linear expansion coefficient (CTE2) when the glass transition temperature was exceeded were calculated. The results are shown in Table 1.

(Mold shrinkage)
About each Example and each comparative example, the molding shrinkage rate 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.) at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds. This was performed according to JIS K 6911. The results are shown in Table 1.

About each Example and each comparative example, the elasticity modulus at the time of the obtained resin composition was measured. Transfer molding was performed using the 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. It is a thermal elastic modulus when the obtained test piece was measured using DMA (Dynamic mechanical analysis / dynamic viscoelasticity measuring device) 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.
FIG. 3 shows the relationship between the molding shrinkage (%) and the thermal elastic modulus (MPa) in the resin compositions of the examples and comparative examples. In FIG. 3, diamonds indicate examples, and squares indicate comparative examples.

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

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

Claims (7)

A thermosetting resin;
The resin composition used for an electronic component containing a cyclic carbodiimide compound. The resin composition according to claim 1,
A resin composition further comprising a curing agent. The resin composition according to claim 1 or 2,
A resin composition further comprising an inorganic filler. The resin composition according to claim 3,
A resin composition in which the inorganic filler contains silica. The resin composition according to any one of claims 1 to 4,
A resin composition further comprising a curing accelerator. The resin composition according to any one of claims 1 to 5,
Content of the said cyclic carbodiimide compound is a resin composition which is 0.1 to 2.0 mass% with respect to the whole said resin composition. The resin composition according to any one of claims 1 to 6,
The resin composition in which the said thermosetting resin contains an epoxy resin.

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