JP6686457B2 - Sealing resin composition and electronic device - Google Patents

Description

  The present invention relates to a sealing resin composition and an electronic device.

  Various techniques have been studied so far as a sealing resin composition for sealing a semiconductor element. A curing agent is mixed with the epoxy resin for the purpose of improving the adhesion to the lead frame. As such a technique, the technique described in Patent Document 1 can be cited. In this document, a 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 polycarbodiimide compound having a monocyanate introduced at the terminal is used as a curing agent. The document describes that a polycarbodiimide compound having an average molecular weight of 300,000 to 300,000 is used in order to improve the moisture resistance reliability of the protective film covering the semiconductor element.

JP, 2006-176549, A JP, 9-8181, A

  As a result of examination by the present inventor, the following has been clarified. The polycarbodiimide compounds described in the above documents may compete with other curing agents. For this reason, it has been found difficult to stably obtain a sealing resin composition with low shrinkage.

  The present inventor has further studied and found that the monomer of the carbodiimide compound can be used as a curing accelerator. As a result of further studies based on such knowledge, it was found that a sealing resin composition having low shrinkage can be stably obtained by using the monomer of the carbodiimide compound, and the present invention has been completed.

According to the invention,
A thermosetting resin,
With a carbodiimide compound monomer having a carbodiimide group in the molecule, and having no isocyanate group,
A filler,
A resin composition for encapsulation, comprising:
The thermosetting resin contains an epoxy resin,
The monomer of the carbodiimide compound is selected from the group consisting of dicyclohexylcarbodiimide, ethylcyclohexylcarbodiimide, diphenylcarbodiimide, dimethylcarbodiimide, diethylcarbodiimide, diisopropylcarbodiimide, diisobutylcarbodiimide, t-butylisopropylcarbodiimide, di-t-butylcarbodiimide, dioctylcarbodiimide. One or two or more
There is provided a sealing resin composition in which the content of the filler is 80% by mass or more and 95% by mass or less with respect to the entire sealing resin composition.

  According to the present invention, there is provided an electronic device including a cured product of the above sealing resin composition.

  According to the present invention, a sealing resin composition excellent in low shrinkage characteristics and an electronic device are 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.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same constituents will be referred to with the same numerals, and the description thereof will not be repeated.

  The encapsulating resin composition according to the present embodiment includes a thermosetting resin and a carbodiimide compound monomer. The monomer of the carbodiimide compound is a compound that has a carbodiimide group in the molecule and does not have an isocyanate group. In the present embodiment, the carbodiimide compound monomer means that a polycarbodiimide compound containing three or more carbodiimide group-containing structural units in one molecule is not included.

  From various experimental results, the present inventor has found a novel function that the monomer of the carbodiimide compound of the present embodiment acts as a curing accelerator. Although the detailed mechanism is not clear, since the glass transition temperature (Tg) is increased without lowering the flow characteristics such as gel time and melt viscosity, the monomer of the carbodiimide compound of the present embodiment is crosslinked during post cure. It is thought to work to increase the density. Further, it is possible to suppress competition with other curing agents. Therefore, by utilizing the monomer of the carbodiimide compound as the curing accelerator, it becomes possible to stably obtain the low shrinkage property of the encapsulating resin composition of the present embodiment.

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

(Thermosetting resin (A))
The encapsulating resin composition according to the present embodiment has a thermosetting resin (A).
The thermosetting resin (A) is, for example, one or two kinds selected from the group consisting of 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 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), all monomers, oligomers, and polymers having two or more epoxy groups in one molecule can be used, and the molecular weight and the molecular structure thereof are particularly 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 tetramethylbisphenol F type epoxy resin; a stilbene type epoxy resin; a phenol novolac type epoxy resin. Resin, cresol novolak type epoxy resin or other novolak type epoxy resin; triphenol methane type epoxy resin, polyfunctional epoxy resin such as trisphenol type epoxy resin such as alkyl-modified triphenol methane type epoxy resin; 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 resin such as naphthol aralkyl type epoxy resin having a nylene skeleton; dihydroxynaphthalene type epoxy resin, naphthol type epoxy resin such as epoxy resin obtained by glycidyl etherification of dihydroxynaphthalene dimer, triglycidyl isocyanurate, Triazine nucleus-containing epoxy resin such as monoallyl diglycidyl isocyanurate; One or more selected from the group consisting of bridged cyclic hydrocarbon compound-modified phenolic epoxy resin such as dicyclopentadiene modified phenolic epoxy resin . 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, biphenyl type epoxy resin, polyfunctional epoxy resin, and phenol aralkyl type epoxy resin are selected from these. It is more preferable to contain one or two or more kinds thereof, and it is particularly preferable to contain at least a polyfunctional epoxy resin.

  In the present embodiment, the content of the thermosetting resin (A) is preferably 1% by mass or more, and more preferably 2% by mass or more, based on the entire encapsulating resin composition. It is particularly preferable that the content is 5% by mass or more. 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 encapsulating resin composition. Is particularly preferable. Thereby, the moisture resistance reliability and the reflow resistance of the electronic component can be improved. Further, by controlling the content of the thermosetting resin (A) in such a range, it may contribute to suppressing warpage of a molded body obtained by sealing an electronic element or the like with a sealing resin composition. It is possible.

(Curing agent (B))
The encapsulating resin composition of the present embodiment can include, for example, a curing agent (B). The curing agent (B) contained in the encapsulating 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 diaminodiphenyl sulfone (DDS), polyamine compounds containing dicyandiamide (DICY), organic acid dihydralazide, etc .; hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride ( Acid anhydrides containing alicyclic acid anhydrides such as MTHPA), trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), aromatic acid anhydrides such as benzophenonetetracarboxylic acid (BTDA); novolak type Phenol resin type 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 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); 2-methyl. Imidazole compounds such as imidazole and 2-ethyl-4-methylimidazole (EMI24); and 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 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 includes two or more types.

  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, all monomers, oligomers and polymers having two or more phenolic hydroxyl groups in one molecule can be used, and their molecular weight and molecular structure are not particularly limited. Examples of the phenol resin type curing agent used as the curing agent (B) include novolac type phenol resins such as phenol novolac resin, cresol novolac resin and bisphenol novolac; polyfunctional phenol resins such as polyvinyl phenol and triphenol methane type phenol resin; Modified phenolic resins such as terpene-modified phenolic resins and dicyclopentadiene-modified phenolic resins; phenolaralkyl-type phenolic resins such as phenolaralkyl resins having a phenylene skeleton and / or biphenylene skeleton, naphtholaralkyl resins having a phenylene and / or biphenylene skeleton; bisphenols A, one or more selected from the group consisting of bisphenol compounds such as bisphenol F are included. Among these, at least one of a polyfunctional phenol resin and a phenol aralkyl type phenol resin is included from the viewpoint of suppressing warpage of a molded body obtained by sealing an electronic element or the like with a sealing resin composition. Is more preferable. In the present embodiment, one or both of a polyfunctional epoxy resin as a thermosetting resin (A) and a polyfunctional phenol resin as a curing agent (B) are contained in the encapsulating resin composition. The case can be mentioned as an example of a preferred embodiment.

  In the present embodiment, the content of the curing agent (B) is preferably 0.5% by mass or more, and more preferably 1% by mass or more, based on the entire encapsulating resin composition. It is particularly preferable that the content is 5% by mass or more. As a result, excellent fluidity can be achieved during molding, and filling properties 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 7% by mass or less based on the whole encapsulating resin composition. Is particularly preferable. Thereby, the moisture resistance reliability and the reflow resistance of the 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 suppressing warpage of a molded product obtained by sealing an electronic element or the like with a sealing resin composition. is there.

(Curing accelerator (C))
The encapsulating resin composition according to the present embodiment may include, for example, a curing accelerator (C). The curing accelerator (C) may be any one as long as it accelerates the crosslinking reaction between the thermosetting resin resin (A) (for example, epoxy resin) and the curing agent (B) (for example, phenol resin 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, an adduct of a phosphonium compound and a silane compound, and the like. Compounds: nitrogen atom-containing compounds such as 1,8-diazabicyclo [5,4,0] undecene-7, benzyldimethylamine, 2-methylimidazole, amidines and tertiary amines, quaternary salts of the amidines and amines It may contain one or more selected from the compounds. Among these, it is more preferable to include a phosphorus atom-containing compound from the viewpoint of improving curability.

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

  Examples of the tetra-substituted phosphonium compound that can be used in the encapsulating 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 above 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. AH represents an anion of an aromatic organic acid having at least one functional group in the aromatic ring, wherein 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, x and y are numbers from 1 to 3, z is a number from 0 to 3, and x = y.)

The compound represented by the general formula (6) can be obtained, for example, as follows, but is not limited thereto. First, a tetra-substituted phosphonium halide, an aromatic organic acid, and a base are mixed in an organic solvent and uniformly mixed to generate an aromatic organic acid anion in the solution system. Then, by adding water, 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 the aromatic ring, that is, phenols. And A is preferably the 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, 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 encapsulating 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 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) 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 substituting the triaromatic-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 encapsulating 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 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 represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and may be the same or different, and R ¹⁴ and R ¹⁵ are bonded to each other. And may have a ring structure.)

  Examples of the phosphine compound used for the adduct of the phosphine compound and the quinone compound include aromatic compounds 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 preferable, and examples of the substituent such as an alkyl group and an alkoxyl group include those having a carbon number of 1 to 6. From the viewpoint of easy availability, triphenylphosphine is preferable.

  In addition, examples of the quinone compound used for the 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 the organic tertiary phosphine and the benzoquinone 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), 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 from the viewpoint of lowering the elastic modulus of the cured product of the encapsulating resin composition when heated.

  Examples of the adduct of the phosphonium compound and the silane compound that can be used in the encapsulating 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 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 heterocycle, or a fatty group. R ²⁰ represents a group group and 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 is a group Y ⁴ and Y ⁵ . 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 bond with a silicon atom to form a chelate structure. Y ⁴ and Y ⁵ represent a group in which a proton donating group releases a proton, and the groups Y ⁴ and Y ⁵ in the same molecule bond 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, It is a group.)

In formula (9), R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are, for example, phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group. , An ethyl group, an n-butyl group, an n-octyl group, a cyclohexyl group, and the like. Among these, a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, an alkyl group such as a hydroxynaphthyl group, and an alkoxy group. 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 the groups Y ² and Y ³ . Similarly, R ²¹ is an organic group bonded to the groups Y ⁴ and Y ⁵ . Y ² and Y ³ are groups formed by releasing a proton from a proton donating group, and the groups Y ² and Y ³ in the same molecule bond with a silicon atom to form a chelate structure. Similarly, Y ⁴ and Y ⁵ are groups formed by releasing a proton from a proton donating group, and the groups Y ⁴ and Y ⁵ in the same molecule bond 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 the group represented by —Y ² —R ²⁰ —Y ³ — and Y ⁴ —R ²¹ —Y ⁵ — in the general formula (9), a 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 adjacent carbon atoms forming 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 forming an aromatic ring is more preferable, and 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-hi Roxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, glycerin and the like can be mentioned. 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 , A mercapto group, an alkyl group having an amino group, a reactive substituent such as a vinyl group, and the like. Among these, a methyl group, an ethyl group, a phenyl group, a naphthyl group, and a biphenyl group are preferable from the viewpoint of thermal stability. , And more preferable.

  As a method for producing an adduct of a phosphonium compound and a silane compound, a flask containing methanol is dissolved by adding a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene, and then dissolving at room temperature. A sodium methoxide-methanol solution is added dropwise with stirring. Further, a solution prepared by dissolving a tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide in methanol prepared in advance therein is added dropwise under stirring at room temperature to precipitate crystals. 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 the present embodiment, the content of the curing accelerator (C) is preferably 0.05% by mass or more, and more preferably 0.10% by mass or more, based on the whole encapsulating resin composition. , 0.15 mass% or more is particularly preferable. 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, and more preferably 4.0% by mass or less, based on the whole encapsulating resin composition. It is particularly preferable that the content is 0.5% by mass or less. Thereby, the fluidity at the time of sealing and molding can be improved.

［一般式（Ｉ）中、Ｒ^１及びＲ^２はそれぞれ独立に有機基を示す。Ｒ^１及とＲ^２は互いに環を形成してもよい。］ The carbodiimide compound monomer according to the present embodiment may be a carbodiimide compound represented by the following general formula (I). The carbodiimide compound represented by the following general formula (I) may have two carbodiimide groups or one carbodiimide group in one molecule.

[In the general formula (I), R ¹ and R ² each independently represent an organic group. R ¹ and R ² may form a ring with each other. ]

The above R ¹ and R ² each represent a linear, branched or cyclic alkyl group or a substituted or unsubstituted aryl group, and may be the same or different.
The alkyl group is not particularly limited, but is preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3 , 3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, cyclohexylmethyl group, n-octyl group and the like are used.

The aryl group is not particularly limited, but for example, an aryl group having 6 to 20 carbon atoms is used. Such an aryl group may be unsubstituted or may have a substituent.
In the present embodiment, the aryl group represents, for example, a carbocyclic aromatic group such as a phenyl group and a naphthyl group, and a heterocyclic aromatic group such as a furyl group, a thienyl group and a pyridyl group. Further, the substituent of the aryl group is not particularly limited, and examples thereof include a halogen atom, a sulfur atom, a carboxyl group, a cyano group, a nitro group, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. , A linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, and the like. In this embodiment, the substituents may be linked to each other to form a ring.

In the present embodiment, R ¹ and R ² each preferably have a cyclic structure containing a substituted or unsubstituted cycloalkyl group or a substituted or unsubstituted aromatic group, and a substituted or unsubstituted aromatic group. It is more preferable to have a group group, and it is further preferable to have a substituted aromatic group.

  The monomer of the carbodiimide compound of the present embodiment is not particularly limited, and examples thereof include dicyclohexylcarbodiimide, ethylcyclohexylcarbodiimide, diphenylcarbodiimide, dimethylcarbodiimide, diethylcarbodiimide, diisopropylcarbodiimide, diisobutylcarbodiimide, t-butylisopropylcarbodiimide, di-t- Butyl carbodiimide, dioctyl carbodiimide and the like may be used. From these, one kind or two or more kinds may be used.

  In the present embodiment, the lower limit value of the content of the monomer of the carbodiimide compound is not particularly limited, but is preferably 0.1% by mass or more with respect to the entire encapsulating resin composition according to the present embodiment, and is 0.15%. Mass% or more is more preferable, and 0.2 mass% or more is particularly preferable. On the other hand, the upper limit of the content of the carbodiimide compound monomer 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 monomer of the carbodiimide compound within the above range, not only a low shrinkage property can be obtained, but also a sealing resin composition having an excellent balance of crosslink density and fluidity property can be obtained.

  In the present embodiment, the resin design of the resin composition can be more easily controlled by using the monomer of the carbodiimide compound in combination with the curing accelerator (C). Therefore, for example, the balance between low shrinkage and low elasticity can be enhanced.

(Filler (D))
The encapsulating resin composition of this embodiment may include 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 more than 1 μm and ₅₀ μm or less. By setting the average particle diameter to be the above lower limit or more, it becomes possible to improve the fluidity of the encapsulating resin composition and to improve the moldability more effectively. Further, by setting the average particle diameter to be equal to or less than the above upper limit, it is possible to reliably suppress the occurrence of gate clogging and the like. In addition, in this 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 taken 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 further preferably 85% by mass or more with respect to the entire encapsulating resin composition. Especially preferred. As a result, low hygroscopicity and low thermal expansion can be improved, and the moisture resistance reliability and reflow resistance of the 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 90% by mass or less with respect to the entire encapsulating resin composition. Is particularly preferable. This makes it possible to more effectively improve the fluidity and filling properties of the encapsulating resin composition during molding. Further, 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 sealing resin composition. is there.

Further, as the filler (D), for example, two or more kinds of fillers having different average particle diameters (D ₅₀ ) can be used in combination. Thereby, the filling property of the filler (D) with respect to the whole encapsulating resin composition can be more effectively enhanced. Therefore, it is possible to contribute to the suppression of warpage of the molded body. In addition, in the present embodiment, the inclusion of 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 1 μm or more and 50 μm or less makes the sealing resin composition. From the viewpoint of improving the filling property and suppressing the warp of the molded body, it is mentioned as one of the preferable embodiments.

  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 1 μm or more and 50 μm or less are included, the average particle size of 1 μm with respect to the entire filler (D). The content of the second filler having a larger size of 50 μm or less is, for example, preferably 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 body. On the other hand, the upper limit of the content of the second filler having an average particle size of 1 μm or more and 50 μm or less with respect to the entire filler (D) is not particularly limited and can be, for example, 99 mass% or less.

(Other ingredients)
In the encapsulating resin composition of the present embodiment, if necessary, for example, 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. One kind or two or more kinds among them can be appropriately mixed.

  In the encapsulating 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 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, for example, epoxysilane, Aminosilane, ureidosilane, mercaptosilane and the like can be mentioned.

  Examples of the epoxy silane include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4epoxycyclohexyl) ethyltrimethoxy. Examples include silane. 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 the 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 an aldehyde, and the aminosilane may have a secondary amino group. Are thermally decomposed, for example, γ-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, and bis (3-triethoxysilylpropyl) disulfide. Examples of the silane coupling agent include a silane coupling agent that exhibits the same function as the mercapto silane coupling agent, etc. Further, these silane coupling agents may be preliminarily hydrolyzed. Two types of ring agents, even if used alone It may be used in combination with the above.

  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, particularly preferably 0.1% by mass, based on the whole encapsulating resin composition. % Or more. When the content of the coupling agent is at least the above lower limit, the interfacial 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, based on the whole encapsulating resin composition. It is the following. When the content of the coupling agent is not more than the above upper limit, the interfacial 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 is one or two types selected from natural waxes such as carnauba wax, synthetic waxes such as montanic acid ester wax and oxidized polyethylene wax, higher fatty acids such as zinc stearate and metal salts thereof, and paraffin. The above can be included.
The flame retardant may include, for example, one kind or two or more kinds selected from magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene. The colorant can include, for example, carbon black.
The ion scavenger may include one or more selected from hydrotalcites or hydrous oxides of elements selected from magnesium, aluminum, bismuth, titanium and zirconium.
The colorant may include one kind or two or more kinds selected from carbon black, red iron oxide, and titanium oxide.
The low stress agent may include one or more selected from polybutadiene compounds, acrylonitrile butadiene copolymer compounds, silicone oils, and silicone compounds such as silicone rubber.

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

  The concentration of the halogen ion can be obtained as follows. First, the encapsulating resin composition 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 is treated in pure water at 120 ° C. for 24 hours to extract ions in pure water, which can then be measured using ICP-MS (inductively coupled plasma ion source mass spectrometer). In the present embodiment, the halogen atom includes a binding halogen component contained in the epoxy resin of the encapsulating resin composition and a halogen component free from the epoxy resin. The halogen ion whose concentration is measured refers to the free halogen component derived from the two.

  Hereinafter, a method for evaluating the properties of the encapsulating resin composition will be described.

  In the present embodiment, the glass transition temperature of a cured product obtained by heat-treating the encapsulating resin composition at 175 ° C. for 120 seconds and then at 175 ° C. for 4 hours is preferably 100 ° C. or higher. , 120 ° C. or higher 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 may 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 points of the epoxy resin and the curing agent.

  In the present embodiment, the coefficient of linear expansion (CTE1) of the cured product obtained by heat-treating the encapsulating resin composition at 175 ° C. for 120 seconds and then at 175 ° C. for 4 hours at a glass transition temperature or lower. Is preferably 15 ppm / ° C. or lower, and more preferably 12 ppm / ° C. or lower. Further, the coefficient of linear expansion (CTE1) at the glass transition temperature or lower is preferably, for example, 1 ppm / ° C. or higher. By controlling CTE1 in this way, it is possible to more reliably suppress the warp 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 coefficient of linear expansion (CTE2) of the cured product obtained by heat-treating the encapsulating resin composition at, for example, 175 ° C. for 120 seconds and then at 175 ° C. for 4 hours when the glass transition temperature is exceeded. Is preferably 40 ppm / ° C. or lower, and more preferably 38 ppm / ° C. or lower. Further, the coefficient of linear expansion (CTE2) at a temperature exceeding the glass transition temperature is preferably, for example, 5 ppm / ° C. or more. By controlling CTE2 in this way, it is possible to more reliably suppress the warp of the molded body due to the difference in the linear expansion coefficient between the electronic element and the sealing resin, especially 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 encapsulating resin composition can be measured, for example, as follows. First, using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.), a sealing resin composition was injection-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 10 mm × 4 mm × 4 mm is obtained. Then, after the obtained test piece was post-cured at 175 ° C. for 4 hours, a thermomechanical analyzer (manufactured by Seiko Denshi Kogyo Co., Ltd., TMA100) was used to measure temperature range 0 ° C. to 320 ° C. at a heating rate. The measurement is performed under the condition of 5 ° C / min. From the measurement results, the glass transition temperature, the coefficient of linear expansion (CTE1) below 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 of the molding shrinkage rate of the encapsulating resin composition is preferably less than 0.13%, more preferably 0.125% or less, and 0.12% or less. Is particularly preferable. By suppressing the upper limit of the molding shrinkage ratio to a low value, it is possible to suppress warpage of the molded body. On the other hand, the lower limit of the molding shrinkage of the encapsulating resin composition is, for example, preferably −0.5% or more, and more preferably −0.3% or more. By setting the shrinkage ratio of the molding shrinkage ratio within the above range, the molded product can be more easily demolded. The molding shrinkage is measured by using, for example, a resin composition for sealing, 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. It can be performed according to JIS K 6911 for a test piece produced under the condition of time 120 seconds. In the present embodiment, for example, according to the composition of the thermosetting resin in the resin composition for encapsulation, by adjusting the addition amount of the carbodiimide compound, to suppress the molding shrinkage ratio to a desired value. You can

  In the present embodiment, the encapsulating resin composition preferably has a spiral flow flow length of 90 cm or more, more preferably 100 cm or more, and particularly preferably 110 cm or more. This makes it possible to more effectively improve the filling property when molding the encapsulating resin composition. The upper limit of the flow length of the spiral flow is not particularly limited, but can be 200 cm or less, for example. The spiral flow is measured, for example, by using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.) and a mold temperature of 175 ° C. for a mold for spiral flow measurement according to EMMI-1-66. Can be performed by injecting the encapsulating resin composition under the conditions of an injection pressure of 6.9 MPa and a curing time of 120 seconds, and measuring the flow length. In the present embodiment, the spiral flow can be increased by, for example, using fused spherical silica as the 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 encapsulating resin composition preferably has a gel time of, for example, 10 seconds or more and 50 seconds or less, and more preferably 15 seconds or more and 45 seconds or less. This makes it possible to accelerate the molding cycle while improving the moldability of the encapsulating resin composition. The gel time can be measured by measuring the time (gel time) until the resin composition for sealing is melted on a hot plate heated to 175 ° C. and then cured while kneading with a spatula. In the present embodiment, for example, the gel time can be reduced by increasing the amounts of the curing accelerator and the carbodiimide compound.

  In the present embodiment, for example, a cured product obtained by heat-treating the encapsulating resin composition at 175 ° C. for 120 seconds and then at 175 ° C. for 4 hours has a storage elastic modulus (measured at 260 ° C. The lower limit of E ′) is not particularly limited, but is preferably 800 MPa or higher, more preferably 900 MPa or higher, and even more preferably 1000 MPa or higher. On the other hand, the upper limit value of the storage elastic modulus (E ′) is not particularly limited, but is preferably 1500 MPa or less, more preferably 2000 MPa or less, still more preferably 3000 MPa or less. By setting the thermal modulus of elasticity of the encapsulating resin composition (storage modulus at 260 ° C.) within the above range, it is possible to suppress the warpage of the substrate and realize a highly reliable semiconductor device structure. it can.

  Examples of the method for measuring the elastic modulus during heat of the present embodiment include the following methods. Transfer molding is performed using the encapsulating 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 transfer molding conditions are a molding temperature of 125 ° C. and a curing time of 7 minutes. The obtained test piece was measured using a DMA (Dynamic mechanical analysis / dynamic viscoelasticity measuring instrument) under conditions of a three-point bending mode, a frequency of 10 Hz, and a measuring temperature of 260 ° C., and a storage elastic modulus at 260 ° C. Find (E '). The unit is MPa.

  In the present embodiment, the glass transition temperature, molding shrinkage, spiral flow, gel time and thermal modulus of elasticity are, for example, the types and mixing ratios of the components of the encapsulating resin composition, the method for preparing the encapsulating resin composition, etc. Can be controlled by adjusting each of them appropriately. Among these, for example, by using a carbodiimide compound, it can be mentioned as an element for keeping the above-mentioned spiral flow and gel time within desired numerical ranges.

  Hereinafter, the method for producing the encapsulating resin composition according to this embodiment will be described.

  The method for producing the encapsulating resin composition of the present embodiment is not particularly limited, for example, the above components are mixed by a known means, and further melt-kneaded with a kneader such as a roll, a kneader or an extruder, Granules that have been crushed after cooling, those that have been tablet-molded into tablets after crushing, and if necessary, the above crushed products can be sieved, centrifugally milled, hot-cut, etc. Granules and the like produced by the condyle method in which the fluidity and the like are adjusted can be used as the sealing resin composition.

  The configuration of the electronic device according to this embodiment will be described below with reference to FIG. FIG. 1 is a sectional view showing an example of an electronic component 100 according to this embodiment.

An outline of the electronic device (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 the metal member. The sealing resin 20 is composed of a cured product of the sealing resin composition according to the present embodiment. Moreover, as the electronic element 10 and the metal member, for example, those exemplified above can be used.

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

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

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

Next, a method of manufacturing the electronic component 100 will be described.
The method of manufacturing the electronic component 100 includes a step of sealing and molding the electronic element 10 or the metal member using the above-mentioned sealing resin composition. As a result, it is possible to suppress the occurrence of warpage in the molded body 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 this embodiment. In FIG. 2, a method of forming a wafer level package is illustrated by using a pseudo wafer formed by mounting a plurality of electronic elements 10 which are semiconductor elements on a carrier 50. According to the manufacturing method shown in FIG. 2, it is possible to reduce the thickness of the electronic component 100. The method of 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 sealing resin composition. The electronic component 100 may be manufactured by, for example, MAP (Mold Array Package) molding or the like.
Hereinafter, an example of a method of 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 a mount film 52 formed on a 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-peelable film whose adhesiveness to the electronic element 10 is reduced 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 surface of the electronic element 10 on which the external electrodes are provided faces the mount film 52.

  Next, as shown in FIG. 2B, the electronic element 10 is encapsulated with the encapsulating resin composition. The step of sealing and molding is performed on the electronic device 10 at the wafer level, for example. Note that performing the sealing molding at the wafer level means collectively encapsulating a plurality of electronic elements 10 constituting a pseudo wafer with a sealing resin composition as shown in FIG. It is a concept including encapsulating the circuit surface of the above in one step with the encapsulating resin composition. As a result, a molded body 200 including the plurality of electronic elements 10 and the sealing resin 20 that seals the plurality of electronic elements 10 is formed. In the present embodiment, the molded body 200 is formed using the above sealing resin composition. Therefore, it is possible to suppress the warp even in the molded body 200 having a large area and a thin film thickness.

  The encapsulation molding with the encapsulating resin composition of the present embodiment is not particularly limited, but can be performed by compression molding, for example. In this case, the compression molding is more preferably performed under a temperature condition of, for example, 120 ° C. or higher and 160 ° C. or lower. Thereby, the sealing resin composition can be sufficiently cured. Further, when the molded body 200 is cooled, it is possible to prevent the molded body 200 from warping due to 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 is, for example, the above-described insulating layer 30, the via 40 embedded in the insulating layer 30, the wiring 42 provided on the insulating layer 30, the insulating layer 30 and the insulating layer provided on the wiring 42. 32, and. Next, a plurality of solder balls 44 connected to the wiring 42 are formed on the rewiring layer. Then, 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 manner.

（上記一般式（Ｉ）中、Ｒ ^１ 及びＲ ^２ はそれぞれ独立に有機基を示す。］
＜３＞
＜２＞に記載の封止用樹脂組成物であって、
前記一般式（Ｉ）中のＲ ^１ 及びＲ ^２ は、それぞれ置換又は無置換のシクロアルキル基、または置換又は無置換の芳香族基を含む環状構造を有している、封止用樹脂組成物。
＜４＞
＜１＞から＜３＞のいずれか一つに記載の封止用樹脂組成物であって、
前記カルボジイミド化合物のモノマーが、ジシクロヘキシルカルボジイミド、エチルシクロヘキシルカルボジイミド、ジフェニルカルボジイミド、ジメチルカルボジイミド、ジエチルカルボジイミド、ジイソプロピルカルボジイミド、ジイソブチルカルボジイミド、ｔ−ブチルイソプロピルカルボジイミド、ジ−ｔ−ブチルカルボジイミド、ジオクチルカルボジイミドから＜なる群から＜選択される一種または二種以上である、封止用樹脂組成物。
＜５＞
＜１＞から＜４＞のいずれか一つに記載の封止用樹脂組成物であって、
前記カルボジイミド化合物のモノマーの含有量が、前記封止用樹脂組成物の全体に対して０．１質量％以上２．０質量％以下である、封止用樹脂組成物。
＜６＞
＜１＞から＜５＞のいずれか一つに記載の封止用樹脂組成物であって、
当該封止用樹脂組成物を１７５℃、１２０秒で成形した際の成形収縮率が０．１３％未満である、封止用樹脂組成物。
＜７＞
＜１＞から＜６＞のいずれか一つに記載の封止用樹脂組成物であって、
前記熱硬化性樹脂がエポキシ樹脂を含む、封止用樹脂組成物。
＜８＞
＜１＞から＜７＞のいずれか一つに記載の封止用樹脂組成物であって、
当該封止樹脂組成物の硬化物のハロゲンイオンの含有量が２０ｐｐｍ以下である、封止用樹脂組成物。
＜９＞
＜１＞から＜８＞のいずれか一つに記載の封止用樹脂組成物であって、
当該封止用樹脂組成物の１７５℃におけるゲルタイムが、１０秒以上、５０秒以下である、封止用樹脂組成物。
＜１０＞
＜１＞から＜９＞のいずれか一つに記載の封止用樹脂組成物であって、
当該封止用樹脂組成物のスパイラルフローの流動長が、９０ｃｍ以上である、封止用樹脂組成物。
＜１１＞
＜１＞から＜１０＞のいずれか一つに記載の封止用樹脂組成物の硬化物を備える、電子装置。 It should be noted that the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the scope of achieving the object of the present invention are included in the present invention.
Hereinafter, an example of the reference mode of the present invention will be shown.
<1>
A thermosetting resin,
A resin composition for encapsulation, comprising a carbodiimide compound monomer having a carbodiimide group in the molecule and not having an isocyanate group.
<2>
The encapsulating resin composition according to <1>,
A resin composition for encapsulation, wherein the monomer of the carbodiimide compound is represented by the following general formula (I).

(In the general formula (I), R ¹ and R ² each independently represent an organic group.]
<3>
The encapsulating resin composition according to <2>,
R ¹ and R ² in the general formula (I) each have a cyclic structure containing a substituted or unsubstituted cycloalkyl group or a substituted or unsubstituted aromatic group, and a sealing resin composition. .
<4>
The encapsulating resin composition according to any one of <1> to <3>,
The monomer of the carbodiimide compound is dicyclohexylcarbodiimide, ethylcyclohexylcarbodiimide, diphenylcarbodiimide, dimethylcarbodiimide, diethylcarbodiimide, diisopropylcarbodiimide, diisobutylcarbodiimide, t-butylisopropylcarbodiimide, di-t-butylcarbodiimide, dioctylcarbodiimide < A resin composition for encapsulation, which is one kind or two or more kinds selected.
<5>
The encapsulating resin composition according to any one of <1> to <4>,
The encapsulating resin composition, wherein the content of the carbodiimide compound monomer is 0.1% by mass or more and 2.0% by mass or less with respect to the entire encapsulating resin composition.
<6>
The encapsulating resin composition according to any one of <1> to <5>,
The encapsulating resin composition has a molding shrinkage of less than 0.13% when the encapsulating resin composition is molded at 175 ° C. for 120 seconds.
<7>
The encapsulating resin composition according to any one of <1> to <6>,
A resin composition for encapsulation, wherein the thermosetting resin contains an epoxy resin.
<8>
The encapsulating resin composition according to any one of <1> to <7>,
A resin composition for encapsulation, wherein the cured product of the encapsulating resin composition has a halogen ion content of 20 ppm or less.
<9>
The encapsulating resin composition according to any one of <1> to <8>,
The encapsulating resin composition, wherein the gel time of the encapsulating resin composition at 175 ° C. is 10 seconds or more and 50 seconds or less.
<10>
The encapsulating resin composition according to any one of <1> to <9>,
The encapsulating resin composition having a spiral flow length of 90 cm or more.
<11>
An electronic device comprising the cured product of the encapsulating resin composition according to any one of <1> to <10>.

  Next, examples of the present invention will be described.

(Preparation of sealing resin composition)
For each example, a sealing resin composition was prepared as follows. First, according to the formulation shown in Table 1, a thermosetting resin (A), a curing agent (B), a carbodiimide compound, a curing accelerator (C), a silane coupling agent, a release agent, and a colorant were used in a mixer. And mixed to obtain a mixture. Next, the filler (D) was added to the above 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 mixture after kneading was cooled and pulverized to obtain a powdery granular resin composition for sealing.

  Regarding the comparative example, a sealing 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 release agent, and the colorant were mixed using a mixer. To give a mixture. Next, the filler (D) was added to the above 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 mixture after kneading was cooled and pulverized to obtain a powdery granular resin composition for sealing.

  The unit of the mixing ratio of each component in Table 1 is% by mass. The details of each component in Table 1 are 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.)

Carbodiimide compound: dicyclocarbodiimide (N, N'-dicyclohexylcarbodiimide, manufactured by Tokyo Kasei Co., Ltd.)

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

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

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

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

(Spiral flow)
For each of the Examples and Comparative Examples, spiral flow measurement was performed on the obtained sealing resin composition. For the spiral flow measurement, a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.) was used to mold the spiral flow measurement mold according to EMMI-1-66 at a mold temperature of 175 ° C. and an injection pressure. The encapsulating 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, linear expansion coefficient)
For each Example and Comparative Example, the glass transition temperature (Tg) and the coefficient of linear expansion (CTE1, CTE2) of the obtained cured resin composition for encapsulation were measured as follows. First, using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.), a sealing resin composition was injection-molded at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds, A 10 mm × 4 mm × 4 mm test piece was obtained. Then, after the obtained test piece was post-cured at 175 ° C. for 4 hours, a thermomechanical analyzer (manufactured by Seiko Denshi Kogyo Co., Ltd., TMA100) was used to measure temperature range 0 ° C. to 320 ° C. at a heating rate. The measurement was performed under the condition of 5 ° C./min. From the measurement results, the glass transition temperature (Tg), the linear expansion coefficient (CTE1) below the glass transition temperature, and the linear expansion coefficient (CTE2) above the glass transition temperature were calculated. The results are shown in Table 1.

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

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

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 (10)

A thermosetting resin,
With a carbodiimide compound monomer having a carbodiimide group in the molecule, and having no isocyanate group,
A filler,
A resin composition for encapsulation, comprising:
The thermosetting resin contains an epoxy resin,
The monomer of the carbodiimide compound is selected from the group consisting of dicyclohexylcarbodiimide, ethylcyclohexylcarbodiimide, diphenylcarbodiimide, dimethylcarbodiimide, diethylcarbodiimide, diisopropylcarbodiimide, diisobutylcarbodiimide, t-butylisopropylcarbodiimide, di-t-butylcarbodiimide, dioctylcarbodiimide. One or two or more
The encapsulating resin composition, wherein the content of the filler is 80% by mass or more and 95% by mass or less with respect to the entire encapsulating resin composition. The encapsulating resin composition according to claim 1 , wherein
The encapsulating resin composition, wherein the content of the carbodiimide compound monomer is 0.1% by mass or more and 2.0% by mass or less with respect to the entire encapsulating resin composition. The encapsulating resin composition according to claim 1 or 2 , wherein
The encapsulating resin composition has a molding shrinkage of less than 0.13% when the encapsulating resin composition is molded at 175 ° C. for 120 seconds. The encapsulating resin composition according to any one of claims 1 to 3 ,
A resin composition for encapsulation, wherein the cured product of the encapsulating resin composition has a halogen ion content of 20 ppm or less. The encapsulating resin composition according to any one of claims 1 to 4 ,
The encapsulating resin composition, wherein the gel time of the encapsulating resin composition at 175 ° C. is 10 seconds or more and 50 seconds or less. The encapsulating resin composition according to any one of claims 1 to 5 ,
The resin composition for encapsulation, wherein the flow length of the spiral flow of the resin composition for encapsulation is 90 cm or more.   The encapsulating resin composition according to any one of claims 1 to 6,
  The encapsulating resin composition, wherein the filler is one kind or two or more kinds selected from the group consisting of fused silica, crystalline silica, alumina, aluminum hydroxide, silicon nitride, and aluminum nitride.   The encapsulating resin composition according to any one of claims 1 to 7,
  A resin composition for encapsulation, which further comprises a curing agent.   The encapsulating resin composition according to any one of claims 1 to 8,
  A resin composition for encapsulation, which further comprises a curing accelerator agent. An electronic device comprising the cured product of the encapsulating resin composition according to any one of claims 1 to 9 .

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