KR102373908B1 - Epoxy resin composition and semiconductor device - Google Patents

Abstract

The epoxy resin composition of the present invention contains an epoxy resin, a phenol resin, a curing accelerator, and a curing retarder, the curing retarder contains a lactone compound, and the epoxy resin composition is in a molten state at 175°C. When heated to , the melt viscosity initially decreases, and after reaching the minimum melt viscosity, it has a characteristic that rises further. S3/S1 is 3.5 or more and 15 or less when S1 is the time from the start of the measurement to reaching η1, and S3 is the time from reaching η1 to η3 is reached.

Description

Epoxy resin composition and semiconductor device TECHNICAL FIELD

The present invention relates to an epoxy resin composition and a semiconductor device.

In recent years, in the market trend of miniaturization, weight reduction, and high functionality of electronic devices, high integration and thinness of semiconductor devices are progressing every year, and surface mounting of semiconductor devices is promoted. An area-mounted semiconductor device obtained by mounting a semiconductor element on a substrate such as a ceramic substrate, electrically connecting the substrate and the semiconductor element with a connecting member, and then molding and sealing the semiconductor element and the connecting member with a mold material. implementation is in progress. As an area mount type semiconductor device, BGA (Ball Grid Array), CSP (Chip Scale Package) which pursued further miniaturization, etc. are mentioned as a typical example.

It is calculated|required that the sealing material used for such an area-mount type semiconductor device selects the material of an epoxy resin, a hardening|curing agent, and hardening accelerator suitably according to various purposes. As this kind of technique, the epoxy resin composition of patent document 1 is mentioned, for example.

According to the same document, an epoxy resin composition containing an epoxy resin, a phenol resin, and a curing accelerator is described (Claim 1 described in Patent Document 1, Examples, etc.). However, this document does not describe adding a curing retardant to the epoxy resin composition.

Japanese Patent Laid-Open No. 2009-191122

However, when the present inventor examined, in the epoxy resin composition described in the said document, the time which can keep melt viscosity low is insufficient, As a result, it became clear that there was room for improvement in the point of manufacturing stability.

MEANS TO SOLVE THE PROBLEM This inventor paid attention to the above melt-viscosity characteristics, and performed various examination about the epoxy resin composition containing a hardening accelerator. As a result, it became clear that the melt viscosity characteristic in the epoxy resin composition containing a hardening accelerator can be suitably controlled by using a predetermined|prescribed lactone compound as the said hardening retarder while using a hardening retarder.

Based on these findings, intensive studies have shown that the lowest melt viscosity of the epoxy resin composition is η1, the viscosity three times that of η1 is η3, the time from the start of the measurement to η1 is S1, and after reaching η1 It turned out that the said melt-viscosity characteristic can be evaluated suitably by making S3/S1 at the time of making time until it reach|attain η3 S3 as an index|index. And, by setting the index S3/S1 to a predetermined value or more, in the epoxy resin composition containing the curing accelerator, the time for keeping the melt viscosity low can be sufficiently secured, so that the production stability of the epoxy resin composition can be improved. It was discovered that there is, and came to complete the present invention.

According to the present invention,

epoxy resin,

phenolic resin,

a curing accelerator;

An epoxy resin composition comprising a curing retardant, comprising:

The curing retardant includes a lactone compound,

When the epoxy resin composition is heated to a molten state at 175 ° C., the melt viscosity initially decreases, and after reaching the lowest melt viscosity, it has a characteristic that further increases,

Let the lowest melt viscosity of the epoxy resin composition be η1, the viscosity three times that of η1 be η3, the time from the start of measurement to reaching η1 is S1, the time from reaching η1 to reaching η3 When S3 is set, S3/S1 is 3.5 or more and 15 or less, The epoxy resin composition is provided.

Moreover, when earnest examination based on the said discovery, it turned out that the said melt viscosity characteristic can be evaluated suitably by making the exothermic onset temperature in the DSC curve of an epoxy resin composition an index|index. And, by making the exothermic onset temperature higher than or equal to a predetermined value, in the epoxy resin composition containing the curing accelerator, the time for keeping the melt viscosity low can be sufficiently secured, so that the production stability of the epoxy resin composition can be improved. found, and came to complete the present invention.

In addition, according to the present invention,

epoxy resin,

phenolic resin,

a curing accelerator;

An epoxy resin composition comprising a curing retardant, comprising:

The curing retardant includes a lactone compound,

The exothermic onset temperature in the DSC curve of the epoxy resin composition obtained when the temperature is raised from 30°C to 300°C under the condition of a temperature increase rate of 10°C/min using a differential scanning calorimeter is in the range of 94°C or more and 135°C or less. , an epoxy resin composition is provided.

In addition, according to the present invention,

a semiconductor device,

A semiconductor device comprising a sealing member for sealing the semiconductor element,

There is provided a semiconductor device in which the sealing member is composed of a cured product of the epoxy resin composition.

ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition excellent in manufacturing stability, and the semiconductor device using the same can be provided.

The above and other objects, features and advantages are made clearer by the preferred embodiment described below and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows an example of the semiconductor device in this embodiment.
2 is a cross-sectional view showing an example of a structure according to the present embodiment.
3 is a diagram showing the measurement results of DSC of Examples 3, 6, and Comparative Example 1. FIG.
4 is a view showing changes with time of melt viscosity of Examples 3, 6, and Comparative Example 1. FIG.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described using drawings. In addition, in all the drawings, the same code|symbol is attached|subjected to the same component, and description is abbreviate|omitted suitably.

The epoxy resin composition of this embodiment can contain an epoxy resin (A), a phenol resin (B), a hardening accelerator (C), and the hardening retarder (E) containing a lactone compound.

Moreover, when the said epoxy resin composition is heated to a molten state at 175 degreeC, melt viscosity decreases initially, and after reaching a minimum melt viscosity, it has the characteristic which rises further. And let the lowest melt viscosity of the said epoxy resin composition be η1, let the viscosity three times of η1 be η3, let the time from the start of measurement to reach η1 be S1, after reaching η1 until reaching η3 When the time of is S3, S3/S1 can be set to 3.5 or more and 15 or less.

It became clear that the melt viscosity characteristic in the epoxy resin composition containing a hardening accelerator can be suitably controlled by this inventor using a predetermined|prescribed lactone compound as the said hardening retarder while using a hardening retarder.

When earnest examination based on these findings, it turned out that the said melt viscosity characteristic can be evaluated suitably by using S3/S1 mentioned above as an index|index. In other words, S3/S1 of this embodiment can represent the length of time for which the state with a low melt viscosity is maintained.

By making this index S3/S1 to 3.5 or more, in the epoxy resin composition containing the curing accelerator, the time for keeping the melt viscosity low can be sufficiently secured, so that the production stability of the epoxy resin composition can be improved. found, and came to complete the present invention.

Moreover, in the epoxy resin composition of this embodiment, when using a differential scanning calorimeter and heating up from 30 degreeC to 300 degreeC under the conditions of a temperature increase rate of 10 degreeC/min, the exothermic onset temperature in the DSC curve of the said epoxy resin composition obtained when can be within the range of 94°C or higher and 135°C or lower.

When earnest examination based on the said discovery, it turned out that the melt viscosity characteristic of an epoxy resin composition can be evaluated suitably by making the exothermic onset temperature in the DSC curve of an epoxy resin composition an index|index. Here, the degree of reaction of the epoxy resin composition can be understood from the result of the DSC curve. Incidentally, the exothermic start temperature in the DSC curve is the temperature at which the reaction starts. Therefore, since the viscosity of the epoxy resin composition increases as the reaction progresses, by setting the exothermic initiation temperature to be high at 94 ° C. or higher, in the epoxy resin composition containing the curing accelerator, a desired molten state can be maintained, for example For example, since the time which can keep melt viscosity low enough can be ensured, it discovered that the manufacturing stability of the said epoxy resin composition could be improved, and came to complete this invention.

The epoxy resin composition of this embodiment is excellent in manufacturing stability, and can be used as a resin composition for sealing used in order to seal a semiconductor element, for example.

Moreover, since the epoxy resin composition of this embodiment has the outstanding melt-viscosity characteristic, it can use suitably for various processes, such as injection molding, large area die-molding, and sealing of the semiconductor element which has a wire bonding connection.

The component of the epoxy resin composition of this embodiment is demonstrated in detail.

[Epoxy Resin (A)]

The epoxy resin composition of this embodiment can contain an epoxy resin (A).

As the epoxy resin (A) of the present embodiment, a monomer, an oligomer, or an overall polymer having two or more epoxy groups in one molecule can be used, and the molecular weight and molecular structure thereof are not particularly limited. In this embodiment, it is preferable to employ|adopt a non-halogenated epoxy resin especially as an epoxy resin (A).

As said epoxy resin (A), For example, a biphenyl type epoxy resin; Bisphenol-type epoxy resins, such as a bisphenol A epoxy resin, a bisphenol F-type epoxy resin, and a tetramethylbisphenol F-type epoxy resin; stilbene-type epoxy resin; novolac-type epoxy resins such as phenol novolak-type epoxy resins and cresol novolak-type epoxy resins; polyfunctional epoxy resins such as triphenylmethane-type epoxy resins and alkyl-modified triphenylmethane-type epoxy resins; Biphenyl aralkyl type epoxy resins, such as a phenol aralkyl type epoxy resin which has a phenylene structure, and a phenol aralkyl type epoxy resin which has a biphenylene structure; naphthol-type epoxy resins such as dihydroxynaphthalene-type epoxy resins and epoxy resins obtained by glycidyl-etherifying a dimer of dihydroxynaphthalene; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; Glued cyclic hydrocarbon compound modified phenol type epoxy resins, such as dicyclopentadiene modified phenol type epoxy resin, etc. are mentioned. These may be used independently and may be used in combination of 2 or more type.

Among these, from the viewpoint of improving the balance between moisture resistance reliability and moldability, at least one of a bisphenol type epoxy resin, a biphenyl type epoxy resin, a novolak type epoxy resin, a phenol aralkyl type epoxy resin, and a triphenylmethane type epoxy resin is used. also be Moreover, you may use at least one of a phenol aralkyl type epoxy resin and a novolak type epoxy resin from a viewpoint of suppressing the curvature of a semiconductor device. In order to improve fluidity|liquidity, you may use a biphenyl type epoxy resin. In order to control the elastic modulus of high temperature, you may use a biphenyl aralkyl type epoxy resin. Among these, a triphenylmethane type epoxy resin or a biphenyl aralkyl type epoxy resin can be used.

The said triphenylmethane type epoxy resin contains the structural unit represented by the following general formula (4) and/or the following general formula (5).

[Formula 1]

[Formula 2]

(In the general formulas (4) and (5), R ₁₀ , R ₁₁ , and R ₁₂ are a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and may be the same as or different from each other. a and c are an integer of 0 to 3, b is an integer of 0 to 4, and may be the same or different from each other, X ₁ is a single bond or any of the following general formulas (5A), (5B), or (5C) In the following general formulas (5A), (5B) and (5C), R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon having 6 to 14 carbon atoms. group, and may be the same or different from each other. d is an integer of 0 to 2, e, f and g are integers of 0 to 4, and may be the same or different from each other.)

[Formula 3]

The said biphenyl aralkyl type epoxy resin contains the structural unit represented by following General formula (6).

[Formula 4]

(X ₂ represents a hydrogen atom or a group represented by the following general formula (6B).)

[Formula 5]

The lower limit of content of the epoxy resin (A) of this embodiment is, for example, 1 weight% or more is preferable with respect to all 100 weight% of an epoxy resin composition, 3 weight% or more is more preferable, 5 weight% or more This is more preferable. Further, the upper limit of the content of the epoxy resin (A) is, for example, preferably 90% by weight or less, more preferably 80% by weight or less, and more preferably 70% by weight or less with respect to 100% by weight of the total amount of the epoxy resin composition. desirable. By making content of the said epoxy resin (A) into the said preferable range, low hygroscopicity can be improved. Moreover, the solder crack resistance of the semiconductor device obtained can be improved by making content of the said epoxy resin (A) into said more preferable range. In the present embodiment, the improvement of the solder crack resistance means that the obtained semiconductor device is less prone to cracking or peeling defects even when exposed to high temperatures in, for example, solder immersion or solder reflow process. indicates.

In this embodiment, content with respect to the whole epoxy resin composition refers to content with respect to the whole solid component except the solvent in an epoxy resin composition, when an epoxy resin composition contains a solvent.

Moreover, the lower limit of content of the epoxy resin (A) which is a biphenyl aralkyl type epoxy resin or a triphenylmethane type epoxy resin is, with respect to the whole epoxy resin (A), 85 weight% or more is preferable, for example, 90 weight% or more More preferably, 95% by weight or more. Thereby, fluidity|liquidity can be improved. On the other hand, although the upper limit of content of the epoxy resin (A) which is a biphenyl aralkyl type epoxy resin or a triphenylmethane type epoxy resin is not specifically limited with respect to the whole epoxy resin (A), For example, even if it is 100 weight% or less It is good also as 99 weight% or less, and good also as 98 weight% or less.

[Phenolic resin (B)]

The epoxy resin composition of this embodiment can contain a phenol resin (B).

The phenol resin (B) of this embodiment is a monomer, an oligomer, and the general polymer which have two or more phenolic hydroxyl groups in 1 molecule, The molecular weight and molecular structure are not specifically limited.

Examples of the phenol resin (B) include phenol novolac resin, cresol novolac resin and other phenols, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, α-naphthol, β- A novolak resin obtained by condensing or co-condensing phenols such as naphthol and dihydroxynaphthalene with formaldehyde or ketones under an acidic catalyst, a ratio synthesized from the above phenols and dimethoxyparaxylene or bis(methoxymethyl)biphenyl Phenyl aralkyl type phenol resins, such as a phenol aralkyl resin which has a phenylene frame|skeleton, and a phenol aralkyl resin which has a phenylene frame|skeleton, triphenylmethane type phenol resin etc. which have a trisphenolmethane frame|skeleton are mentioned. These may be used independently and may be used in combination of 2 or more type. Among these, a triphenylmethane type phenol resin or a biphenyl aralkyl type phenol resin may be used.

The said triphenylmethane type phenol resin contains the structural unit represented by the following general formula (7) and/or the following general formula (8).

[Formula 6]

[Formula 7]

(In the general formulas (7) and (8), R ₁₇ , R ₁₈ , and R ₁₉ are a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and may be the same as or different from each other. Y ₃ represents a hydroxyl group.h and j represent an integer of 0 to 3, i is an integer of 0 to 4, and may be the same or different from each other. Y ₁ represents a single bond or the following general formulas (8A) and (8B) , or a group represented by any one of (8C) In the general formulas (8A) to (8C), R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ are a hydrocarbon group having 1 to 6 carbon atoms or aromatic carbonization having 6 to 14 carbon atoms. It is a hydrogen group, and may be the same as or different from each other. k is an integer of 0 to 2, l, m and n are integers of 0 to 4, and may be the same or different from each other.)

[Formula 8]

The said biphenyl aralkyl type phenol resin contains the structural unit represented by following General formula (9).

[Formula 9]

(Y ₂ represents a hydrogen atom or a group represented by the following general formula (9B).)

[Formula 10]

The lower limit of content of the phenol resin (B) of this embodiment is, for example, 1 weight% or more is preferable with respect to all 100 weight% of an epoxy resin composition, 2 weight% or more is more preferable, 3 weight% or more This is more preferable. In addition, the upper limit of the content of the phenol resin (B) is, for example, preferably 60% by weight or less, more preferably 50% by weight or less, and further 40% by weight or less with respect to 100% by weight of the total amount of the epoxy resin composition. desirable. By making content of the said phenol resin (B) into the said preferable range, low hygroscopicity and fluidity|liquidity can be improved. Moreover, the solder crack resistance of the semiconductor device obtained can be improved by making content of the said phenol resin (B) into said more preferable range.

Moreover, the lower limit of content of the phenol resin (B) which is a biphenyl aralkyl type phenol resin or a triphenylmethane type phenol resin is preferably 95 weight% or more with respect to the whole phenol resin (B), 96 weight% More preferably, 97% by weight or more is more preferable. Thereby, fluidity|liquidity can be improved. In addition, although the upper limit of content of the phenol resin (B) which is a biphenyl aralkyl type phenol resin or a triphenylmethane type phenol resin is not specifically limited with respect to the whole phenol resin (B), For example, even if it is 100 weight% or less It is good also as 99 weight% or less, and good also as 98 weight% or less.

[curing accelerator (C)]

The epoxy resin composition of this embodiment can contain a hardening accelerator (C).

The hardening accelerator (C) of this embodiment should just accelerate|stimulate the crosslinking reaction of an epoxy resin (A) and a phenol resin (B), and what is used for the resin composition for general semiconductor sealing can be used. The curing accelerator (C) may include, for example, a cationic curing accelerator.

As the curing accelerator (C) of the present embodiment, for example, an organic phosphine, a tetrasubstituted 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, etc. phosphorus atom-containing compounds; 1,8-diazabicyclo(5,4,0)undecene-7, benzyldimethylamine, 2-methylimidazole, etc. Amidines and tertiary amines, quaternary salts of the above amidines and amines, etc. It may include one or two or more types selected from nitrogen atom-containing compounds of Among these, it is more preferable to contain a phosphorus atom containing compound from a viewpoint of improving sclerosis|hardenability. In addition, from the viewpoint of improving the balance between moldability and curability, those having latent properties such as a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound It is more preferable to include

As an organic phosphine which can be used with the epoxy resin composition of this embodiment, For example, 1st phosphine, such as an ethyl phosphine and a phenyl phosphine; second phosphine such as dimethylphosphine and diphenylphosphine; 3rd phosphine, such as a trimethyl phosphine, a triethyl phosphine, a tributyl phosphine, and a triphenyl phosphine, is mentioned.

As a tetra-substituted phosphonium compound which can be used with the epoxy resin composition of this embodiment, the compound etc. which are represented, for example by following General formula (10) are mentioned.

[Formula 11]

(In the general formula (10), P represents a phosphorus atom. R ⁴ , R ⁵ , R ⁶ and R ⁷ represent an aromatic group or an alkyl group. A is a hydroxyl group, a carboxyl group, and a thiol group Represents the anion of the aromatic organic acid having at least one of the functional groups in the aromatic ring. AH represents the aromatic organic acid having at least one of the functional groups selected from the group consisting of hydroxyl group, carboxyl group and thiol group in the aromatic ring. x, y is a number from 1 to 3, z is a number from 0 to 3, and x=y.)

Although the compound represented by General formula (10) 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 uniformly mixed to generate an aromatic organic acid anion in the solution system. Then, when water is added, the compound represented by the general formula (10) can be precipitated. In the compound represented by the general formula (10), R ⁴ , R ⁵ , R ⁶ and R ⁷ bonded to a phosphorus atom are a phenyl group, and AH is a compound having a hydroxyl group in the aromatic ring, that is, phenols, and A is It is preferable that it is an anion of the phenols. Examples of the phenols include monocyclic phenols such as phenol, cresol, resorcin, and catechol; condensed polycyclic phenols such as naphthol, dihydroxynaphthalene and anthraquinol; bisphenols such as bisphenol A, bisphenol F, and bisphenol S; phenylphenol and polycyclic phenols such as biphenol.

As a phosphobetaine compound which can be used with the epoxy resin composition of this embodiment, the compound etc. which are represented, for example by following General formula (11) are mentioned.

[Formula 12]

(In the general formula (11), P represents a phosphorus atom. 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 number.)

The compound represented by General formula (11) is obtained as follows, for example. First, it is obtained through the process of making a triaromatic-substituted phosphine which is a 3rd phosphine and a diazonium salt contact, and substituting the diazonium group which a triaromatic-substituted phosphine and a diazonium salt have. However, the present invention is not limited thereto.

As an adduct of a phosphine compound and a quinone compound which can be used with the epoxy resin composition of this embodiment, the compound etc. which are represented, for example by following General formula (12) are mentioned.

[Formula 13]

(In the general formula (12), 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 may be the same as or different from each other. R ¹³ , R ¹⁴ and R ¹⁵ represent 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 may be bonded to each other to form a cyclic structure.)

Examples of the phosphine compound used for the adduct of the phosphine compound and the quinone compound include triphenylphosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, trinaphthylphosphine, tris(benzyl) It is preferable that unsubstituted or substituents, such as an alkyl group and an alkoxyl group, exist in aromatic rings, such as a phosphine, and what has C1-C6 as substituents, such as an alkyl group and an alkoxyl group, is mentioned. 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, benzoquinone and anthraquinones are mentioned, Especially, p-benzoquinone is preferable at the point of storage stability.

As a method for producing an adduct of a phosphine compound and a quinone compound, an adduct can be obtained by contacting and mixing them in a solvent in which both organic tertiary phosphine and benzoquinones can be dissolved. The solvent is preferably a ketone such as acetone or methyl ethyl ketone, which has low solubility in adducts. However, the present invention is not limited thereto.

Examples of the compound represented by the general formula (12) include a compound in which R ¹⁰ , R ¹¹ and R ¹² bonded to a phosphorus atom are a phenyl group, and R ¹³ , R ¹⁴ and R ¹⁵ are a hydrogen atom, that is, 1,4-benzoquinone; A compound to which triphenylphosphine is added is preferable from the viewpoint of lowering the thermal elastic modulus of the cured product of the epoxy resin composition.

As an adduct of a phosphonium compound and a silane compound which can be used with the epoxy resin composition of this embodiment, the compound etc. which are represented, for example by following General formula (13) are mentioned.

[Formula 14]

(In the general formula (13), 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 ring. represents a group, and may be the same as or different from each other, wherein R ²⁰ is an organic group bonded to Y ² and Y ³ , wherein R ²¹ is an organic group bonded to Y ⁴ and Y ^5. Y ² and Y ³ represents a group formed by a proton ^- donating group releasing a proton, and Y ² and Y ^{3 in} the same molecule combine with a silicon atom to form a chelate structure. represents a group formed, and Y ⁴ and Y ⁵ in the same molecule combine with a silicon atom to form a chelate structure, R ²⁰ and R ²¹ may be the same or different from each other, and Y ² , Y ³ , Y ⁴ and Y ⁵ may be the same as or different from each other. Z ¹ is an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group.)

In the general formula (13), as R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ , for example, a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, a naphthyl group, a hydroxynaphthyl group, a benzyl group, a methyl group, ethyl group, n-butyl group, n-octyl group, cyclohexyl group, etc. are mentioned, Among these, Alkyl groups, such as a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, and a hydroxynaphthyl group, an alkoxy group, a hydroxyl group, etc. An aromatic group having a substituent of or an unsubstituted aromatic group is more preferable.

Moreover, in General formula ( ¹³ ), ^R20 is an organic group ^couple |bonded with Y2 and Y3. Similarly, R ²¹ is an organic group bonded to Y ⁴ and Y ⁵ . Y ² and Y ³ are groups formed by a proton-donating group releasing a proton, and Y ² and Y ³ in the same molecule combine with a silicon atom to form a chelate structure. Similarly, Y ⁴ and Y ⁵ are groups formed by a proton-donating group releasing a proton, and Y ⁴ and Y ⁵ in the same molecule combine with a silicon atom to form a chelate structure. The groups R ²⁰ and R ²¹ may be the same as or different from each other, and Y ² , Y ³ , Y ⁴ , and Y ⁵ may be the same or different from each other. The groups represented by -Y ² -R ²⁰ -Y ³ - and -Y ⁴ -R ²¹ -Y ⁵ - in the general formula (13) are constituted by a group in which 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, an aromatic compound having at least two carboxyl groups or hydroxyl groups on adjacent carbons constituting an aromatic ring is preferable, and an aromatic ring An aromatic compound having at least two hydroxyl groups on adjacent carbons constituting it is more preferable, for example, catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2' -Biphenol, 1,1'-bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, Although 1,2-cyclohexanediol, 1,2-propanediol, glycerol, etc. are mentioned, Among these, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferable.

In addition, Z ¹ in the general formula (13) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring, and specific examples thereof include aliphatic carbonization such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group. An alkyl group having an aromatic hydrocarbon group such as a hydrogen group, a phenyl group, a benzyl group, a naphthyl group and a biphenyl group, a glycidyloxy group such as a glycidyloxypropyl group, a mercaptopropyl group, and an aminopropyl group, a mercapto group, and an amino group; Reactive substituents, such as a vinyl group, etc. are mentioned, Among these, a methyl group, an ethyl group, a phenyl group, a naphthyl group, and a biphenyl group are more preferable from the point of thermal stability.

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 and dissolved in a flask containing methanol, and then dissolved at room temperature. The sodium methoxide-methanol solution is added dropwise under stirring. Furthermore, when a solution prepared in advance by dissolving tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide in methanol is added dropwise thereto under stirring at room temperature, crystals are precipitated. When the precipitated crystals are filtered, washed with water and vacuum dried, an adduct of a phosphonium compound and a silane compound is obtained. However, the present invention is not limited thereto.

The lower limit of the content of the curing accelerator (C) of the present embodiment is, for example, preferably 0.05 wt% or more, more preferably 0.08 wt% or more, and 0.1 wt% or more with respect to 100 wt% of the total amount of the epoxy resin composition. This is more preferable. In addition, the upper limit of the content of the curing accelerator (C) is, for example, preferably 10% by weight or less, more preferably 7.5% by weight or less, and more preferably 5% by weight or less with respect to 100% by weight of the total amount of the epoxy resin composition. desirable. By making content of the said hardening accelerator (C) more than the said lower limit, appropriate hardening can be performed. Moreover, storage property and fluidity|liquidity can be improved by carrying out content of the said hardening accelerator (C) below the said upper limit.

[Cure retardant (E)]

The epoxy resin composition of this embodiment can contain a hardening retarder (E). The said curing retarder (E) can contain a lactone compound.

In this embodiment, as a lactone compound, the lactone compound which has the hydroxyl group couple|bonded with the lactone ring can be used. For this reason, the epoxy resin composition excellent in melt viscosity characteristics can be implement|achieved. Moreover, the balance of melt viscosity characteristic and hardening characteristic can be improved by appropriately controlling the structure of a lactone compound, and its content.

The present inventors recognized the existence of a compound capable of controlling the curing properties of the curing accelerator, and as a result of further investigation, by using a lactone compound in which a hydroxyl group is bonded to a lactone ring, an epoxy resin composition using a curing accelerator , led to the discovery that the melt viscosity properties can be appropriately controlled.

The detailed mechanism is not certain, but it is speculated as follows. In this embodiment, since the lactone compound has the hydroxyl group couple|bonded with the lactone ring, it has a low pKa (acid dissociation constant). Since the lactone compound becomes an anion and the hardening accelerator becomes a cation, the hydroxyl group couple|bonded with the lactone ring will coordinate or ionic bond to the hardening accelerator. It is thought that the melt viscosity characteristic of the epoxy resin composition containing a hardening accelerator can be controlled suitably by such interaction.

In the present embodiment, the upper limit of the pKa of the lactone compound may be, for example, 6 or less, 5.5 or less, 5 or less, or 4.6 or less. Thereby, the melt viscosity characteristic of an epoxy resin composition can be improved. Although the lower limit of pKa of a lactone compound is not specifically limited, It is good also as 2 or more, for example.

Here, for example, it is known that the pKa of the hydroxy group of the aromatic described in Unexamined-Japanese-Patent No. 2013-32510 is about 9-10. For example, the pKa of a 6-membered ring lactone having a hydroxyl group bonded to an aromatic ring as shown in the following formula is 9.5. In such a lactone compound, from the result of examination by this inventor, it turned out that it is difficult to acquire the effect of melt viscosity characteristic similar to this embodiment.

[Formula 15]

It is preferable that the said lactone compound contains the lactone compound containing the following structural unit (1) which has at least 1 or more hydroxyl group in the lactone ring A.

[Formula 16]

(In the structural unit (1), m represents an integer of 1 or 2, and n represents an integer of 1 to 6. B represents a monovalent or divalent organic group. Ra is each independently a hydrogen atom, a hydroxyl Represents a period and an alkyl group. When n is 2 or more, Ra may combine with each other to form a ring. Ra may be unsubstituted or may have a substituent.)

The said lactone ring A may have a 5- to 7-membered ring heterocyclic compound, for example, More preferably, it may have a 6-membered ring heterocyclic compound. In this case, the hetero atom of the heterocyclic compound is an oxygen atom.

In the lactone ring A of the 6-membered ring, the benzene skeleton, the naphthalene skeleton, or the pyridine skeleton may be condensed with the lactone ring A (lactone skeleton) of the six-membered ring by condensing adjacent carbon atoms.

The lactone compound of the present embodiment may have a coumarin structure or a biscoumarin structure.

As a lactone compound which has a coumarin structure, the structure represented by the following general formula (I) can be included.

[Formula 17]

R ₁ to R ₈ in the general formula (I) may be the same as or different from each other. R ₁ to R ₈ are a hydrogen atom, a hydroxyl group, and 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, a linear or branched alkyl group, or 6 to 20 carbon atoms , an aryl group, an alkaryl group, or an aralkyl group. However, at least 1 or more of _R1 - _R4 is a hydroxyl group. In this embodiment, in general formula (I), R< ₄ > may have a hydroxyl group.

Although it does not specifically limit as a lactone compound which has a biscoumarin structure, For example, it is good also as a structure which connected two said coumarin structures with a predetermined crosslinking group (via B in the said structural formula (1)).

As a lactone compound which has such a biscumarine structure, the structure represented by the following general formula (II) can be included.

[Formula 18]

R in the said general formula (II) is selected from the following formula.

[Formula 19]

In this embodiment, the lactone compound which has a biscoumarin structure can heighten the effect of the melt viscosity characteristic of an epoxy resin composition rather than the lactone compound which has a coumarin structure. Although the detailed mechanism is not certain, it is thought as follows. That is, the dicoumarol skeleton in which two coumarin skeletons are bonded has a structure in which physical movement is limited. For this reason, the coordination bond between an anion and a cation can be more stabilized. At this time, while the coordination bond or ionic bond (interaction) by the dicoumarol skeleton with respect to the cation of a hardening accelerator becomes strong, it is thought that a cation can be stabilized further. For this reason, by using the lactone compound which has a biscoumarin structure, compared with the case of the lactone compound which has a coumarin structure, even with a small addition amount, the effect equal or more than that can be acquired.

In the present embodiment, the lower limit of the molar ratio of the content of the curing retarder (E) (or the lactone compound) to the content of the curing accelerator (C) in the epoxy resin composition may be, for example, 0.1 or more, preferably It is 0.2 or more, More preferably, it is 0.3 or more. Thereby, the melt viscosity characteristic and fluidity|liquidity of an epoxy resin composition can be improved. Furthermore, the storability of an epoxy resin composition can be improved. The upper limit of the molar ratio of the content of the curing retarder (E) (or the lactone compound) to the content of the curing accelerator (C) in the epoxy resin composition is not particularly limited, but may be, for example, 4 or less, preferably Preferably it is 3 or less, More preferably, it is 2 or less. Thereby, the balance of melt viscosity characteristic and hardening characteristic of an epoxy resin composition can be improved.

In this embodiment, the lower limit of the content of the curing retarder (E) (or lactone compound) may be, for example, 0.01% by weight or more, preferably 0.02% by weight or more, based on the entire epoxy resin composition, More preferably, it is 0.025 weight% or more. Thereby, the melt viscosity characteristic and fluidity|liquidity of an epoxy resin composition can be improved. Furthermore, the storability of an epoxy resin composition can be improved. In addition, the upper limit of the content of the curing retarder (E) (or lactone compound) is not particularly limited with respect to the entire epoxy resin composition, but may be, for example, 1.5% by weight or less, preferably 1.25% by weight or less. , more preferably 1% by weight or less. Thereby, the balance of melt viscosity characteristic and hardening characteristic of an epoxy resin composition can be improved.

[Inorganic Filling (D)]

The epoxy resin composition of this embodiment can further contain an inorganic filler (D).

In this embodiment, although it does not specifically limit as an inorganic filler (D), For example, fused silica, fused silica, crystalline silica, secondary agglomerated silica, alumina, titanium white, aluminum hydroxide, talc, clay, glass fiber and the like. It can use 1 type or in combination of 2 or more types among these. Among these, as said inorganic filler (D), it is preferable that it is especially fused silica. Since fused silica lacks reactivity with a hardening accelerator (C), even when it mix|blends abundantly in the epoxy resin composition of this embodiment, it can prevent that the hardening reaction of an epoxy resin composition is inhibited. Moreover, the reinforcement effect of the semiconductor device obtained improves more by using fused silica as an inorganic filler (D).

As a shape of an inorganic filler (D), although any, such as a granular form, a block form, and a scale form, may be sufficient, for example, a granular form (particularly, spherical shape) is preferable among these.

1 micrometer or more is preferable, for example, and, as for the lower limit of the average particle diameter of the inorganic filler (D) of this embodiment, 3 micrometers or more are more preferable. 100 micrometers or less are preferable, for example, and, as for the upper limit of the average particle diameter of an inorganic filler (D), 50 micrometers or less are more preferable. By carrying out the average particle diameter of the said inorganic filler (D) in the said range, fillability can be improved and the raise of the melt viscosity of an epoxy resin composition can be suppressed.

The lower limit of content of the inorganic filler (D) of this embodiment is, for example, 40 weight% or more is preferable with respect to all 100 weight% of an epoxy resin composition, 50 weight% or more is more preferable, 60 weight% or more This is more preferable. In addition, the upper limit of the content of the inorganic filler (D) is, for example, preferably 97.5% by weight or less, more preferably 97% by weight or less, and more preferably 95% by weight or less with respect to 100% by weight of the total amount of the epoxy resin composition. desirable. By making the content of the inorganic filler (D) equal to or more than the lower limit, the curvature of the package molded using the epoxy resin composition of the present embodiment can be suppressed, and the amount of moisture absorption and the decrease in strength can be reduced. there is. Moreover, by making content of the said inorganic filler (D) below the said upper limit, the fluidity|liquidity of the epoxy resin composition of this embodiment can be raised and moldability can be made favorable.

The epoxy resin composition of this embodiment can contain other additives as needed other than the compound of said (A)-(E). Examples of the other additives include a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a colorant such as carbon black, a flame retardant such as a brominated epoxy resin, antimony oxide, a phosphorus compound, a silicone oil, a silicone rubber, etc. Various additives such as stress components, natural waxes, synthetic waxes, higher fatty acids or metal salts thereof, release agents such as paraffin, and antioxidants can be used. You may use these 1 type or 2 or more types.

In the manufacturing method of the epoxy resin composition of this embodiment, for example, in addition to the compound of the said (A)-(E), other additives etc. are mixed using a mixer at room temperature as needed, a hot roll, a heat kneader, etc. It is obtained by heating and kneading using, cooling and pulverizing.

Next, the physical property of the epoxy resin composition of this embodiment is demonstrated.

When the epoxy resin composition is heated to a molten state at 175 ° C., the melt viscosity initially decreases, and after reaching the lowest melt viscosity, it has a characteristic that further increases,

Let the lowest melt viscosity of the epoxy resin composition be η1, the viscosity three times that of η1 be η3, the time from the start of the measurement to reach η1 is S1, the time to reach η3 after reaching η1 is S3 do. At this time, the lower limit of S3/S1 is 3.5 or more, for example, Preferably it is 3.8 or more, More preferably, it is 4.5 or more. Thereby, the manufacturing stability of an epoxy resin composition can be improved. On the other hand, the upper limit of S3/S1 is, for example, 15 or less, Preferably it is 11 or less, More preferably, it is 8.0 or less. Thereby, sclerosis|hardenability of an epoxy resin can be improved.

Let the lowest melt viscosity of the epoxy resin composition be η1, the viscosity ten times that of η1 be η10, the time from the start of the measurement to reach η1 is S1, the time to reach η10 after reaching η1 is S10 do. At this time, the lower limit of |S10/S1-S3/S1| is, for example, 2.2 or more, Preferably it is 2.5 or more, More preferably, it is 3.0 or more. Thereby, sclerosis|hardenability of an epoxy resin composition can be improved. On the other hand, the upper limit of |S10/S1-S3/S1| is, for example, 7 or less, Preferably it is 6 or less, More preferably, it is 5 or less. Thereby, the manufacturing stability of an epoxy resin composition can be improved. In the epoxy resin composition containing an inorganic filler, a wire sweep amount can be made small, for example.

The epoxy resin composition is molded into a tablet form and stored at 40° C. for 48 hours, then the lowest melt viscosity of the epoxy resin composition after storage is η1, the viscosity three times that of η1 is η3, and η1 from the start of the measurement Let Sh ₄₈ 1 be the time to reach , and the time to reach η3 after reaching η1 is S _48h 3 . At this time, the lower limit of _S48h3 / _S48h1 is, for example, 3.5 or more, Preferably it is 3.8 or more, More preferably, it is 4.5 or more. Thereby, the manufacturing stability of an epoxy resin composition can be improved. On the other hand, the upper limit of _S48h3 / _S48h1 is, for example, 15 or less, Preferably it is 11 or less, More preferably, it is 8.0 or less. Thereby, sclerosis|hardenability of an epoxy resin can be improved.

In the epoxy resin composition of this embodiment, the lower limit of the exothermic onset temperature in the DSC curve of the epoxy resin composition obtained when the temperature is raised from 30°C to 300°C under the conditions of a temperature increase rate of 10°C/min using a differential scanning calorimeter. Silver is, for example, 94°C or higher, preferably 95°C or higher, and more preferably 100°C or higher. Thereby, the manufacturing stability of an epoxy resin composition can be improved. In the epoxy resin composition containing an inorganic filler (D), a slit burr can be suppressed, for example. On the other hand, the upper limit of the exothermic onset temperature is not particularly limited, and for example, may be 135°C or lower, preferably 130°C or lower, and more preferably 120°C or lower. Thereby, low-temperature curing characteristics can be improved.

In this embodiment, as the exothermic start temperature, the difference between the exothermic height H1 at 70 ° C and the exothermic height H _MAX at the maximum exothermic peak temperature is ΔH1, and the exothermic height is Let the temperature when 3% of ?H1 is reached as the above-mentioned exothermic start temperature.

Further, in the DSC curve of the epoxy resin composition of this embodiment, the difference between the exothermic height H1 at 70 ° C and the exothermic height H _MAX at the maximum exothermic peak temperature is ΔH1, and the exothermic height H1 and 120 ° C. When the difference in the heat generation height H2 in the case is ΔH2, (ΔH2/ΔH1)×100 represents the ratio of the heating height at 120°C.

The upper limit of the heating height ratio at 120°C is, for example, 40 or less, preferably 39 or less, and more preferably 38 or less. Thereby, the manufacturing stability of an epoxy resin composition can be improved. In the epoxy resin composition containing an inorganic filler (D), a slit burr can be suppressed, for example. On the other hand, the lower limit of the heating height ratio at 120°C is, for example, 0.5 or more, preferably 0.8 or more, and more preferably 1.0 or more. Thereby, low-temperature curing characteristics can be improved.

Moreover, in this embodiment, when the curing torque of the said epoxy resin composition is measured with time at a mold temperature of 175 degreeC using a Curelastometer, the maximum curing torque up to 600 seconds after the start of measurement Let the value be T _max , the generation time be T1 , and the elapsed time from the start of the measurement to reach the curing torque value of 80% of T _max is T2 . At this time, the lower limit of T2/T1 is, for example, 1.20 or more, Preferably it is 2.65 or more, Preferably it is 2.7 or more, More preferably, it is 2.9 or more. Thereby, the manufacturing stability of an epoxy resin composition can be improved. The upper limit of T2/T1 is, for example, 4.50 or less, Preferably it is 4.0 or less, More preferably, it is 3.9 or less. Thereby, sclerosis|hardenability of an epoxy resin can be improved.

Moreover, in said T2/T1, 38 s or more and 95 s or less are preferable, and, for example, T1 is more preferable 40 s or more and 60 s or less. By making T1 more than a lower limit, the fluidity|liquidity of an epoxy resin composition can be improved. By making T1 or less into an upper limit, sclerosis|hardenability of an epoxy resin composition can be improved.

In the present embodiment, for example, by appropriately selecting the type and compounding amount of each component contained in the epoxy resin composition, the exothermic onset temperature and 120 in the S3/S1, S _48h 3/S _48h 1 and the DSC curve It is possible to control the calorific value in °C. Among these, for example, the use of a type having at least one or more hydroxyl groups in the lactone ring A as the lactone compound, or appropriately controlling the content ratio of the lactone compound to the curing accelerator, is S3/S1, _S48h 3 /S _48h 1 and the heat generation onset temperature in the DSC curve and the amount of heat generated at 120°C are mentioned as factors for making the desired numerical range.

The epoxy resin composition of this embodiment can be used as a resin composition for sealing used for sealing of electronic components, such as a semiconductor element, for example. Moreover, the epoxy resin composition of this embodiment can be used for sealing objects, such as the object for transfer molding, the object for MAP molding, the object for compression molding, or the object for an underfill material.

The semiconductor device of this embodiment can be equipped with a semiconductor element and the sealing member which seals a semiconductor element. Such a sealing member is comprised from the hardened|cured material of the epoxy resin composition of this embodiment. The semiconductor device of this embodiment is obtained by hardening-molding the said epoxy resin composition using molding methods, such as a transfer mold, a compression mold, an injection mold, for example, and sealing electronic components, such as a semiconductor element.

Although it does not specifically limit as a semiconductor device of this embodiment, For example, SIP (Single Inline Package), HSIP (SIP with Heatsink), ZIP (Zig-zag Inline Package), DIP (Dual Inline Package), SDIP (Shrink Dual) Inline Package), SOP(Small Outline Package), SSOP(Shrink Small Outline Package), TSOP(Thin Small Outline Package), SOJ(Small Outline J-leaded Package), QFP(Quad Flat Package), QFP(FP)(QFP) Fine Pitch), TQFP (Thin Quad Flat Package), QFJ (PLCC) (Quad Flat J-leaded Package), BGA (Ball Grid Array), etc. are mentioned.

Next, the semiconductor device 100 will be described with reference to FIG. 1 .

1 is a cross-sectional view showing an example of a semiconductor device 100 .

The semiconductor device 100 includes a substrate 10, a semiconductor element 20 mounted on one surface of the substrate 10, and an encapsulation resin layer ( 30) is a semiconductor package provided with. That is, the semiconductor device 100 is a single-sided sealing type semiconductor package in which the other surface of the substrate 10 opposite to the one surface is not sealed by the encapsulation resin layer 30 . The sealing resin layer 30 is comprised by the hardened|cured material of the epoxy resin composition of this embodiment. Thereby, since the coefficient of linear expansion of the sealing resin layer 30 at the time of heat can be enlarged, the difference of the coefficient of thermal expansion of the sealing resin layer 30 and the board|substrate 10 can be made small. For this reason, at the time of use in a high-temperature environment, the warp of the whole semiconductor device 100 can be suppressed.

In this embodiment, the upper surface of the semiconductor element 20 may be covered with the sealing resin layer 30 (FIG. 1), and may be exposed from the sealing resin layer 30 (not shown).

In the example shown in FIG. 1 , an organic substrate is used as the substrate 10 . A plurality of solder balls 12 are provided on the back surface of the substrate 10 opposite to the front surface (mounting surface) on which the semiconductor element 20 is mounted, for example. Moreover, the semiconductor element 20 is flip-chip mounted on the board|substrate 10, for example. The semiconductor element 20 is electrically connected to the board|substrate 10 via the some bump 22, for example. As a modification, the semiconductor element 20 may be electrically connected to the substrate 10 via a bonding wire.

In the present example shown in FIG. 1 , the gap between the semiconductor element 20 and the substrate 10 is filled with the underfill 32 , for example. As the underfill 32, for example, a film-like or liquid underfill material can be used. Although the underfill 32 and the sealing resin layer 30 may be comprised from different materials, they may be comprised from the same material. The epoxy resin composition of this embodiment can be used as a mold underfill material. For this reason, while the underfill 32 and the sealing resin layer 30 can be comprised with the same material, it is also possible to form by the same process. Specifically, the sealing process of sealing the semiconductor element 20 with the epoxy resin composition and the filling process of filling the gap between the substrate 10 and the semiconductor element 20 with the epoxy resin composition are performed in the same process (batch). can be carried out.

In the present embodiment, the thickness of the sealing resin layer 30 is, for example, from the mounting surface of the substrate 10 (one surface opposite to the surface on which the solder ball 12 for external connection is formed), the sealing resin layer ( 30) may be the shortest distance to the ceiling surface. In addition, the thickness of the sealing resin layer 30 refers to the thickness of the sealing resin layer 30 on the basis of the said one surface in the normal line direction of the one surface on which the semiconductor element 20 in the board|substrate 10 is mounted. In this case, the upper limit of the thickness of the sealing resin layer 30 is good also as 0.4 mm or less, for example, is good also as 0.3 mm or less, and is good also as 0.2 mm or less. In addition, although the lower limit of the thickness of the sealing resin layer 30 is not specifically limited, For example, it is good also as 0 mm or more (exposed type), and good also as 0.01 mm or more.

Moreover, the upper limit of the thickness of the board|substrate 10 is good also as 0.8 mm or less, and good also as 0.4 mm or less, for example. In addition, although the lower limit of the thickness of the board|substrate 10 is not specifically limited, It is good also as 0.1 mm or more, for example.

According to the present embodiment, the thickness of the semiconductor package can be reduced in this way. Moreover, even if it is a thin semiconductor package, it becomes possible to suppress the curvature of the semiconductor device 100 by forming the sealing resin layer 30 using the epoxy resin composition which concerns on this embodiment. Moreover, in this embodiment, the thickness of the sealing resin layer 30 can be made into the thickness of the board|substrate 10 or less, for example. Accordingly, the semiconductor device 100 can be more efficiently reduced in thickness.

Next, the structure 102 will be described.

2 is a cross-sectional view showing an example of the structure 102 . The structure 102 is a molded article formed by MAP molding. For this reason, by dividing the structure 102 into individual pieces for each semiconductor element 20, a plurality of semiconductor packages are obtained.

The structure 102 includes a substrate 10 , a plurality of semiconductor elements 20 , and a sealing resin layer 30 . The plurality of semiconductor elements 20 are arranged on one surface of the substrate 10 . In FIG. 2 , the case in which each semiconductor element 20 is flip-chip mounted with respect to the board|substrate 10 is illustrated. In this case, each semiconductor element 20 is electrically connected to the substrate 10 via a plurality of bumps 22 . In addition, each semiconductor element 20 may be electrically connected to the board|substrate 10 via a bonding wire. In addition, as the board|substrate 10 and the semiconductor element 20, the thing similar to what was illustrated in the semiconductor device 100 can be used.

In the example shown in FIG. 2 , the gap between each semiconductor element 20 and the substrate 10 is filled with the underfill 32 , for example. As the underfill 32, for example, a film-like or liquid underfill material can be used. On the other hand, the above-mentioned epoxy resin composition can also be used as a mold underfill material. In this case, sealing of the semiconductor element 20 and filling of the clearance gap between the board|substrate 10 and the semiconductor element 20 are performed collectively.

The encapsulating resin layer 30 seals the one surface of the plurality of semiconductor elements 20 and the substrate 10 . In this case, the other surface of the substrate 10 opposite to the one surface is not sealed by the encapsulation resin layer 30 . Moreover, the sealing resin layer 30 is comprised with the hardened|cured material of the above-mentioned epoxy resin composition. Thereby, the warpage of the structure 102 and the semiconductor package obtained by dividing the structure 102 into pieces can be suppressed. The sealing resin layer 30 is formed by sealingly molding an epoxy resin composition using well-known methods, such as a transfer molding method or a compression molding method, for example. Moreover, in this embodiment, the upper surface of each semiconductor element 20 may be sealed with the sealing resin layer 30, and may be exposed from the sealing resin layer 30, as shown in FIG.

In this embodiment, although the case where the epoxy resin composition of this invention is used as a sealing material of a semiconductor device was demonstrated, as a use of the epoxy resin composition of this invention, it is not limited to this.

As mentioned above, although embodiment of this invention was described with reference to drawings, these are illustrations of this invention, and various structures other than the above can also be employ|adopted.

Example

Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited to description of these Examples.

The components used in each Example and each comparative example are shown below.

(Preparation of epoxy resin composition)

First, in Examples 1 to 8 and Comparative Example 1, each raw material blended according to Table 1 was mixed at room temperature by a mortar, and then melt-mixed on a hot plate at 120° C. for 3 minutes. After cooling, it pulverized again at room temperature using a mortar to obtain an epoxy resin composition.

Moreover, in Examples 9-16 and Comparative Example 2, each raw material mix|blended according to Table 1 was mixed at room temperature using a mixer, and then roll-kneaded at 70-100 degreeC. After cooling, it grind|pulverized and obtained the epoxy resin composition.

The detail of each component in Table 1 is as follows. In addition, the unit in Table 1 is weight%.

Epoxy resin (A)

Epoxy resin 1: phenol aralkyl type epoxy resin having a biphenylene skeleton (Nippon Kayaku Co., Ltd. NC-3000, epoxy equivalent 276 g/eq, softening point 57° C.)

Epoxy resin 2: triphenylmethane type epoxy resin (Mitsubishi Chemical Co., Ltd. 1032H-60, epoxy equivalent 163 g/eq)

Phenolic Resin (B)

Phenolic resin 1: Phenol aralkyl resin having a biphenylene skeleton (Nippon Kayaku Co., Ltd. GPH-65, hydroxyl equivalent 196 g/eq, softening point 65° C.)

Phenolic resin 2: Phenolic resin having a triphenylmethane skeleton (Meiwa Kasei Co., Ltd. MEH-7500, hydroxyl equivalent 97 g/eq, softening point 110° C.)

hardening accelerator (C)

Curing accelerator 1: triphenylphosphine (TPP) (manufactured by K-I Kasei Co., Ltd., PP360)

Cure retardant (E)

Curing retardant 1: dicoumarol represented by the following formula (manufactured by Tokyo Kasei Co., Ltd., M0216)

[Formula 20]

Curing retardant 2: 4-hydroxycoumarin represented by the following formula (manufactured by Tokyo Kasei Co., Ltd., H0235)

[Formula 21]

Inorganic Filling (D)

Inorganic filler 1: fused spherical silica (average particle size: 31 µm, specific surface area: 1.6 m ² /g, manufactured by Denka Corporation, FB-508S)

(additive)

Silane coupling agent 1: 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-403)

Colorant 1: Carbon black (manufactured by Mitsubishi Chemical Co., Ltd., MA600)

Release agent 1: glycerin montanic acid ester (melting point 80°C, Clariant Co., Ltd., Recolve WE4)

Ion trapping agent 1: hydrotalcite (manufactured by Kyowa Chemical Industries, Ltd., DHT-4H)

Stress reducing agent 1: Epoxy polyether-modified siloxane (Toray Dow Corning Co., Ltd., FZ-3730)

Stress reducing agent 2: carboxyl group-terminated butadiene/acrylonitrile copolymer (PTI Japan Co., Ltd., CTBN1008-SP)

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

About each Example and each comparative example, each evaluation of the epoxy resin composition was performed as follows, respectively. An evaluation result is shown to Tables 2-5.

(DSC)

Using a differential scanning calorimeter (DSC-6100 manufactured by Seiko Instruments), 10 mg of the epoxy resin composition was measured under a nitrogen stream at a temperature increase rate of 10°C/min in a temperature range of 30°C to 300°C. The difference between the exothermic height H1 at 70°C and the exothermic height H _MAX at the maximum exothermic peak temperature is ΔH1, and the exothermic height when the exothermic height H1 is taken as a reference is the temperature when 3% of ΔH1 is reached. , was set as the above-mentioned exothermic initiation temperature. Further, when the difference between the exothermic height H1 and the exothermic height H2 at 120°C is ΔH2, (ΔH2/ΔH1)×100 represents the ratio of the exothermic height at 120°C. A result is shown in Table 2. 3 is a diagram showing the measurement results of DSC of Examples 3, 6, and Comparative Example 1. FIG.

(lowest melt viscosity)

The lowest melt viscosity was measured using a viscometer as follows.

First, it measured about the tablet-type epoxy resin composition using the corn plate type viscometer (The Toa Kogyo Co., Ltd. make, manufacture number CV-1S). As the tablet-type epoxy resin composition, 100 mg of the epoxy resin composition was put into a mold of 25 mm phi , and what was tableted for 3 t 1 minute was used. Moreover, the epoxy resin composition tested the sample A immediately after tablet preparation, and tested the sample B after storage at 40 degreeC for 48 hours.

As a measurement procedure of the melt viscosity by a viscometer, a measurement is started immediately after placing Sample A (tablet-type epoxy resin composition) on a hot plate. Let 0 s immediately after the sample is placed on a hot plate at 175° C., the lowest melt viscosity is η1, the viscosity three times η1 is η3, the time from the start of measurement to reach η1 is S1, η1 is reached The time from the time until reaching (eta)3 was made into S3.

In the same manner as in Sample A, the melt viscosity of Sample B is measured, and immediately after the sample is placed on a hot plate at 175 ° C. The time from the start of the measurement to reaching η1 was _S48h1 , and the time from reaching η1 to reaching η3 was _S48h3 . In addition, the viscosity increase rate in Table 3 represents the lowest melt viscosity η1 of the sample B 1 - the lowest melt viscosity η1| of the sample A after storage at 40° C. for 48 hours, and the lowest viscosity increase rate is the lowest melt viscosity η1 of the sample A , represents the rate of increase of the lowest melt viscosity η1 of sample B. A result is shown in Table 3. 4 is a view showing changes with time of melt viscosity of Examples 3, 6, and Comparative Example 1. FIG. In FIG. 4 , the solid line indicates sample A (0 h before storage), and the dotted line indicates sample B (after storage at 40° C. for 48 hours).

(Slit Burr)

40.0 g of the obtained epoxy resin composition is placed in a mold of 40 mmφ, and the tablet-type epoxy resin composition compressed under the conditions of 60 kgf/cm ² is injected and molded into a grooved mold at 175° C., 10 MPa, and 120 seconds with a low-pressure transfer molding machine. When it did, the length of the resin which flowed out to each slit (80, 60, 40, 20, 10, 5 micrometers width) was measured, and it was set as the fillability index|index. What flowed out 4 micrometers or more in 80, 60 micrometers width, and less than 4 micrometers flowed out in 40, 20, 10, and 5 micrometers width was made into (double-circle). What flowed out 4 micrometers or more in 80, 60 micrometers width, or less than 4 micrometers flowed out in 40, 20, 10, or 5 micrometers width was made into (circle). In 80, 60 micrometers width, less than 4 micrometers, and in 40, 20, 10, and 5 micrometers width, 4 micrometers or more flowed out was made into x. A result is shown in Table 4.

(Amount of wire deflection)

4.1 g of the obtained epoxy resin composition was put in a mold of 13 mmφ, and the tablet-type epoxy resin composition tableted under the conditions of 30 kgf/cm ² was subjected to a low-pressure transfer molding machine at 175° C., 6.9 MPa, and 120 seconds. 208 for wire deflection evaluation test Each 10 pin QFP package (dimension; 28×28×2.4mmt, Cu lead frame, test element; 9×9mm, wire; Au, 1.2mils, 5mm) was molded, and the molded 208-pin QFP package was soft X-rayed. It observed with the permeation|transmission apparatus (Axlon International Co., Ltd. product, product number PMS-160).

As a method of calculating the amount of wire deflection, the deflection amount of the wire that is most deflected (deformed) in one package is (F) and the length of the wire is (L), the deflection amount = F/L × 100 (%) It was calculated and the average value of 10 packages was shown in the table|surface.

As determination of the amount of wire deflection, less than 5% was made into (double-circle), 5 to 6% was made into (circle), and 6% or more was made into x.

A result is shown in Table 4.

(Cure Lasting @ 175℃)

Measure the curing torque of the epoxy resin composition over time at a mold temperature of 175° C. using a curing meter (A&DJ Co., Ltd., Curelastometer WP type), and after 600 seconds from the start of the measurement The maximum cure-last torque value up to this point was taken as the saturation torque value. Moreover, as for the tablet, what put 4.3 g of epoxy resin compositions in the metal mold|die of 25 mm (phi), and what was tableted for 5 t and 1 minute was used. In addition, the epoxy resin composition tested the sample immediately after tablet preparation. In addition, the generation time of curelast was observed when about 60% of reactive functional groups reacted. A result is shown in Table 5.

From Examples 1-16, it turned out that the epoxy resin composition of this invention is excellent in a melt viscosity characteristic, and manufacture stability is acquired. Moreover, from Examples 9-16, it turned out that the semiconductor sealing material excellent in a melt viscosity characteristic is obtained by using the epoxy resin composition of this invention.

As mentioned above, although this invention was demonstrated more concretely based on an Example, these are an illustration of this invention, and various structures other than the above can also be employ|adopted.

This application claims priority on the basis of Japanese Patent Application No. 2016-172600 for which it applied on September 5, 2016, and uses all the indication here.

Claims (12)

epoxy resin,
phenolic resin,
a curing accelerator;
An epoxy resin composition comprising a curing retardant, comprising:
The curing retardant includes a lactone compound having a hydroxyl group bonded to a lactone ring,
When the epoxy resin composition is heated to a molten state at 175 ° C., the melt viscosity initially decreases, and after reaching the lowest melt viscosity, it has a characteristic that further increases,
Let the lowest melt viscosity of the epoxy resin composition be η1, the viscosity three times that of η1 be η3, the time from the start of measurement to reaching η1 is S1, the time from reaching η1 to reaching η3 S3/S1 is 3.5 or more and 15 or less when S3 is made into S3, The epoxy resin composition. The method according to claim 1,
The epoxy resin composition was molded into a tablet form and stored at 40° C. for 48 h,
Let the lowest melt viscosity of the epoxy resin composition be η1, the viscosity three times that of η1 is η3, the time from the start of the measurement to reach η1 is S _48h 1, from reaching η1 until reaching η3 When the time of S _48h 3 is set, S _48h 3/S _48h 1 is 3.5 or more and 15 or less, the epoxy resin composition. The method according to claim 1,
Let the lowest melt viscosity of the epoxy resin composition be η1, the viscosity ten times that of η1 be η10, the time from the start of measurement to reaching η1 is S1, the time from reaching η1 to reaching η10 is S10, and |S10/S1-S3/S1| is 2.20 or more and 7 or less, The epoxy resin composition. epoxy resin,
phenolic resin,
a curing accelerator;
An epoxy resin composition comprising a curing retardant, comprising:
The curing retardant includes a lactone compound having a hydroxyl group bonded to a lactone ring,
The exothermic onset temperature in the DSC curve of the epoxy resin composition obtained when the temperature is raised from 30°C to 300°C under the condition of a temperature increase rate of 10°C/min using a differential scanning calorimeter is in the range of 94°C or more and 135°C or less , an epoxy resin composition. 5. The method according to claim 4,
In the DSC curve of the epoxy resin composition, the difference between the exothermic height H1 at 70°C and the exothermic height H _MAX at the maximum exothermic peak temperature is ΔH1, and the exothermic height H1 and the exothermic height H2 at 120°C An epoxy resin composition, wherein (ΔH2/ΔH1)×100 is 0.5 or more and 40 or less when the difference of ΔH2 is ΔH2. 5. The method according to claim 1 or 4,
The epoxy resin composition, wherein the lactone compound has a coumarin structure or a biscoumarin structure. 5. The method according to claim 1 or 4,
The pKa of the said lactone compound is 2 or more and 6 or less, The epoxy resin composition. 5. The method according to claim 1 or 4,
The epoxy resin composition whose molar ratio of content of the said hardening retarder with respect to content of the said hardening accelerator in the said epoxy resin composition is 0.1 or more and 4 or less. 5. The method according to claim 1 or 4,
Content of the said curing retarder is 0.01 weight% or more and 1.5 weight% or less with respect to the said whole epoxy resin composition, The epoxy resin composition. 5. The method according to claim 1 or 4,
Further comprising an inorganic filler, the epoxy resin composition. 5. The method according to claim 1 or 4,
The epoxy resin composition used for sealing of a semiconductor element. a semiconductor device,
A semiconductor device comprising a sealing member for sealing the semiconductor element,
The semiconductor device in which the said sealing member is comprised with the hardened|cured material of the epoxy resin composition of Claim 1 or 4.

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