KR20190127770A - Paste Resin Composition - Google Patents

Abstract

The paste resin composition containing (A) epoxy resin, (B) liquid hardening | curing agent, (C) heat conductive filler, and (D) dispersing agent.

Description

Paste Resin Composition

The present invention relates to a paste-like resin composition. Moreover, it is related with the circuit board, semiconductor chip package, and electronic member which used paste-like resin composition.

In recent years, miniaturization and high functionalization of electronic devices advance, and there exists a tendency for the mounting density of the semiconductor element in a printed wiring board to become high. In addition to the enhancement of the semiconductor device to be mounted, a technology for efficiently dissipating heat generated by the semiconductor device is required.

For example, Patent Document 1 discloses heat dissipation by using, for a circuit board, an insulating layer cured of a resin composition containing a resin and an alumina satisfying a predetermined requirement.

Japanese Laid-Open Patent Publication No. 2012-77123

The present inventors examined to more efficiently radiate the heat which the semiconductor element generate | occur | produces. As a result, for example, when silicon carbide is contained in the resin composition, the thermal conductivity of the insulating layer can be increased, but the viscosity of the resin composition increases, and it has been found that the resin composition may not be applied to a circuit board or the like.

This invention is made | formed in view of the above, The paste-like resin composition with low viscosity which can obtain the hardened | cured material with high thermal conductivity; And a circuit board, a semiconductor chip package, and an electronic member using the pasty resin composition.

In order to achieve the subject of this invention, as a result of earnestly examining by the present inventors, the hardened | cured material with high thermal conductivity is contained by containing (A) epoxy resin, (B) liquid curing agent, (C) thermal conductive filler, and (D) dispersing agent. Could get Moreover, it turned out that the pasty resin composition with a low viscosity can be provided and came to complete this invention.

That is, this invention includes the following content.

[1] (A) epoxy resin,

(B) liquid curing agent,

(C) a thermally conductive filler, and

(D) Paste-shaped resin composition containing a dispersing agent.

[2] The paste-like resin composition according to [1], wherein the content of the organic solvent contained in the paste-like resin composition is less than 1.0% by mass relative to the total mass of the paste-like resin composition.

[3] The paste-like resin composition according to [1] or [2], wherein the thermal conductivity of the cured product of the paste-like resin composition is 2.0 W / mK or more.

[4] The paste-like resin composition according to any one of [1] to [3], in which the component (D) contains an oxyalkylene-containing phosphate ester.

[5] The paste-like resin composition according to any one of [1] to [4], in which the component (C) contains at least one member selected from silicon carbide, boron nitride, aluminum nitride, and aluminum oxide.

[6] The paste-like resin composition according to any one of [1] to [5], in which the component (C) contains silicon carbide.

[7] The paste-like resin composition according to [6], wherein the silicon carbide has an average particle diameter of 1 µm or more and 30 µm or less.

[8] The paste-like resin composition according to [6] or [7], in which the component (C) further contains at least one member selected from boron nitride, aluminum nitride, and aluminum oxide.

[9] The paste form according to any one of [1] to [8], wherein the content of the component (C) is 60% by mass to 95% by mass when the nonvolatile component in the pasty resin composition is 100% by mass. Resin composition.

[10] The paste-like resin composition according to any one of [1] to [9], in which the component (B) contains at least one member selected from a polythiol compound and a liquid phenol resin.

[11] The component (B) is trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) ), Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, tris (3-mercaptopropyl) isocyanurate, thioglycolate octyl, ethylene glycol bisthioglycolate, trimethylol Propanetristhioglycolate, pentaerythritol tetrakisthioglycolate, 3-mercaptopropionic acid, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1, 3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropanetris (3-mercapto Butyrate), trimethylolethanetris (3-mercaptobutyrate), 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril, and 4,4'-iso Containing at least one polythiol compound selected from propylidenebis [(3-mercaptopropoxy) benzene] and a liquid phenol resin selected from alkenyl group-containing novolac phenol resins, The paste resin composition as described in any one of 1]-[10].

[12] The paste-like resin composition according to any one of [1] to [11], wherein the viscosity at 25 ° C. of the paste-like resin composition is 350 Pa · s or less.

[13] A circuit board comprising an insulating layer formed of the cured product of the paste-like resin composition according to any one of [1] to [12].

[14] A semiconductor chip package, comprising the circuit board according to [13] and a semiconductor chip mounted on the circuit board.

[15] A semiconductor chip package comprising the semiconductor chip sealed by the paste-like resin composition according to any one of [1] to [12].

[16] An electronic member having a heat sink, a cured product of the paste-like resin composition according to any one of [1] to [12] provided on the heat sink, and an electronic component mounted on the cured product.

According to this invention, the paste-like resin composition with low viscosity which can obtain the hardened | cured material with high thermal conductivity; And a circuit board, a semiconductor chip package, and an electronic member using the pasty resin composition.

1 is a schematic cross-sectional view showing an example of a semiconductor chip package (Fan-out type WLP) of the present invention.

Hereinafter, the paste-like resin composition, the circuit board, the semiconductor chip package, and the electronic member of the present invention will be described in detail.

Paste Resin Compositions

The paste resin composition contains (A) an epoxy resin, (B) a liquid curing agent, (C) a thermally conductive filler, and (D) a dispersant. By containing (A)-(D) component, the viscosity of a pasty resin composition can be made low and the thermal conductivity of the hardened | cured material can be made high. Moreover, since a paste resin composition is paste form, adhesiveness of the hardened | cured material and electronic members, such as a circuit board, improves. Since the hardened | cured material of a pasty resin composition has high thermal conductivity and adhesiveness improves, the heat radiation efficiency of the said electronic member can be improved. The paste resin composition is paste at 25 ° C. The paste shape refers to a full-phase property having a viscosity that can be applied to electronic members such as a circuit board.

The paste-like resin composition may further contain (E) a curing accelerator, (F) flame retardant, and (G) optional additives in addition to the components (A) to (D) as necessary. Hereinafter, each component contained in a paste resin composition is demonstrated in detail.

<(A) Epoxy Resin>

The paste resin composition contains the epoxy resin (A). By containing (A) component, insulation reliability can be improved.

As the component (A), for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol Epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, Glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclo Hexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin, Li may be mentioned methyl olhyeong epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that (A) component contains the epoxy resin which has two or more epoxy groups in 1 molecule. When the nonvolatile component of an epoxy resin is 100 mass%, it is preferable that at least 50 mass% or more is an epoxy resin which has two or more epoxy groups in 1 molecule. It is preferable that a resin composition contains liquid epoxy resin (henceforth "liquid epoxy resin") at 20 degreeC, and is a liquid epoxy resin and epoxy resin (henceforth "solid epoxy resin") solid at temperature 20 degreeC. It is more preferable to contain in combination). As a liquid epoxy resin, the liquid epoxy resin which has two or more epoxy groups in 1 molecule is preferable, and the aromatic liquid epoxy resin which has two or more epoxy groups in 1 molecule is more preferable. As a solid epoxy resin, the solid epoxy resin which has three or more epoxy groups in 1 molecule is preferable, and the aromatic solid epoxy resin which has three or more epoxy groups in 1 molecule is more preferable. In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.

Examples of the liquid epoxy resin include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, and phenol novolac type epoxy resins. , An alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a bisphenol A type epoxy resin and a bisphenol F type epoxy resins and cyclohexane type epoxy resins are more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation, "828US", "jER828EL", "825" and "Epicoat" manufactured by Mitsubishi Chemical Co., Ltd. 828EL "(bisphenol A type epoxy resin)," jER807 "," 1750 "(bisphenol F type epoxy resin)," jER152 "(phenol novolak type epoxy resin)," 630 "," 630LSD "(glycidylamine type) Epoxy resin), "ZX1059" by Shinnitetsu Sumikin Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" by Nagase Chemtex Co., Ltd. (glycidyl ester type epoxy) Resin), "Ceroxide 2021P" manufactured by Daicel Co., Ltd. (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having butadiene structure), "ZX1658" manufactured by Shinnitetsu Sumikin Chemical Co., Ltd., " ZX1658GS "(Liquid 1,4-glycidylcyclohexane-type epoxy resin), Mitsubishi Chemical "630LSD" (glycidyl amine-type epoxy resin) of the product of and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

As a solid epoxy resin, a bixylenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, a non- Phenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, tetraphenylethane type epoxy resins are preferred, and bixylenol type epoxy resins, naphthalene type epoxy resins, More preferred are bisphenol AF type epoxy resins and naphthylene ether type epoxy resins. As a specific example of a solid epoxy resin, "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin) by a DIC company, "N-690" (cresol novolak) Type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA-7311" "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN-502H" by Nihon Kayaku Co., Ltd. Phenolic epoxy resin), `` NC7000L '' (naphthol novolac type epoxy resin), `` NC3000H '', `` NC3000 '', `` NC3000L '', `` NC3100 '' (biphenyl type epoxy resin), manufactured by Shinnitetsu Sumikin Chemical Co., Ltd. ESN475V '' (naphthalene type epoxy resin), `` ESN485 '' (naphthol novolac type epoxy resin), Mitsubishi Chemical Co., Ltd. 'YX4000H', 'YX4000', 'YL6121' (biphenyl type epoxy resin), 'YX4000HK' ( ratio (Synolol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100" by Osaka Gas Chemical Co., Ltd., "CG-500", "YL7760" by Mitsubishi Chemical Co., Ltd. (bisphenol AF type epoxy resin) "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin) by Mitsubishi Chemical Co., Ltd., "jER1031S" (tetraphenylethane type epoxy resin), etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

As a component (A), when using a liquid epoxy resin and a solid epoxy resin together, these ratios (liquid epoxy resin: solid epoxy resin) have a mass ratio, and the range of 1: 0.01-1: 5 is preferable. By setting the ratio between the liquid epoxy resin and the solid epoxy resin in such a range, effects such as obtaining a cured product having sufficient breaking strength can be obtained. From the viewpoint of the above effects, the ratio of the liquid epoxy resin and the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1: 0.05 to 1: 1 by mass ratio, and 1: 0.1 to 1: 0.5. The range of is more preferable.

When content of (A) component makes 100 mass% of the whole non volatile components in paste resin composition from a viewpoint of obtaining the insulating layer which shows favorable mechanical strength and insulation reliability, Preferably it is 1 mass% or more, More preferable Preferably it is 3 mass% or more, More preferably, it is 5 mass% or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention appears, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less.

The epoxy equivalent of (A) component becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, More preferably, it is 110-1000. By setting it as this range, the crosslinking density of hardened | cured material becomes enough and it can bring about the insulating layer with small surface roughness. In addition, an epoxy equivalent can be measured according to JISK7236, and is a mass of resin containing 1 equivalent of epoxy groups.

The weight average molecular weight of (A) component becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of an epoxy resin is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

<(B) Liquid Curing Agent>

The pasty resin composition contains the liquid curing agent (B). The viscosity of a paste-like resin composition can be made low by combining the component (B) and the dispersing agent (D) mentioned later. The component (B) has a function of curing the component (A), and is not particularly limited as long as it is a liquid curing agent at a temperature of 20 ° C. Examples include a polythiol compound, a liquid phenol resin, an acid anhydride, and imidazole. Can be. (B) A component may be used individually by 1 type and may use 2 or more types together.

The component (B) contains at least one member selected from a polythiol compound and a liquid phenol resin from the viewpoint of being able to cure the paste resin composition in a low temperature region and greatly contribute to the low viscosity of the paste resin composition. It is preferable to, and it is preferable to contain either a polythiol compound and a liquid phenol resin.

The polythiol compound is not particularly limited as long as it is a compound that crosslinks or polymerizes an epoxy group. However, the number of thiol groups in one molecule is preferably 2 to 6 (bifunctional to 6 functional), and 3 to 6 (trifunctional to 6 functional). It is preferable. As such a polythiol compound, trimethylol propane tris (3-mercaptopropionate) (abbreviation: TMTP), pentaerythritol tetrakis (3-mercaptopropionate) (abbreviation: PEMP), dipenta Erythritol hexakis (3-mercaptopropionate) (abbreviated as DPMP), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate (abbreviated as: TEMPIC), tris (3-mercapto Propyl) isocyanurate (abbreviation: TMPIC), octyl thioglycolate (abbreviation: OTG), ethylene glycol bisthioglycolate (abbreviation: EGTG), trimethylolpropane tristhioglycolate (abbreviation: TMTG), pentaerythritol tetra Kisthioglycolate (abbreviation: PETG), 3-mercaptopropionic acid (abbreviation: 3-MPA), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane , 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylol Lophantris (3-mercaptobutyrate) (abbreviation: TPMB), trimethylolethane tris (3-mercaptobutyrate) (abbreviation: TEMB), 1,3,4,6-tetrakis (2-mercaptoethyl) glycol Usyl, 4,4'-isopropylidene bis [(3-mercaptopropoxy) benzene], etc. are mentioned. These compounds can be synthesized by a known method, for example, tris (3-mercaptopropyl) isocyanurate (abbreviated as TMPIC) or 4,4'-isopropylidenebis [(3-mercaptoprop Foxy) benzene] can be synthesized, for example, by the method described in JP-A-2012-153794 or JP-A-2001 / 00698.

The polythiol compound may use a commercial item, and as a commercial item, for example, "PEMP" (made by SC Yuki Chemical Co., Ltd.), "OTG", "EGTG", "TMTG", "PETG", "3-MPA", `` TMTP '', `` PETP '' (manufactured by Yodogagaku Co., Ltd.), `` TEMP '', `` PEMP '', `` TEMPIC '', `` DPMP '' (manufactured by Sakai Chemical Co., Ltd.), `` PE-1 '' (pentaerythritol tetrakis ( 3-mercaptobutyrate)), "BD-1" (1,4-bis (3-mercaptobutyryloxy) butane), "NR-1" (1,3,5-tris (3-mercaptobuty) Reyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione), "TPMB", "TEMB" (made by Showa Denko), "TS-G (Mercaptoethyl glycol) (manufactured by Shikoku Chemical Co., Ltd.). You may use a polythiol compound 1 type or in combination of 2 or more types.

The thiol group equivalent of the polythiol compound is preferably 50 to 500 g / eq, more preferably 75 to 300 g / eq, still more preferably 100 to 200 g / eq. A "thiol group equivalent" is the number of grams (g / eq) of resin containing a 1-gram equivalent thiol group, and can be measured by a well-known method, for example, the urea solution titration method which uses a starch as an indicator.

The liquid phenol resin is not particularly limited as long as it is a liquid resin at a temperature of 20 ° C. containing a phenolic hydroxyl group. Examples of the liquid resin at a temperature of 20 ° C. containing a phenolic hydroxyl group include cresol resins, novolak type phenol resins (phenol novolak resins, cresol novolak resins, and modified substances thereof), liquid alkenyl group-containing phenol resins, and the like. These are mentioned, A liquid alkenyl-group containing phenol resin is preferable. Carbon number of an alkenyl group becomes like this. Preferably it is 2-10, More preferably, it is 2-6, More preferably, it is 2-4, Especially preferably, it is 3. Among these, as an alkenyl group, 2-propenyl group (allyl group) is preferable.

As a liquid alkenyl group containing phenol resin, an alkenyl group containing novolak-type phenol resin is mentioned, The phenol resin represented by following General formula (1) is preferable.

In Chemical Formula 1,

R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkenyl group,

R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group,

j represents an integer of 0 to 5, provided that at least one of R ¹ , R ² , R ³ , R ^4, and R ⁵ is an alkenyl group.

In said Formula (1), R <^1> , R <^2> , R <^3> , R <^4> and R <^5> represent a hydrogen atom or an alkenyl group each independently. However, in general formula (1), at least 1 of R <^1> , R <^2> , R <^3> , R <^4> and R <^5> is an alkenyl group. Carbon number of an alkenyl group becomes like this. Preferably it is 2-10, More preferably, it is 2-6, More preferably, it is 2-4, Especially preferably, it is 3. Among these, as an alkenyl group, 2-propenyl group (allyl group) is preferable.

In Formula (1), the number of alkenyl groups is not particularly limited as long as it is 1 or more, but preferably one or two per one benzene ring, and more preferably one per one benzene ring.

In Formula (1), a plurality of R ¹ may be the same as or different from each other. The same applies to R ² , R ³ , R ^4, and R ⁵ .

In formula (1), R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, 1 to 3, or 1.

In Formula 1, when two or more R <^7> exists, these may be same or different. The same applies to R ⁸ .

In formula (1), j is an integer of 0-5, Preferably it is an integer of 0-3, More preferably, it is 0 or 1, More preferably, it is 0.

R ¹ to R ⁸ may not have a substituent and may have a substituent. There is no restriction | limiting in particular as a substituent, For example, a halogen atom, -OH, -OC _1-6 alkyl group, -N (C _1-6 alkyl group) ₂ , C _1-6 alkyl group, C _6-10 aryl group,- NH _2- , -CN, -C (O) OC _1-6 alkyl group, -COOH, -C (O) H-, -NO ₂ and the like. Here, the term "C _pq " (p and q are positive integers and satisfies p <q) indicates that the number of carbon atoms in the organic group described immediately after this term is p to q. For example, the expression "C _1-6 alkyl group" represents an alkyl group having 1 to 6 carbon atoms. Said substituent may have an additional substituent (henceforth a "secondary substituent"). As a secondary substituent, the thing similar to the said substituent may be used unless there is particular notice.

A liquid phenol resin may use a commercial item. As a commercial item of a liquid phenol resin, Meiwa Kasei Co., Ltd. "MEH-8000H", "MEH-8005", etc. are mentioned, for example.

The phenolic hydroxyl group equivalent of a liquid phenol resin becomes like this. Preferably it is 50-500 g / eq, More preferably, it is 75-300 g / eq, More preferably, it is 100-200 g / eq. Phenolic hydroxyl group equivalent can be measured according to JIS K0070, and is the mass of resin containing 1 equivalent of phenolic hydroxyl group.

The ratio between the epoxy resin and the liquid curing agent is preferably in the range of 1: 0.1 to 1:10 in the ratio of [total number of epoxy groups of epoxy resin]: [total number of reactors of liquid curing agent], and 1: 0.5 to 1 : 5 is more preferable, and 1: 0.5-1: 3 are still more preferable. Here, the reactor of a liquid curing agent is a thiol group, a phenolic hydroxyl group, etc., and changes with kinds of liquid curing agent. The total number of epoxy groups of the epoxy resin is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent and the total number of all epoxy resins. The total number of reactors of the liquid curing agent is the solid content mass of each liquid curing agent. The value divided by the reactor equivalent is the sum of all liquid curing agents. By making the ratio of an epoxy resin and a liquid hardening | curing agent into such a range, the heat resistance of the hardened | cured material of a pasty resin composition improves more.

When content of (B) component makes 100 mass% of the whole non volatile components in paste resin composition from a viewpoint of the low viscosity of a pasty resin composition, Preferably it is 1 mass% or more, More preferably, it is 2 mass % Or more, More preferably, it is 3 mass% or more. Preferably an upper limit is 20 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less.

When the total content of the component (A) and the component (B) is 100% by mass of the nonvolatile component in the paste-like resin composition from the viewpoint of lowering the viscosity of the paste-like resin composition and improving the insulation reliability, preferably 2 It is mass% or more, More preferably, it is 5 mass% or more, More preferably, it is 8 mass% or more. Although the upper limit of the said total content is not specifically limited, Preferably it is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less.

<(C) Thermally Conductive Filler>

The pasty resin composition contains the (C) thermally conductive filler. By containing (C) component, hardened | cured material (insulating layer) with high thermal conductivity can be obtained.

Examples of the material of the component (C) include silicon carbide, silicon nitride, aluminum nitride, aluminum oxide (alumina), and the like. (C) A component may be used individually by 1 type and may be used in combination of 2 or more type. Moreover, you may use combining 2 or more types of the same materials. Especially, it is preferable that (C) component contains a silicon carbide from a viewpoint of obtaining the hardened | cured material with high thermal conductivity. The component (C) preferably contains at least one member selected from silicon carbide, boron nitride, aluminum nitride, and aluminum oxide from the viewpoint of lowering the viscosity while obtaining a cured product having high thermal conductivity. It is more preferable to contain 2 or more types selected from silicon, boron nitride, aluminum nitride, and aluminum oxide, and it is more preferable to contain 1 or more types chosen from boron nitride, aluminum nitride, and aluminum oxide with silicon carbide. desirable.

The thermal conductivity of the thermally conductive filler is preferably 30 W / m · K or more, more preferably 170 W / m · K or more, and even more preferably 270 W / m · K or more from the viewpoint of obtaining a cured product having high thermal conductivity. Although an upper limit is not specifically limited, It can be 1000 W / m * K or less.

The average particle diameter of silicon carbide is preferably 45 µm or less, more preferably 40 µm or less, and even more preferably 35 µm or less from the viewpoint of obtaining a cured product having high thermal conductivity. The minimum of an average particle diameter becomes like this. Preferably it is 0.1 micrometer or more, More preferably, it is 0.5 micrometer or more, More preferably, it is 1 micrometer or more.

The average particle diameter of the component (C) excluding silicon carbide is preferably 2.5 µm or less, more preferably 2 µm or less, from the viewpoint of obtaining a cured product having high thermal conductivity and decreasing the viscosity of the pasty resin composition. Preferably it is 1.5 micrometers or less. The minimum of an average particle diameter becomes like this. Preferably it is 0.01 micrometer or more, More preferably, it is 0.05 micrometer or more, More preferably, it is 0.08 micrometer or more.

The average particle diameter of (C) component can be measured by the laser diffraction scattering method based on the Mie scattering theory. Specifically, it can measure by making a particle size distribution of an inorganic filler by volume basis with a laser diffraction scattering type particle size distribution measuring device, and making the median diameter into an average particle diameter. The measurement sample can use preferably what disperse | distributed (C) component in water by the ultrasonic wave. As a laser diffraction scattering particle size distribution measuring apparatus, "LA-500" by Horiba Sesaku Sho Co., Ltd. "SALD2200" by Shimadzu Sekushoku Co., etc. can be used.

The specific surface area of the component (C) is preferably 0.01 m 2 / g or more, more preferably 0.025 m 2 / g or more, and even more preferably 0.05 m 2 / g or more from the viewpoint of obtaining a cured product having excellent thermal conductivity. Preferably an upper limit is 30 m <2> / g or less, More preferably, it is 25 m <2> / g or less, More preferably, it is 20 m <2> / g or less. The specific surface area of (C) component can be measured by the nitrogen BET method. Specifically, it can measure using an automatic specific surface area measuring device, and "Macsorb HM-1210" by Mountain Tech Co., Ltd. can be used as an automatic specific surface area measuring device.

The aspect ratio of the component (C) is preferably 8 or less, more preferably 5 or less, still more preferably 3 or less, 2 or less, or 1.5 or less. The lower limit can be 1.0 or more. By containing (C) component which has aspect ratio in such a range in paste resin composition, the hardened | cured material excellent in thermal conductivity can be obtained without raising a viscosity. The aspect ratio refers to the value obtained by dividing the length of the long side of the powder of the component (C) by the length of the short side.

You may use a commercial item for (C) component. As a commercial item, for example, "Danko Corporation DAW-0525", "ASFP-20", Shinano Denki styrene company "SSC-A01", "SSC-A15", "SSC-A30", Tokuyama company "HF" -01 "," MBN-010T "by Mitsui Chemical Co., Ltd., etc. are mentioned.

The component (C) is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane compound, an organosilazane compound, or a titanium from the viewpoint of improving moisture resistance and dispersibility. You may be processed by 1 or more types of surface treating agents, such as a nate coupling agent. As a commercial item of a surface treating agent, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxy propyl trimethoxysilane), Shin-Shin Chemical Co., Ltd. "KBM803" (3-mercaptopropyl trimethoxy, for example) Silane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. High School SZ-31 (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long chain epoxy type silane coupler) Ring agent), and the like.

It is preferable that the grade of the surface treatment by a surface treating agent is surface-treated with 0.2-5 mass parts of surface treating agents with respect to 100 mass parts of (C) component from a viewpoint of the dispersibility improvement of (C) component, and is 0.2- It is preferable to surface-treat at 3 mass parts, and it is preferable to surface-treat at 0.3-2 mass parts.

The degree of surface treatment by a surface treating agent can be evaluated by the amount of carbon per unit surface area of (C) component. From the viewpoint of improving the dispersibility of the component (C), the amount of carbon per unit surface area of the component (C) is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, further 0.2 mg / m 2 or more desirable. On the other hand, 1 mg / m <2> or less is preferable, 0.8 mg / m <2> or less is more preferable, and 0.5 mg / m <2> or less is more preferable from a viewpoint of suppressing a raise of melt viscosity.

The amount of carbon per unit surface area of the component (C) can be measured after the component (C) after surface treatment is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, in addition to the component (C) surface-treated with a surface treating agent, a sufficient amount of MEK as a solvent is ultrasonically cleaned at 25 ° C. for 5 minutes. After removing a supernatant liquid and drying solid content, the carbon amount per unit surface area of (C) component can be measured using a carbon analyzer. As the carbon analysis system, "EMIA-320V" manufactured by Horiba Sesaku Sho, Inc., etc. can be used.

It is preferable to use (C) component in combination of 2 types of the same material from which an average particle diameter differs. By setting it as such a structure, hardened | cured material with a higher thermal conductivity can be obtained and the viscosity of a pasty resin composition can be further reduced. In the same two kinds of materials, when the (C) component having a small average particle diameter is set to C1 and the (C) component having a large average particle diameter is set to C2, the mass ratio (C1 / C2) is preferably 0.1. As mentioned above, More preferably, it is 0.2 or more, More preferably, it is 0.3 or more. The upper limit is preferably 1 or less, more preferably 0.9 or less, and still more preferably 0.8 or less.

When content of (C) component obtains the hardened | cured material excellent in thermal conductivity and lowers the viscosity of a pasty resin composition, when the non volatile component in pasty resin composition is 100 mass%, Preferably it is 60 mass%. As mentioned above, More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more. Preferably an upper limit is 95 mass% or less, More preferably, it is 93 mass% or less, More preferably, it is 90 mass% or less.

The content of component (C) is preferably 30 vol% when the nonvolatile component in the pasty resin composition is 100 vol% from the viewpoint of obtaining a cured product having excellent thermal conductivity and lowering the viscosity of the pasty resin composition. More preferably, it is 40 volume% or more, More preferably, it is 50 volume% or more or 55 volume% or more. Preferably an upper limit is 90 volume% or less, More preferably, it is 85 volume% or less, More preferably, it is 80 volume% or less or 75 volume% or less.

<(D) Dispersant>

The pasty resin composition contains the dispersant (D). By containing (D) component together with (B) component, the fluidity | liquidity of a pasty resin composition improves and as a result, the viscosity of a pasty resin composition can be reduced. The component (D) is not particularly limited as long as the viscosity of the pasty resin composition can be reduced, and examples thereof include oxyalkylene-containing phosphate esters, titanate coupling agents, polyacrylic acids, and polycarboxylic acid dispersants. And oxyalkylene-containing phosphate esters and titanate-based coupling agents are preferred. (D) component may be used individually by 1 type and may use 2 or more types together.

As oxyalkylene containing phosphate ester, polyoxyalkylene alkyl ether phosphate ester, polyoxyalkylene alkyl phenyl ether phosphate ester, etc. are mentioned, for example, A polyoxyalkylene alkyl ether phosphate ester is preferable.

The polyoxyalkylene alkyl ether phosphate ester has a form in which one to three alkyl-oxy-poly (alkyleneoxy) groups are bonded to a phosphorus atom of a phosphate salt.

The number of repeat units of the alkyleneoxy of the poly (alkyleneoxy) moiety in the alkyl-oxy-poly (alkyleneoxy) group is not particularly limited, but for example, 2 to 30 is preferable, and 3 to 20 More preferred.

As the alkylene group in the poly (alkyleneoxy) moiety, an alkylene group having 2 to 4 carbon atoms is preferable. As such an alkylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutyl group, etc. are mentioned, for example.

As the alkyl group in the alkyl-oxy-poly (alkyleneoxy) group, an alkyl group having 6 to 30 carbon atoms is preferable, and an alkyl group having 8 to 20 carbon atoms is more preferable. As such an alkyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, etc. are mentioned, for example.

When the polyoxyalkylene alkyl ether phosphate ester has a plurality of alkyl-oxy-poly (alkyleneoxy) groups, the plurality of alkyl groups and the alkylene groups at the poly (alkyleneoxy) moiety may be different. May be the same. The oxyalkylene-containing phosphate ester may be a mixture with an amine or the like.

The acid value of the oxyalkylene-containing phosphate ester is preferably 10 or more, more preferably 15 or more, and preferably 200 or less, and more preferably 150 or less. The acid value is measured by neutralization titration or the like.

A commercial item may be used for the oxyalkylene containing phosphate ester, As a commercial item, for example, the HIPLAAD series (for example, "ED152", "ED153", "ED154", "ED118", "ED174" of Kusumoto Chemical Co., Ltd.), ED251 etc.) etc. are mentioned.

As a titanate coupling agent, for example, isopropyl tris stearoyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, tetraisopropyl bis (dioctyl pyrophosphite) titanate, tetraoctyl bis ( Ditridecyl phosphite) titanate, tetraisopropylbis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (Dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl tridecyl benzenesulfonyl titanate, isopropyl tri (dioctyl phosphate) titanate , Isopropyl dimethacrylic isostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tricumyl phenyl titanate And dicumylphenyloxyacetate titanate, diisostearoylethylene titanate, and the like, and tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate desirable.

A titanate coupling agent may use a commercial item, and examples of the commercially available product include "Frenc Acto (PLENACT) 55", "Frenc Acto TTS" and "Frenc Acto 46B" manufactured by Ajinomoto Fine Techno Co., Ltd.

When content of (D) component makes the whole non volatile component in paste resin composition into 100 mass% from a viewpoint of the low viscosity of a paste resin composition, Preferably it is 0.1 mass% or more, More preferably, it is 0.3 mass % Or more, More preferably, it is 0.5 mass% or more. Preferably an upper limit is 10 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 5 mass% or less.

<(E) Curing Accelerator>

In one embodiment, the paste-like resin composition can contain the (E) hardening accelerator. As a hardening accelerator, a phosphorus hardening accelerator, an amine hardening accelerator, an imidazole hardening accelerator, a guanidine hardening accelerator, a metal hardening accelerator, etc. are mentioned, for example, A phosphorus hardening accelerator, an amine hardening accelerator, imidazole hardening An accelerator and a metal-based hardening accelerator are preferable, and a phosphorus-based hardening accelerator is preferable from a viewpoint of reducing the viscosity of a pasty resin composition and improving the adhesiveness of the hardened | cured material of a pasty resin composition.

As a phosphorus hardening accelerator, a triphenyl phosphine, a phosphonium borate compound, tetraphenyl phosphonium tetraphenyl borate, n-butyl phosphonium tetraphenyl borate, tetrabutyl phosphonium decanoic acid, tetrabutyl phosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, and the like, and triphenylphosphine, tetrabutylphosphonium decanoic acid and salts thereof desirable.

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, and 1,8. -Diazabicyclo (5,4,0) -undecene and the like, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferred.

As an imidazole series hardening accelerator, 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2- dimethyl imidazole, 2-ethyl-4-methyl, for example. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl imidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s- Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazineisocyanuric acid addition , 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3- Dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc. Adduct of an imidazole compound, an imidazole compound, and an epoxy resin is mentioned, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As an imidazole series hardening accelerator, you may use a commercial item, For example, "P200-H50" by Mitsubishi Chemical Co., Ltd. is mentioned.

Examples of the guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, and diphenylguanidine. , Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1- (o-tolyl) biguanide, and the like. Preference is given to 1,5,7-triazabicyclo [4.4.0] deca-5-ene.

As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and salts (II) acetylacetonate. Organic iron complexes, such as an organic zinc complex and iron (III) acetylacetonate, organic nickel complexes, such as nickel (II) acetylacetonate, organic manganese complexes, such as manganese (II) acetylacetonate, etc. are mentioned. Examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate and zinc stearate.

When the pasty resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.05% by mass when the entire nonvolatile component in the pasty resin composition is 100% by mass. As mentioned above, More preferably, it is 0.1 mass% or more. Preferably an upper limit is 3 mass% or less, More preferably, it is 2 mass% or less, More preferably, it is 1 mass% or less. By making content of a hardening accelerator into this range, a viscosity can be reduced and the adhesiveness of hardened | cured material can also be improved.

<(F) flame retardant>

In one embodiment, the pasty resin composition can contain the (F) flame retardant. As a flame retardant, an organophosphorus flame retardant, an organic nitrogen containing phosphorus compound, a nitrogen compound, a silicone flame retardant, a metal hydroxide, etc. are mentioned, for example. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

As a flame retardant, a commercial item may be used, for example, "HCA-HQ" by Sanko Corp., "PX-200" by Daihachi Chemical Co., Ltd., etc. are mentioned. As a flame retardant, a thing which is hard to hydrolyze is preferable, For example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphafaphenanthrene-10-oxide etc. are preferable.

When the pasty resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but when the nonvolatile component in the pasty resin composition is 100% by mass, preferably 0.5 to 20% by mass, more preferably 0.5 15 mass%, More preferably, 0.5-10 mass% is more preferable.

<(G) any additive>

The resin composition may further contain other additives as necessary, and as such other additives, for example, a thermoplastic resin, an inorganic filler (except those corresponding to the component (C)), and an organic filler And organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and resin additives such as binders, thickeners, antifoaming agents, leveling agents, adhesion imparting agents, and coloring agents.

<Physical Properties and Uses of Paste Resin Compositions>

The content of the organic solvent contained in the pasty resin composition is preferably less than 1.0 mass%, more preferably 0.8 mass% or less, still more preferably 0.5 mass% or less, relative to the total mass of the pasty resin composition. It is mass% or less. Although a minimum does not have a restriction | limiting in particular, It is 0.001 mass% or more, or does not contain. The pasty resin composition of this invention can make the viscosity low, even if it does not contain the organic solvent. Since the generation of voids due to volatilization of the organic solvent can be suppressed because the amount of the organic solvent is small in this manner, adhesion to electronic members such as a circuit board can be improved, and as a result, The heat dissipation efficiency can be improved. Here, an organic solvent means the component which is a liquid at 25 degreeC which does not have the function to harden | cure the (A) component.

The viscosity at 25 degrees C of a pasty resin composition becomes like this. Preferably it is 350 Pa * s or less, More preferably, it is 330 Pa * s or less, More preferably, it is 310 Pa * s or less. Although a minimum does not have a restriction | limiting in particular, It can be set to 1 Pa * s or more, 10 Pa * s or more. A viscosity can be measured according to description of the [measurement of viscosity] mentioned later. By making the viscosity of a paste resin composition into such a range, the fluidity | liquidity of a paste resin composition becomes high and adhesiveness also improves.

Hardened | cured material of a paste-like resin composition (For example, the hardened | cured material obtained by thermosetting a paste-like resin composition for 60 minutes at 150 degreeC, the hardened | cured material obtained by thermosetting the paste-like resin composition for 60 minutes at 120 degreeC, and paste-like resin composition. After heat-hardening at 150 degreeC for 60 minutes, the hardened | cured material obtained by further thermosetting at 180 degreeC for 60 minutes) shows the outstanding thermal conductivity. That is, an insulation layer with high thermal conductivity is brought about. As thermal conductivity, it is 1.0W / m * K or more, Preferably it is 2.0W / m * K or more, More preferably, it is 3.0W / m * K or more, More preferably, it is 5.0W / m * K or more. Although the upper limit of thermal conductivity is not specifically limited, It can be 10 W / m * K or less. Evaluation of thermal conductivity can be measured according to the method as described in [measurement of thermal conductivity] mentioned later.

The hardened | cured material obtained by thermosetting paste resin composition at 150 degreeC for 60 minutes shows the outstanding adhesiveness. That is, the insulating layer excellent in adhesiveness is brought about. As Die Shear strength of the said hardened | cured material, Preferably it is 10N or more, More preferably, it is 20N or more. The upper limit is not particularly limited, but may be 200 N or less. Evaluation of adhesiveness can be measured in accordance with the method as described in [evaluation of adhesiveness] mentioned later. Since the said hardened | cured material shows the outstanding adhesiveness and the outstanding thermal conductivity, heat dissipation efficiency to the electronic member etc. which contact | connect with hardened | cured material can be made high.

Since the pasty resin composition is a paste having high fluidity, for example, the pasty resin composition is injected into a syringe, and the pasty resin composition is pressurized to be widened to a uniform thickness to form a resin composition layer. For this reason, as described in Unexamined-Japanese-Patent No. 2012-77123, the resin varnish is produced using the organic solvent, the resin varnish is dried, the organic solvent is removed, and it shape | molded in the film form (resin composition layer Need not be formed). Since the paste-like resin composition does not need to produce a resin varnish using an organic solvent, there exists no possibility that the heat radiation efficiency of an electronic member may fall because an organic solvent exists.

The paste resin composition of the present invention can result in an insulating layer having high thermal conductivity and high adhesion. Therefore, the paste resin composition of this invention is a paste resin composition (paste resin composition for adhesion of heat sinks) for bonding a heat sink and an electronic component, and a paste resin composition for forming the insulating layer of a semiconductor chip package. (Paste-like resin composition for an insulating layer of a semiconductor chip package) and a paste-like resin composition (paste-like resin composition for an insulating layer of a circuit board) for forming an insulating layer of a circuit board (including a printed wiring board), It can be used suitably as a paste resin composition (paste resin composition for interlayer insulation layers of the circuit board which forms a conductor layer by plating) for forming the interlayer insulation layer in which the conductor layer is formed by plating on it. Moreover, it can use suitably also as paste resin composition (paste resin composition for semiconductor chip sealing) for sealing a semiconductor chip, and paste resin composition (paste resin composition for semiconductor chip wiring formation) for forming wiring in a semiconductor chip. Can be.

[Circuit board]

The circuit board of this invention contains the insulating layer formed of the hardened | cured material of the paste resin composition of this invention.

The manufacturing method of the circuit board of this invention,

(1) a step of preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one side of the substrate;

(2) Process of apply | coating paste-form resin composition on the base material with wiring layer so that a wiring layer may be embedded, thermosetting, and forming an insulating layer,

(3) The process of connecting an interconnect layer interlayer is included. In addition, the manufacturing method of a circuit board,

(4) You may include the process of removing a base material.

The step (3) is not particularly limited as long as the wiring layer can be interlayer connected, but at least one of the steps of forming a via hole in the insulating layer, forming the wiring layer, and polishing or grinding the insulating layer to expose the wiring layer. Is preferably.

<Step (1)>

Process (1) is a process of preparing the base material with wiring layer which has a base material and the wiring layer provided in at least one surface of the said base material. Usually, the base material with a wiring layer has the 1st metal layer and the 2nd metal layer which are a part of base material on both surfaces of a base material, respectively, and has a wiring layer in the surface on the opposite side to the surface of the base material side of a 2nd metal layer. In detail, a dry film (photosensitive resist film) is laminated | stacked on a base material, and it exposes and develops on predetermined conditions using a photomask, and forms a pattern dry film. After forming a wiring layer by the electroplating method using the developed pattern dry film as a plating mask, a pattern dry film is peeled off.

As a base material, board | substrates, such as a glass epoxy board | substrate, a metal board | substrate (such as stainless steel and a cold rolled steel plate (SPCC)), a polyester board | substrate, a polyimide board | substrate, BT resin board | substrate, and a thermosetting polyphenylene ether board | substrate, are mentioned, for example. Moreover, metal layers, such as copper foil, may be formed in the board | substrate surface. Moreover, metal layers, such as the 1st metal layer and the 2nd metal layer (for example, ultra-thin copper foil with carrier copper foil by Mitsui Kinzoku Co., Ltd. make, brand name "Micro Thin") which can peel on the surface, may be formed.

As a dry film, as long as it is a photosensitive dry film which consists of a photoresist composition, it will not specifically limit, For example, dry films, such as a novolak resin and an acrylic resin, can be used. You may use a commercial item for a dry film.

What is necessary is just to perform lamination | stacking of a base material and a dry film by the vacuum lamination method. In the vacuum lamination method, the hot pressing temperature is preferably in the range of 60 to 160 ° C, more preferably 80 to 140 ° C, and the hot pressing pressure is preferably 0.098 to 1.77 MPa, more preferably 0.29 to It is the range of 1.47 MPa, and heat-compression time is for 20 to 400 second preferably, More preferably, it is the range for 30 to 300 second. Lamination is preferably performed under reduced pressure conditions of 13 hPa or less.

After laminating | stacking a dry film on a base material, in order to form a desired pattern with respect to a dry film, it exposes and develops on predetermined conditions using a photomask.

The line (circuit width) / space (width between circuits) ratio of the wiring layer is not particularly limited, but is preferably 20/20 µm or less (that is, pitch is 40 µm or less), more preferably 10/10 µm or less, further preferably Preferably it is 5/5 micrometer or less, More preferably, it is 1/1 micrometer or less, Especially preferably, it is 0.5 / 0.5 micrometer or more. The pitch does not need to be the same throughout the wiring layer. The minimum pitch of the wiring layer may be 40 µm or less, 36 µm or less, or 30 µm or less.

After the pattern formation of a dry film, a wiring layer is formed and a dry film is peeled off. Here, formation of a wiring layer can be performed by the plating method using the dry film which formed the desired pattern as a plating mask.

The conductor material used for a wiring layer is not specifically limited. In a suitable embodiment, the wiring layer comprises at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. . The wiring layer may be either a short metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the group described above (for example, a nickel chromium alloy, a copper nickel alloy, and a copper titanium alloy). The thing formed by) is mentioned. Among these, in view of the versatility of the wiring layer formation, the cost, the ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloy, copper-nickel alloy, An alloy layer of a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy is more preferable, and a single metal layer of copper More preferred.

Although the thickness of a wiring layer changes with design of a desired wiring board, Preferably it is 3-35 micrometers, More preferably, it is 5-30 micrometers, More preferably, it is 10-20 micrometers, or 15-20 micrometers. In the step (3), when the step of grinding or grinding the insulating layer and exposing the wiring layer to interconnect the wiring layer is adopted, the thickness of the wiring to be connected between the layers and the wiring not to be connected is preferably different. The thickness of the wiring layer can be adjusted by repeating the above-described pattern formation. Although the thickness of the wiring layer (electroconductive filler) which has the thickest among each wiring layer changes with design of a desired wiring board, Preferably it is 2 micrometers or more and 100 micrometers or less. In addition, the wiring connected between layers may be convex.

After forming a wiring layer, a dry film is peeled off. Peeling of a dry film can be performed using alkaline peeling liquids, such as a sodium hydroxide solution, for example. If necessary, unnecessary wiring patterns may be removed by etching or the like to form desired wiring patterns. The pitch of the wiring layer to be formed is as described above.

<Step (2)>

Process (2) is a process of apply | coating a paste resin composition on the base material with wiring layer so that a wiring layer may be embedded, thermosetting, and forming an insulating layer. Specifically, the paste-like resin composition is applied onto the wiring layer of the substrate with wiring layer obtained in the above-described step (1), and the paste-like resin composition is thermosetted to form an insulating layer.

Application | coating of a wiring layer and a paste resin composition can be performed, for example by inject | pouring a paste resin composition with a syringe, pressurizing a paste resin composition, and forming the resin composition layer of uniform thickness.

After apply | coating paste resin composition on the base material with wiring layer so that a wiring layer may be embedded, a resin composition layer is thermosetted and an insulating layer is formed. Although the thermosetting conditions of a resin composition layer differ also according to the kind of paste-like resin composition, etc., For example, hardening temperature can be made into the range of 120-240 degreeC, and hardening time is the range of 5 to 120 minutes. Before thermosetting a resin composition layer, you may preheat a resin composition layer to temperature lower than hardening temperature.

After thermosetting a resin composition layer and forming an insulating layer, you may grind the surface of an insulating layer. Although a grinding | polishing method is not specifically limited, What is necessary is just to grind by a well-known method, For example, the surface of an insulating layer can be grind | polished using a planar grinder.

<Step (3)>

Process (3) is a process of connecting an interconnect layer interlayer. In detail, it is a process of forming a via hole in an insulating layer, forming a conductor layer, and connecting a wiring layer between layers. Alternatively, the insulating layer is polished or ground, and the wiring layer is exposed to interconnect the wiring layer.

In the case where a via hole is formed in the insulating layer, a conductor layer is formed, and the wiring layer is connected to each other, the formation of the via hole is not particularly limited, but laser irradiation, etching, mechanical drilling, etc. may be mentioned. It is preferable to be done. This laser irradiation can be performed using any suitable laser processing machine which uses a carbon dioxide laser, a YAG laser, an excimer laser, etc. as a light source.

The conditions of laser irradiation are not specifically limited, Laser irradiation can be performed by any suitable process according to the conventional method according to the selected means.

The shape of the via hole, that is, the contour shape of the opening when viewed in the stretching direction is not particularly limited, but is generally circular (approximately circular).

After via hole formation, what is called a desmear process which is a smear removal process in a via hole may be performed. In the case of forming the conductor layer, which will be described later, by the plating process, for example, a wet desmear treatment may be performed on the via hole, and when the conductor layer is formed by the sputtering process, for example, plasma treatment. You may perform a dry desmear process, such as a process. In addition, the desmear process may also serve as the roughening process process.

Before forming the conductor layer, the via hole and the insulating layer may be roughened. The roughening process can employ | adopt well-known procedures and conditions normally performed. Examples of the dry roughening treatment include plasma treatment. Examples of the wet roughening treatment include a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent and a neutralization treatment with a neutralizing liquid in this order.

As surface roughness Ra of the insulating-layer surface after a roughening process, Preferably it is 350 nm or more, More preferably, it is 400 nm or more, More preferably, it is 450 nm or more. Preferably an upper limit is 700 nm or less, More preferably, it is 650 nm or less, More preferably, it is 600 nm or less. Surface roughness Ra can be measured using a non-contact surface roughness machine, for example.

After the via hole is formed, the conductor layer is formed. The conductor material which comprises a conductor layer is not specifically limited, A conductor layer can be formed by conventionally well-known arbitrary suitable methods, such as plating, sputter | spatter, and vapor deposition, and it is preferable to form by plating. One suitable embodiment can be plated on the surface of an insulating layer by conventionally well-known techniques, such as a semiadditive method and a free additive method, and can form the conductor layer which has a desired wiring pattern. The conductor layer may be a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated.

Specifically, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Subsequently, a mask pattern for exposing a part of the plating seed layer is formed on the formed plating seed layer corresponding to the desired wiring pattern. On the exposed plating seed layer, an electroplating layer is formed by electroplating. At that time, with the formation of the electrolytic plating layer, via holes may be embedded by electroplating to form field vias. After the electroplating layer is formed, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern. In addition, when forming a conductor layer, the dry film used for formation of a mask pattern is the same as that of the said dry film.

The conductor layer may include not only linear wiring but also an electrode pad (land) on which an external terminal can be mounted. In addition, the conductor layer may be comprised only by the electrode pad.

In addition, the conductor layer may be formed by forming an electroplating layer and a field via after forming the plating seed layer without using a mask pattern, and then patterning by etching.

In the case where the insulating layer is polished or ground, and the wiring layer is exposed and the step of connecting the wiring layers is adopted, the wiring layer can be exposed as the polishing method or the grinding method of the insulating layer, and the polishing or grinding surface is not particularly limited. It is possible to apply a conventionally known polishing method or grinding method, and examples thereof include a chemical mechanical polishing method using a chemical mechanical polishing device, a mechanical polishing method such as a buff, a planar grinding method using a grinding wheel, and the like. . A via hole may be formed in an insulating layer, a conductor layer may be formed, and a wiring layer may be connected between layers, and a smear removal process and a roughening process may be performed, or a conductor layer may be formed. In addition, it is not necessary to expose all wiring layers, and a part of wiring layers may be exposed.

<Step (4)>

Process (4) is a process of removing a base material and forming the circuit board of this invention. The removal method of a base material is not specifically limited. In one suitable embodiment, the substrate is peeled off from the circuit board at the interface between the first and second metal layers, and the second metal layer is etched away with, for example, an aqueous copper chloride solution. As needed, you may peel a base material in the state which protected the conductor layer with the protective film.

[Semiconductor Chip Package]

A first aspect of the semiconductor chip package of the present invention is a semiconductor chip package in which a semiconductor chip is mounted on the circuit board. A semiconductor chip package can be manufactured by bonding a semiconductor chip to the said circuit board.

The bonding conditions are not particularly limited as long as the terminal electrodes of the semiconductor chips are connected to the circuit wiring of the circuit board, and any known conditions used in flip chip mounting of the semiconductor chips may be used. Moreover, you may join through an insulating adhesive agent between a semiconductor chip and a circuit board.

One suitable embodiment presses the semiconductor chip onto the circuit board. As the crimping conditions, for example, the crimping temperature is in the range of 120 to 240 ° C (preferably in the range of 130 to 200 ° C, more preferably in the range of 140 to 180 ° C), and the crimping time is in the range of 1 to 60 seconds ( Preferably 5 to 30 seconds).

Moreover, another suitable embodiment reflows and joins a semiconductor chip to a circuit board. As reflow conditions, it can be set as the range of 120-300 degreeC, for example.

After bonding a semiconductor chip to a circuit board, it is also possible to obtain a semiconductor chip package by filling a semiconductor chip with a mold underfill material, for example. The method of filling with a mold underfill material can be performed by a well-known method. The mold underfill material may use a paste resin composition.

The second aspect of the semiconductor chip package of the present invention is, for example, a semiconductor chip package (Fan-out type WLP) as shown in Fig. 1. The semiconductor chip package (Fan-out type WLP) 100 which shows an example in FIG. 1 is the semiconductor chip package which produced the sealing layer 120 from the paste resin composition of this invention. The semiconductor chip package 100 is grown on the surface opposite to the side covered with the semiconductor chip 110, the encapsulation layer 120 formed to cover the semiconductor chip 110, and the encapsulation layer of the semiconductor chip 110. A line forming layer (insulating layer) 130, a conductor layer (rewiring layer) 140, a solder resist layer 150, and a bump 160 are provided. The manufacturing method of such a semiconductor chip package,

(A) process of laminating a temporarily fixed film on a base material,

(B) process of temporarily fixing a semiconductor chip on a temporarily fixed film,

(C) Process of apply | coating paste resin composition of this invention on semiconductor chip, thermosetting, and forming sealing layer,

(D) Process of peeling a base material and a temporarily fixing film from a semiconductor chip,

(E) process of forming a redistribution formation layer (insulation layer) in the surface which peeled the base material and the temporarily fixing film of a semiconductor chip,

(F) forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer),

And

(G) forming a soldering resist layer on the conductor layer.

In addition, the manufacturing method of a semiconductor chip package,

(H) Dicing a plurality of semiconductor chip packages into individual semiconductor chip packages may be included.

<Step (A)>

Process (A) is a process of laminating a temporarily fixed film on a base material. Lamination conditions of a base material and a temporarily fixed film are the same as the lamination conditions of the base material and dry film in the above-mentioned process (1), and its preferable range is also the same.

The material used for a base material is not specifically limited. As a base material, a silicon wafer; Glass wafers; Glass substrates; Metal substrates such as copper, titanium, stainless steel, and cold rolled steel sheet (SPCC); A substrate subjected to thermosetting treatment by injecting an epoxy resin or the like into glass fibers such as an FR-4 substrate; The board | substrate which consists of bismaleimide triazine resins, such as BT resin, etc. are mentioned.

A material will not be specifically limited if a temporarily fixed film can peel from a semiconductor chip in the process (D) mentioned later, and can temporarily fix a semiconductor chip. The temporarily fixed film can use a commercial item. As a commercial item, the Nitto Denko make REVALPHA etc. are mentioned.

<Step (B)>

Process (B) is a process of temporarily fixing a semiconductor chip on a temporarily fixed film. Temporary fixation of a semiconductor chip can be performed using well-known apparatuses, such as a flip chip bonder and a die bonder. The layout and the number of arrangements of the semiconductor chip arrangements can be appropriately set according to the shape, size of the temporarily fixed film, the number of production of the target semiconductor package, and the like, for example, arranged in a plurality of rows and a plurality of columns in a matrix. You can decide.

<Step (C)>

Process (C) is a process of apply | coating the paste resin composition of this invention on a semiconductor chip, thermosetting, and forming a sealing layer.

Application | coating of a paste-like resin composition and thermosetting conditions are the same as the application | coating method of the pasty resin composition in the process (2) in the manufacturing method of the circuit board mentioned above, and thermosetting conditions.

<Step (D)>

Process (D) is a process of peeling a base material and a temporarily fixed film from a semiconductor chip. The method of peeling can be suitably changed according to the material of a temporarily fixed film, etc. For example, the method of heating and foaming (or expanding) a temporarily fixed film, and irradiating an ultraviolet-ray from the base material side, The method of reducing adhesive force and peeling is mentioned.

In the method of heating, foaming (or expanding) and temporarily peeling off a temporarily fixed film, heating conditions are 1 to 90 second or 5 to 15 minutes at 100-250 degreeC normally. Moreover, in the method of irradiating an ultraviolet-ray from the base material side, reducing the adhesive force of a temporarily fixed film, and peeling, the irradiation amount of an ultraviolet-ray is 10-1000mJ / cm <2> normally.

<Step (E)>

Process (E) is a process of forming a redistribution formation layer (insulating layer) in the surface which peeled the base material and the temporarily fixed film of a semiconductor chip.

The material for forming the redistribution forming layer (insulating layer) is not particularly limited as long as it has insulation at the time of forming the redistribution forming layer (insulating layer), and from the viewpoint of ease of manufacture of the semiconductor chip package, a photosensitive resin and a thermosetting resin are preferable. .

After forming the redistribution forming layer (insulating layer), via holes may be formed in the redistribution forming layer (insulating layer) in order to connect the semiconductor chip and the conductor layer described later.

In forming the via hole, when the material for forming the redistribution forming layer (insulating layer) is a photosensitive resin, first, the active energy ray is irradiated by passing a mask pattern through the surface of the redistribution forming layer (insulating layer), and the The wiring layer is photocured.

As an active energy ray, an ultraviolet-ray, a visible ray, an electron beam, X-rays, etc. are mentioned, for example, Especially ultraviolet ray is preferable. The irradiation amount and irradiation time of an ultraviolet-ray can be changed suitably according to the photosensitive resin. As the photosensitive method, any one of a contact exposure method in which a mask pattern is brought into close contact with a redistribution forming layer (insulating layer) and a noncontact exposure method in which the mask pattern is exposed using parallel rays without being in close contact with the redistribution forming layer (insulating layer). You may use it.

Next, via holes are formed by developing a redistribution forming layer (insulating layer) and removing unexposed portions. The development is suitable for any of wet development and dry development. As the developer used in the wet development, a known developer can be used.

As a system of image development, a dip system, a paddle system, a spray system, a brushing system, a scraping system, etc. are mentioned, for example, A paddle system is suitable from a resolution viewpoint.

In the case where the material for forming the redistribution forming layer (insulating layer) is a thermosetting resin, the formation of the via hole is not particularly limited. Examples thereof include laser irradiation, etching, mechanical drilling, and the like, which is preferably performed by laser irradiation. Laser irradiation can be performed using any suitable laser processing machine which uses a carbon dioxide laser, a UV-YAG laser, an excimer laser, etc. as a light source.

The conditions of laser irradiation are not specifically limited, Laser irradiation can be performed by any suitable process according to the conventional method according to the selected means.

The shape of the via hole, that is, the contour shape of the opening when viewed in the stretching direction is not particularly limited, but is generally circular (approximately circular). The top diameter (opening forming layer, opening diameter of the surface of the (insulating layer)) of the via hole is preferably 50 µm or less, more preferably 30 µm or less, still more preferably 20 µm or less. Although a minimum is not specifically limited, Preferably it is 10 micrometers or more, More preferably, it is 15 micrometers or more, More preferably, it is 20 micrometers or more.

<Step (F)>

Step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer). The method of forming a conductor layer on a redistribution formation layer (insulation layer) is the same as the method of forming the conductor layer after forming a via hole in the insulation layer of the process (3) in the manufacturing method of a circuit board, and a preferable range also is same. In addition, the step (E) and the step (F) may be repeated, and the conductor layer (rewiring layer) and the redistribution forming layer (insulating layer) may be alternately stacked (build up).

<Step (G)>

Process (G) is a process of forming a soldering resist layer on a conductor layer.

The material for forming the solder resist layer is not particularly limited as long as it has insulation at the time of forming the solder resist layer, and from the viewpoint of ease of manufacture of the semiconductor chip package, photosensitive resins and thermosetting resins are preferable.

In addition, process (G) may perform bumping process which forms a bump as needed. Bumping can be performed by well-known methods, such as a solder ball and solder plating. In addition, formation of the via hole in bumping process can be performed similarly to process (E).

<Step (H)>

The manufacturing method of a semiconductor chip package may include process (H) other than process (A)-(G). Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into pieces.

The method of dicing a semiconductor chip package to each semiconductor chip package is not specifically limited, A well-known method can be used.

The third aspect of the semiconductor chip package of the present invention is, for example, a redistribution forming layer (insulating layer) 130 and a soldering resist layer in a semiconductor chip package (Fan-out type WLP) shown in FIG. 1 as an example. (150) is a semiconductor chip package manufactured from the paste resin composition of the present invention.

[Semiconductor Device]

Examples of the semiconductor device to which the semiconductor chip package of the present invention is mounted include electrical appliances (for example, computers, mobile phones, smartphones, tablet-type devices, wearable devices, digital cameras, medical devices, and televisions) and vehicles (examples). For example, various semiconductor devices provided to motorcycles, automobiles, trams, ships, aircrafts, etc. can be mentioned.

[Electronic member]

The electronic member of this invention has a heat sink, the hardened | cured material of the paste-like resin composition of this invention provided on the said heat sink, and the electronic component mounted on the said hardened | cured material. Since the hardened | cured material of a pasty resin composition is excellent in thermal conductivity and adhesiveness, for example, it is provided on a heat sink so that the hardened | cured material of a pasty resin composition may adhere to a heat sink, and an electronic component is mounted on the said hardened | cured material. The heat dissipation efficiency of the heat sink of the electronic component is increased. The formation method of hardened | cured material can be performed by the method similar to the above-mentioned process (C).

As an electronic component, a semiconductor chip, a power semiconductor, LED-PKG etc. are mentioned, for example. As an electronic member, a circuit board, a semiconductor chip package, a semiconductor device, etc. are mentioned, for example.

Example

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In addition, in the following description, "part" and "%" which represent quantity mean "mass part" and "mass%", respectively, unless there is particular notice.

[Preparation of Paste Resin Composition]

<Example 1>

17 parts of bisphenol-type epoxy resin ("XX1059" by Shin-Nitetsu Sumikin Chemical Co., Ltd., epoxy equivalent approximately 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type) is a liquid dispersing agent (made by Kusumoto Kasei Co., Ltd. ED152 ", and 1 part of alkylene oxide containing phosphate esters) were added, and it stirred uniformly using the Awaritorentaro manufactured by Sinki Corp., and obtained the epoxy resin composition. Next, to the obtained epoxy resin composition, 14 parts of a liquid curing agent ("TMTP" manufactured by Yodogagaku Kogyo Co., Ltd.), trimethylol propane tris (3-mercaptopropionate), molecular weight 398, trifunctional), and a curing accelerator (Hokko) Kagaku Kogyo Co., Ltd. "TBP-DA" and tetrabutyl phosphonium decanoic acid) 0.14 part were added, it stirred, and the base resin composition was prepared.

69 parts of thermally conductive fillers (spherical alumina powder, "DAW-0525" manufactured by Denka Corporation, an average particle diameter of 5.3 µm, a specific surface area of 0.4 m 2 / g, and an aspect ratio of 1.0) were added to the base resin composition and kneaded to obtain a paste resin composition 1. . The organic solvent content of the pasty resin composition 1 was 0 mass% with respect to the whole mass of the pasty resin composition 1.

<Example 2>

In Example 1, 69 parts of thermally conductive fillers (spherical alumina powder, "DAW-0525" by Denka Co., Ltd., average particle diameter 5.3 micrometers, specific surface area 0.4 m <2> / g, aspect ratio 1.0) were heat conductive fillers (spherical silicon carbide powder) And "SSC-A01" manufactured by Shinano Denkiseren Co., Ltd., with an average particle diameter of 1.4 µm, a specific surface area of 5.0 m 2 / g, and an aspect ratio of 1.25). A paste resin composition 2 was obtained in the same manner as in Example 1 except for the above matters.

<Example 3>

In Example 1, 69 parts of thermally conductive fillers (spherical alumina powder, "DAW-0525" by Denka Co., Ltd., average particle diameter 5.3 micrometers, specific surface area 0.4 m <2> / g, aspect ratio 1.0) were heat conductive fillers (spherical silicon carbide powder) And "SSC-A15" manufactured by Shinano Denkiseren Co., Ltd., having an average particle diameter of 18.6 µm, a specific surface area of 0.3 m 2 / g, and an aspect ratio of 1.25) of 64 parts. A paste resin composition 3 was obtained in the same manner as in Example 1 except for the above matters.

<Example 4>

In Example 1, 69 parts of thermally conductive fillers (spherical alumina powder, "DAW-0525" by Denka Co., Ltd., average particle diameter 5.3 micrometers, specific surface area 0.4 m <2> / g, aspect ratio 1.0) were thermally conductive fillers (Tokuyama Corporation make). Surface-treated spherical aluminum nitride powder of "HF-01" with phenylaminosilane in Adomatex, average particle diameter 0.9-1.4 micrometers, specific surface area 2.3-2.9 m <2> / g, aspect ratio 1.0-1.1) 65 Changed to wealth. A paste resin composition 4 was obtained in the same manner as in Example 1 except for the above matters.

<Example 5>

Bisphenol-type epoxy resin ("ZX1059" made by Shin-Nitetsu Chemical Co., Ltd., epoxy equivalent approximately 169 g / eq, 1: 1 mixed product of bisphenol A type and bisphenol F type), and 1, 4- cyclohexane dimethanol di Three parts of glycidyl ether type epoxy resin ("ZX1658GS" made by Shin-Nitetsu Sumikin Chemical Co., Ltd., epoxy equivalent 130-140 g / eq) are weighed in a metal container, and the tetramethylbiphenol type solid epoxy resin (Mitsubishi Chemical Corporation) Co., Ltd. "YX4000HK" and 1 part of epoxy equivalent 187-197g / eq) were measured. Thereafter, it was dissolved using an IH heater.

After cooling, 4 parts of a dispersing agent ("ED152" by the Kusumoto Chemical Co., Ltd., alkylene oxide containing phosphate ester) was added, and it stirred uniformly, and obtained the epoxy resin composition.

Next, to the obtained epoxy resin composition, 6 parts of a liquid hardening | curing agent ("TMTP" by the Yodogagaku Kogyo Co., Ltd., trimethylol propane tris (3-mercaptopropionate), molecular weight 398, trifunctional), and a hardening accelerator (Hokkoga 0.14 part of "TBP-DA" by Gaku Kogyo Co., Ltd. and tetrabutyl phosphonium decanoic acid) was added and stirred to prepare a base resin composition.

13 parts of a thermally conductive filler (alumina powder, "ASFP-20" by Denka Co., Ltd., average particle diameter 0.2-0.5 micrometer, specific surface area 12-18 m <2> / g, aspect ratio 1.0), and a thermally conductive filler (alumina powder, "DW-0525" by Denka Co., Ltd., 19 micrometers in average particle diameter of 5.3 micrometers, specific surface area of 0.4 m <2> / g, aspect ratio 1.0), a thermally conductive filler (spherical silicon carbide powder, "SSC-A01" by Shinano Denkiseren company, average particle | grains 13 parts of diameter 1.4 micrometers, specific surface area 5.0m <2> / g, aspect ratio 1.25), and a thermally conductive filler (spherical silicon carbide powder, "SSC-A15" by Shinano Denkiserene Co., Ltd., average particle diameter 18.6micrometer, specific surface area 0.3m <2> / g And 38 parts of aspect ratio 1.25) were added and stirred, and the paste-like resin composition 5 was obtained.

<Example 6>

In Example 5,

1) The amount of bisphenol-type epoxy resin ("XX1059" manufactured by Shin-Nitetsu Chemical Co., Ltd., epoxy equivalent of about 169 g / eq, 1: 1 mixed product of bisphenol A type and bisphenol F type) is 3 to 4 parts,

2) The amount of tetramethylbiphenol-type solid epoxy resin ("YX4000HK" by Mitsubishi Chemical Co., Ltd., epoxy equivalent 187-197g / eq) is made into 1 part to 2 parts,

3) 6 parts of liquid curing agents (TMTP manufactured by Yodogagaku Kogyo Co., Ltd., trimethylol propane tris (3-mercaptopropionate), molecular weight 398, trifunctional), liquid curing agent (MEH-8000H manufactured by Meiwa Kasei Co., Ltd.) 2-allyl phenol formaldehyde polycondensate, OH equivalent 139-143 g / eq) to 8 parts,

4) The amount of the dispersant ("ED152" manufactured by Kusumoto Chemical Co., Ltd., alkylene oxide containing phosphate ester) was changed from 4 parts to 1 part.

A paste resin composition 6 was obtained in the same manner as in Example 5 except for the above matters.

<Example 7>

In Example 5, 4 parts of a dispersing agent ("ES152" by Kusumoto Kasei Co., Ltd., alkylene oxide containing phosphate ester), a dispersing agent ("Frencto 55" by Ajinomoto Fine Techno Co., Ltd.), a titanate coupling agent (tetra (2, 2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate) was changed to 4 parts .. A paste-like resin composition 7 was obtained in the same manner as in Example 5 except for the above matters.

<Example 8>

In Example 5, 13 parts of thermally conductive fillers (spherical silicon carbide powder, "SSC-A01" by Shinano Denkiserene Co., Ltd., average particle diameter 1.4 micrometers, specific surface area 5.0 m <2> / g, aspect ratio 1.25) were heat conductive fillers (Toku The surface-treated spherical aluminum nitride powder of Yamaha "HF-01" with phenylaminosilane in Adomatex, the average particle diameter of 0.9-1.4 micrometers, specific surface area 2.3-2.9m <2> / g, aspect ratio 1.0- 1.1) Changed to 13 parts. A paste resin composition 8 was obtained in the same manner as in Example 5 except for the above matters.

Example 9

In Example 5, 13 parts of thermally conductive fillers (spherical silicon carbide powder, "SSC-A01" by Shinano Denkiseren Co., Ltd., average particle diameter 1.4 micrometers, specific surface area 5.0 m <2> / g, aspect ratio 1.25) were heat conductive fillers (nitriding) Boron powder, "MBN-010T" by Mitsui Chemical Co., Ltd., average particle diameter 0.9-1.0 micrometer, specific surface area 13.0 m <2> / g, aspect ratio 5.0) It changed into 13 parts. A paste resin composition 9 was obtained in the same manner as in Example 5 except for the above matters.

<Example 10>

2 parts of bisphenol-type epoxy resin ("XX1059" by Shin-Nitetsu Sumikin Chemical Co., Ltd., epoxy equivalent about 169 g / eq, 1: 1 mixed product of bisphenol A type and bisphenol F type), and 1, 4- cyclohexane dimethanol di 2 parts of glycidyl ether type epoxy resin (manufactured by Shinnitetsu Chemical Co., Ltd., `` ZX1658GS '', epoxy equivalent 130-140 g / eq) was weighed into a metal container, and a tetramethylbiphenol type solid epoxy resin (Mitsubishi Chemical "KX Corporation" YX4000HK "and 1 part of epoxy equivalents 187-197g / eq) were measured. Thereafter, it was dissolved using an IH heater.

After cooling, 3 parts of a dispersing agent ("ED152" by the Kusumoto Chemical Co., Ltd., alkylene oxide containing phosphate ester) were added, and it stirred uniformly, and obtained the epoxy resin composition.

Next, a liquid curing agent ("TMTP" manufactured by Yodogagaku Kogyo Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional) 4 parts to the obtained epoxy resin composition, and a curing accelerator (Hokkoga "TBP-DA" manufactured by Gaku Kogyo Co., Ltd., and 0.09 parts of tetrabutyl phosphonium decanoic acid) were added and stirred, and the base resin composition was prepared.

14 parts of a thermally conductive filler (alumina powder, "ASFP-20" by Denka Co., Ltd., average particle diameter 0.2-0.5 micrometer, specific surface area 12-18 m <2> / g, aspect ratio 1.0), and a thermally conductive filler (alumina powder, "DW-0525" by Denka Co., Ltd., 19 micrometers in average particle diameter of 5.3 micrometers, specific surface area of 0.4 m <2> / g, aspect ratio 1.0), a thermally conductive filler (spherical silicon carbide powder, "SSC-A01" by Shinano Denkiseren company, average particle | grains) 14 micrometers in diameter 1.4 micrometers, specific surface area 5.0m <2> / g, aspect ratio 1.25), and a thermally conductive filler (spherical silicon carbide powder, "SSC-A15" by Shinano Denkiserene Co., Ltd., average particle diameter 18.6micrometer, specific surface area 0.3m <2> / g And 41 parts of aspect ratio 1.25) were added and stirred, and the paste-like resin composition 10 was obtained.

<Example 11>

In Example 10, 41 parts of thermally conductive fillers (spherical silicon carbide powder, "SSC-A15" manufactured by Shinano Denkiserene Co., Ltd., average particle diameter 18.6 µm, specific surface area of 0.3 m2 / g, aspect ratio 1.25), and thermally conductive fillers (spherical shape) The silicon carbide powder, "SSC-A30" by Shinano Denkiseren Co., Ltd., the average particle diameter of 34.4 micrometers, specific surface area 0.1 m <2> / g, aspect ratio 1.25) 41 parts was changed. A paste resin composition 11 was obtained in the same manner as in Example 10 except for the above matters.

<Example 12>

In Example 11, 4 parts of a liquid hardening | curing agent ("TMTP" by Yodogagaku Kogyo Co., Ltd., a trimethylol propane tris (3-mercapto propionate), molecular weight 398, trifunctional) are liquid curing agents (made by Showa Denko) "PE-1" and the pentaerythritol tetrakis (3-mercaptobutyrate)) 4 parts were changed. A paste resin composition 12 was obtained in the same manner as in Example 11 except for the above matters.

Example 13

In Example 12, the amount of the liquid curing agent (&quot; PE-1 &quot; manufactured by Showa Denko Co., Ltd., pentaerythritol tetrakis (3-mercaptobutyrate)) was changed from 4 parts to 3 parts, and further liquid curing agent (Meiwa Kasei Co., Ltd. "MEH-8000H", 2-allyl phenol formaldehyde polycondensate, and OH equivalent 139-143 g / eq) 1 part were added. A paste resin composition 13 was obtained in the same manner as in Example 12 except for the above matters.

Comparative Example 1

In Example 5,

1) Change the amount of bisphenol-type epoxy resin ("XX1059" manufactured by Shin-Nitetsu Chemical Co., Ltd., epoxy equivalent about 169 g / eq, 1: 1 mixed product of bisphenol A type and bisphenol F type) from 3 parts to 4 parts,

2) 6 parts of liquid hardening | curing agent ("TMTP" made from Yodogagaku Kogyo Co., Ltd., trimethylol propane tris (3-mercaptopropionate), molecular weight 398, trifunctional) solid curing agent (phenol novolak resin, Aika SDK phenol company) Manufactured `` BRG-557 '', OH equivalent 103-107 g / eq) to 5 parts

3) The amount of the curing accelerator ("TBP-DA" manufactured by Hokogagaku Kogyo Co., Ltd., tetrabutylphosphonium decanoic acid) was changed from 0.14 parts to 0.16 parts.

A paste resin composition 11 was obtained in the same manner as in Example 5 except for the above matters.

Comparative Example 2

In Example 5,

1) Change the amount of bisphenol-type epoxy resin (`` XX1059 '' manufactured by Shin-Nitetsu Chemical Co., Ltd. ,

2) Change the amount of 1,4-cyclohexanedimethanol diglycidyl ether type epoxy resin ("XX1658GS" manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd., epoxy equivalent 130-140 g / eq) from 3 parts to 4 parts,

3) Change the amount of tetramethylbiphenol type solid epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 187-197g / eq) from 1 part to 2 parts,

4) Change the amount of liquid curing agent ("TMTP" manufactured by Yodogagaku Kogyo Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional) from 6 parts to 8 parts,

5) Change the amount of curing accelerator ("TBP-DA" manufactured by Hokogagaku Kogyo Co., Ltd., tetrabutylphosphonium decanoic acid) from 0.14 parts to 0.19 parts,

6) A dispersant ("ED152" manufactured by Kusumoto Chemical Co., Ltd., alkylene oxide containing phosphate ester) was not added.

A paste resin composition 12 was obtained in the same manner as in Example 5 except for the above matters.

[Measurement of viscosity]

The temperature of the pasty resin composition of each Example and each comparative example was kept at 25 +/- 2 degreeC, and the E-type viscosity meter ("RE-80U" manufactured by Toki Sangyo Co., Ltd., 1 degrees 34 'x R24 cone, rotation speed is 1 rpm). Measured using.

[Measurement of Thermal Conductivity]

Each paste-like resin composition of Examples 1 to 4 was placed in a predetermined container, and thermally cured at 120 ° C. for 60 minutes in a thermocycling oven to prepare a cylindrical cured product having a thickness of 10 mm and a diameter of 36 mm. The thermal conductivity of the obtained cylindrical hardened | cured material was measured by the hot-disk method using "TPS-2500" by Kyoto Denso Kogyo Co., Ltd. in the constant temperature environment of measurement temperature 25 degreeC and 40% RH.

In Example 5, 7-10, and each paste-like resin composition of 2, the conditions which thermoset by a thermocycling oven were made into 120 degreeC 60 minutes to 150 degreeC 60 minutes. Except for the above matters, thermal conductivity was measured in the same manner as in Example 1.

Each paste-like resin composition of Example 6 and Comparative Example 1 was further subjected to 180 ° C. for 60 minutes after heat curing at 120 ° C. for 60 minutes for 150 ° C. for 60 minutes for the conditions of thermosetting in a heat circulation oven. Except for the above matters, thermal conductivity was measured in the same manner as in Example 1.

[Measurement of Adhesiveness]

The paste resin composition was apply | coated on the nickel plating board | substrate, and the capacitor | condenser chip was mounted on it. The paste-like resin composition which protruded from the capacitor | condenser chip was removed so that the adhesive area of a capacitor | tip chip might be 1.2 mm x 2.0 mm, and the test piece was obtained.

Next, the pasty resin composition of the obtained test piece was cured. The curing conditions of Examples 1 to 4 were 120 ° C. for 60 minutes, the curing conditions of Examples 5, 7 to 10 and Comparative Example 2 were 150 ° C. for 60 minutes, and the curing conditions of Example 6 and Comparative 1 were heated to 150 ° C. for 60 minutes. After hardening, it was further made into 180 degreeC 60 minutes.

The die shear strength of the pasty resin composition cured by using the Daisy 4000 series manufactured by scratching the capacitor | condenser chip on the pasty resin composition hardened | cured at the speed | rate of 200 micrometers / s in 25 degreeC environment was measured. This operation was performed 3 times and the average value was calculated | required. In addition, the adhesion was evaluated based on the following criteria.

◎: die shear strength 20N or more

○: die shear strength is less than 10N 20N

△: die shear strength is less than 10N

The component used for preparation of paste resin composition 1-12, and its compounding quantity (mass part of non volatile matter) are shown in the following table. In addition, abbreviation etc. in the following table | surface are as follows.

Content (mass%) of (C) component: Content of (C) component when the non volatile component in paste resin composition is 100 mass%

Content (volume%) of (C) component: Content of (C) component when the non volatile component in paste resin composition is 100 volume%

It is understood that Examples 1 to 13 had a low viscosity and high thermal conductivity. Moreover, since each Example has high die shear strength, it turns out that it is excellent in adhesiveness.

On the other hand, the comparative example 1 which does not contain the (B) component, and the comparative example 2 which does not contain the (D) component are more than 1000 Pa.s, and cannot apply it to metal foil, such as copper foil and aluminum foil, It was not able to be used as a paste-like resin composition.

In Examples 1-13, even if it does not contain (E) component, although it has a difference in degree, it confirms that it results in the same result as the said Example.

Claims (16)

(A) epoxy resin,
(B) liquid curing agent,
(C) a thermally conductive filler, and
(D) Paste-shaped resin composition containing a dispersing agent. The pasty resin composition of Claim 1 whose content of the organic solvent contained in a pasty resin composition is less than 1.0 mass% with respect to the total mass of a pasty resin composition. The paste-like resin composition of Claim 1 or 2 whose heat conductivity of the hardened | cured material of a pasty resin composition is 2.0 W / mK or more. The paste-like resin composition according to any one of claims 1 to 3, wherein the component (D) contains an oxyalkylene-containing phosphate ester. The paste-like resin composition according to any one of claims 1 to 4, wherein the component (C) contains at least one member selected from silicon carbide, boron nitride, aluminum nitride, and aluminum oxide. The paste-like resin composition according to any one of claims 1 to 5, wherein the component (C) contains silicon carbide. The paste-like resin composition of Claim 6 whose average particle diameters of a silicon carbide are 1 micrometer or more and 30 micrometers or less. The paste-like resin composition according to claim 6 or 7, wherein the component (C) further contains at least one member selected from boron nitride, aluminum nitride, and aluminum oxide. The paste-like resin according to any one of claims 1 to 8, wherein the content of the component (C) is 60 mass% or more and 95 mass% or less when the nonvolatile component in the pasty resin composition is 100 mass%. Composition. The paste resin composition as described in any one of Claims 1-9 in which (B) component contains 1 or more types chosen from a polythiol compound and a liquid phenol resin. The component (B) is trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), or dipenta according to any one of claims 1 to 10. Erythritol hexakis (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, tris (3-mercaptopropyl) isocyanurate, thioglycolic acid Octyl, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, 3-mercaptopropionic acid, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3 Mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -tree On, trimethylolpropanetris (3-mercaptobutyrate), trimethylolethanetris (3-mercaptobutyrate), 1,3,4,6-tetraki (2-mercaptoethyl) glycoluril, and at least one polythiol compound selected from 4,4'-isopropylidenebis [(3-mercaptopropoxy) benzene], and an alkenyl group-containing novolak-type phenolic resin Paste-type resin composition containing 1 or more types chosen from liquid phenol resin chosen from. The paste-like resin composition according to any one of claims 1 to 11, wherein the viscosity at 25 ° C of the paste-like resin composition is 350 Pa · s or less. The circuit board containing the insulating layer formed of the hardened | cured material of the pasty resin composition of any one of Claims 1-12. The semiconductor chip package containing the circuit board of Claim 13, and the semiconductor chip mounted on the said circuit board. The semiconductor chip package containing the semiconductor chip sealed by the paste-like resin composition in any one of Claims 1-12. The electronic member which has a heat sink, the hardened | cured material of the pasty resin composition of any one of Claims 1-12 provided on the said heat sink, and the electronic component mounted on the said hardened | cured material.

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