JPWO2018181737A1 - Paste resin composition - Google Patents

Abstract

A paste-like resin composition containing (A) an epoxy resin, (B) a liquid curing agent, (C) a thermally conductive filler, and (D) a dispersant.

Description

  The present invention relates to a paste-like resin composition. Further, the present invention relates to a circuit board, a semiconductor chip package, and an electronic member using the paste-like resin composition.

  2. Description of the Related Art In recent years, as electronic devices have become smaller and more sophisticated, the mounting density of semiconductor elements on printed wiring boards has tended to increase. There is a demand for a technology for efficiently dissipating heat generated by a semiconductor element in combination with the enhancement of the functions of the semiconductor element to be mounted.

  For example, Patent Document 1 discloses that heat is dissipated by using an insulating layer obtained by curing a resin composition containing a resin and alumina satisfying predetermined requirements for a circuit board.

JP 2012-77123 A

  The present inventors have studied to more efficiently radiate the heat generated by the semiconductor element. 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 the resin composition cannot be applied to a circuit board or the like. It was found that there is a possibility.

  The present invention has been made in view of the above, and a paste-like resin composition having a low viscosity, from which a cured product having a high thermal conductivity can be obtained; a circuit board, a semiconductor using the paste-like resin composition It is to provide a chip package and an electronic member.

  In order to achieve the object of the present invention, the inventors of the present invention have conducted intensive studies and have found that (A) an epoxy resin, (B) a liquid curing agent, (C) a thermally conductive filler, and (D) a dispersant. Thus, the present inventors have found that a paste-like resin composition having a low viscosity can be obtained and a cured product having a high thermal conductivity can be obtained, and the present invention has been completed.

That is, the present invention includes the following contents.
[1] (A) epoxy resin,
(B) a liquid curing agent,
A paste-like resin composition containing (C) a thermally conductive filler, and (D) a dispersant.
[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 based on the total mass of the paste-like resin composition. object.
[3] The paste-like resin composition according to [1] or [2], wherein the cured product of the paste-like resin composition has a thermal conductivity of 2.0 W / mK or more.
[4] The paste-like resin composition according to any one of [1] to [3], wherein the component (D) contains an oxyalkylene-containing phosphate.
[5] The paste-like resin composition according to any one of [1] to [4], wherein the component (C) includes at least one 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], wherein the component (C) contains silicon carbide.
[7] The paste-like resin composition according to [6], wherein the average particle size of the silicon carbide is 1 μm or more and 30 μm or less.
[8] The paste resin composition according to [6] or [7], wherein the component (C) further contains at least one selected from boron nitride, aluminum nitride, and aluminum oxide.
[9] Any of [1] to [8], wherein the content of the component (C) is 60% by mass or more and 95% by mass or less when the nonvolatile component in the paste-like resin composition is 100% by mass. The paste-like resin composition according to the above.
[10] The paste resin composition according to any one of [1] to [9], wherein the component (B) includes at least one 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, octyl thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycol , 3-mercaptopropionic acid, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyrate) (Ryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethanetris (3-mercaptobutyrate) ), 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril, at least one polythiol compound selected from 4,4'-isopropylidenebis [(3-mercaptopropoxy) benzene], and an alkenyl group The paste-like resin composition according to any one of [1] to [10], comprising at least one selected from liquid phenolic resins selected from novolak-type phenolic resins.
[12] The paste-like resin composition according to any one of [1] to [11], wherein the viscosity of the paste-like resin composition at 25 ° C. is 350 Pa · s or less.
[13] A circuit board including an insulating layer formed of a cured product of the paste-like resin composition according to any one of [1] to [12].
[14] A semiconductor chip package including the circuit board according to [13] and a semiconductor chip mounted on the circuit board.
[15] A semiconductor chip package including a semiconductor chip sealed with the paste-like resin composition according to any one of [1] to [12].
[16] 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. Electronic components.

  ADVANTAGE OF THE INVENTION According to this invention, the paste-like resin composition with low viscosity which can obtain the hardened | cured material with high thermal conductivity; The circuit board, the semiconductor chip package, and the electronic member using this paste-like resin composition are provided. can do.

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

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

[Paste resin composition]
The paste-like resin composition contains (A) an epoxy resin, (B) a liquid curing agent, (C) a thermally conductive filler, and (D) a dispersant. By containing the components (A) to (D), the viscosity of the paste-like resin composition can be reduced, and the thermal conductivity of the cured product can be increased. Further, since the paste-like resin composition is in the form of a paste, the adhesion between the cured product and an electronic member such as a circuit board is improved. Since the cured product of the paste-like resin composition has high thermal conductivity and improved adhesion, the heat radiation efficiency of the electronic member can be improved. The paste-like resin composition is in the form of a paste at 25 ° C. The paste state refers to a paste-like property having a viscosity that can be applied to an electronic member such as a circuit board.

  The paste-like resin composition may further contain (E) a curing accelerator, (F) a flame retardant, and (G) an optional additive, if necessary, in addition to the components (A) to (D). Good. Hereinafter, each component contained in the paste-like resin composition will be described in detail.

<(A) Epoxy resin>
The paste-like resin composition contains (A) an epoxy resin. By including the component (A), 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 type epoxy resin Resin, naphthol novolak type epoxy resin, phenol novolak type 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, heterocycle Epoxy resins, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. One epoxy resin may be used alone, or two or more epoxy resins may be used in combination.

  The component (A) preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. The resin composition preferably contains a liquid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “liquid epoxy resin”), and a liquid epoxy resin and a solid epoxy resin at a temperature of 20 ° C. (“solid epoxy resin”). ) Is more preferable. As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable, and an aromatic liquid epoxy resin having two or more epoxy groups in one molecule is more preferable. As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable. In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.

  As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin, ester skeleton Alicyclic epoxy resin, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having a butadiene structure are preferable, bisphenol A type epoxy resin, bisphenol F type epoxy resin and cyclohexane type epoxy resin Resins are more preferred. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC, “828US”, “jER828EL”, “825”, and “Epicoat” manufactured by Mitsubishi Chemical Corporation. “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" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corp., manufactured by Daicel Corporation "Ceroxide 20 1P "(alicyclic epoxy resin having an ester skeleton)," PB-3600 "(epoxy resin having a butadiene structure)," ZX1658 "and" ZX1658GS "(manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) (liquid 1,4-glycidylcyclohexane type) Epoxy resin), “630LSD” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These may be used alone or in combination of two or more.

  Examples of the solid epoxy resin include 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, and biphenyl. Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and bixylenol type epoxy resin, naphthalene type epoxy resin and bisphenol AF Epoxy resins and naphthylene ether epoxy resins are more preferred. As specific examples of the solid epoxy resin, “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” (DIC) manufactured by DIC Corporation Cresol novolak type epoxy resin), "N-695" (cresol novolak 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" (Nippon Kayaku) Trisphenol type epoxy resin), "NC7000L" (naphthol novolak type epoxy) Fat), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ), “YX4000H”, “YX4000”, “YL6121” (biphenyl-type epoxy resin), “YX4000HK” (bixylenol-type epoxy resin), “YX8800” (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation, Osaka Gas Chemical Company "PG-100" and "CG-500" manufactured by Mitsubishi Chemical Corporation, "YL7760" (bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin), "jER1010" manufactured by Mitsubishi Chemical Corporation (solid Bisphenol A type Epoxy resin), "jER1031S" (tetraphenyl ethane epoxy resin) and the like. These may be used alone or in combination of two or more.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (A), the ratio by weight (liquid epoxy resin: solid epoxy resin) is 1: 0.01 to 1: 5 by mass. A range is preferred. By setting the ratio of the liquid epoxy resin to the solid epoxy resin in the above range, it is possible to obtain effects such as obtaining a cured product having a sufficient breaking strength. From the viewpoint of the above effects, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably 1: 0.05 to 1: 1 in terms of mass ratio. : 0.1 to 1: 0.5 is more preferable.

  The content of the component (A) is preferably 1% by mass or more when the total amount of the non-volatile components in the paste-like resin composition is 100% by mass, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. , More preferably 3% by mass or more, even more preferably 5% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exerted, but is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less.

  The epoxy equivalent of the component (A) is preferably 50 to 5,000, more preferably 50 to 3,000, further preferably 80 to 2,000, and still more preferably 110 to 1,000. When the content falls within this range, the crosslinked density of the cured product becomes sufficient and an insulating layer having a small surface roughness can be obtained. The epoxy equivalent can be measured according to JIS K7236 and is the mass of a resin containing one equivalent of an epoxy group.

  The weight average molecular weight of the component (A) is preferably from 100 to 5,000, more preferably from 250 to 3,000, even more preferably from 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

<(B) Liquid curing agent>
The paste-like resin composition contains (B) a liquid curing agent. By including the component (B) in combination with the dispersant (D) described below, the viscosity of the pasty resin composition can be reduced. 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., and examples thereof include a polythiol compound, a liquid phenol resin, an acid anhydride, and imidazole. Is mentioned. As the component (B), one type may be used alone, or two or more types may be used in combination.

  The component (B) is selected from a polythiol compound and a liquid phenol resin from the viewpoint that the paste-like resin composition can be cured in a low temperature range and further contributes to lowering the viscosity of the paste-like resin composition. It is preferable to include one or more of these, and it is preferable to include one of 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, but preferably has 2 to 6 (bifunctional to 6 functional) thiol groups in one molecule, and preferably has 3 to 6 (trifunctional to 6 functional). (6 functional groups) are preferred. Examples of such polythiol compounds include trimethylolpropane tris (3-mercaptopropionate) (abbreviation: TMTP), pentaerythritol tetrakis (3-mercaptopropionate) (abbreviation: PEMP), and dipentaerythritol hexakis (3-mercaptopropionate) (abbreviation: DPMP), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate (abbreviation: TEMPIC), tris (3-mercaptopropyl) isocyanurate (abbreviation: TMPIC) Octyl thioglycolate (abbreviation: OTG), ethylene glycol bisthioglycolate (abbreviation: EGTG), trimethylolpropane tristhioglycolate (abbreviation: TMTG), pentaerythritol tetrakisthioglycolate (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, trimethylolpropane tris (3-mercaptobutyrate) (abbreviation: TPMB), Methylolethanetris (3-mercaptobutyrate) (abbreviation: TEMB), 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril, 4,4′-isopropylidenebis [(3-mercaptopropoxy) benzene And the like. These compounds can be synthesized by a known method. For example, tris (3-mercaptopropyl) isocyanurate (abbreviation: TMPIC) and 4,4′-isopropylidenebis [(3-mercaptopropoxy) benzene] For example, it can be synthesized by the method described in JP-A-2012-153794 or WO 2001/006998.

  As the polythiol compound, commercially available products may be used. Examples of commercially available products include “PEMP” (manufactured by SC Organic Chemicals), “OTG”, “EGTG”, “TMTG”, “PETG”, “3-MPA”, "TMTP", "PETP" (manufactured by Yodo Chemical), "TEMP", "PEMP", "TEMPIC", "DPMP" (manufactured by Sakai Chemical Industry), "PE-1" (pentaerythritol tetrakis (3-mercapto) Butyrate)), "BD-1" (1,4-bis (3-mercaptobutyryloxy) butane), "NR-1" (1,3,5-tris (3-mercaptobutyryloxyethyl)-) 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione), "TPMB", "TEMB" (manufactured by Showa Denko KK), "TS-G" (mercaptoethyl glycol) (Shikoku) Conversion Kogyo Co., Ltd.), and the like. The polythiol compounds may be used alone or in combination of two or more.

  The thiol group equivalent of the polythiol compound is preferably 50 to 500 g / eq, more preferably 75 to 300 g / eq, and still more preferably 100 to 200 g / eq. The “thiol group equivalent” is a gram number (g / eq) of a resin containing one gram equivalent of a thiol group, and can be measured by a known method, for example, an iodine solution titration method using 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 resin containing a phenolic hydroxyl group and being liquid at a temperature of 20 ° C. include a cresol resin, a novolak-type phenol resin (a phenol novolak resin, a cresol novolak resin, and a modified product thereof), and a liquid alkenyl group-containing phenol resin. And a liquid alkenyl group-containing phenol resin is preferred. The number of carbon atoms of the alkenyl group is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 3. Among them, a 2-propenyl group (allyl group) is preferable as the alkenyl group.

〔式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立して、水素原子又はアルケニル基を表し、Ｒ^７及びＲ^８は、それぞれ独立して、水素原子又はアルキル基を表し、ｊは０〜５の整数を表す。但し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５の少なくとも１つはアルケニル基である。〕Examples of the liquid alkenyl group-containing phenol resin include an alkenyl group-containing novolak type phenol resin, and a phenol resin represented by the following formula (1) is preferable.

[Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkenyl group, and R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group And j represents an integer of 0 to 5. However, at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is an alkenyl group. ]

In the formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkenyl group. However, in the formula (1), at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is an alkenyl group. The number of carbon atoms of the alkenyl group is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 3. Among them, a 2-propenyl group (allyl group) is preferable as the alkenyl group.

  In formula (1), the number of alkenyl groups is not particularly limited as long as it is 1 or more, but is preferably 1 or 2 per benzene ring, more preferably 1 per benzene ring.

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

In the 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, and still more preferably 1 to 4, 1 to 3, or 1.

In the formula (1), when a plurality of R ⁷ are present, they may be the same or different. The same is true for R ^8.

  In the formula (1), j is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1, and still more preferably 0.

R ^{1 to} R ⁸ may not have a substituent, and may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, —OH, —O—C _1-6 alkyl group, —N (C _1-6 alkyl group) ₂ , C _1-6 alkyl group, and C _{6-6. 10} aryl _{group, -NH 2, -CN, -C (} O) O-C 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 satisfy p <q) means that the number of carbon atoms of the organic group described immediately after this term is p to q. Indicates that there is. For example, the expression “C _1-6 alkyl group” indicates an alkyl group having 1 to 6 carbon atoms. The above substituents may further have a substituent (hereinafter, may be referred to as a “secondary substituent”). As the secondary substituent, the same substituent as described above may be used unless otherwise specified.

  A commercially available liquid phenol resin may be used. Commercially available liquid phenolic resins include, for example, "MEH-8000H" and "MEH-8005" manufactured by Meiwa Kasei Co., Ltd.

  The phenolic hydroxyl group equivalent of the liquid phenol resin is preferably 50 to 500 g / eq, more preferably 75 to 300 g / eq, and further preferably 100 to 200 g / eq. The phenolic hydroxyl group equivalent can be measured according to JIS K0070 and is the mass of the resin containing one equivalent of the phenolic hydroxyl group.

  The ratio between the epoxy resin and the liquid curing agent is a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the liquid curing agent], and is in the range of 1: 0.1 to 1:10. Preferably, the ratio is 1: 0.5 to 1: 5, more preferably 1: 0.5 to 1: 3. Here, the reactive group of the liquid curing agent is a thiol group, a phenolic hydroxyl group, or the like, and differs depending on the type of the liquid curing agent. In addition, the total number of epoxy groups in the epoxy resin is a value obtained by dividing the value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups in the liquid curing agent is The value obtained by dividing the mass of the solid content of each liquid curing agent by the equivalent of the reactive group is the total value of all liquid curing agents. By setting the ratio of the epoxy resin to the liquid curing agent in such a range, the heat resistance of the cured product of the paste-like resin composition is further improved.

  The content of the component (B) is preferably 1% by mass or more, more preferably 1% by mass or more, assuming that the entire nonvolatile component in the paste-like resin composition is 100% by mass from the viewpoint of reducing the viscosity of the paste-like resin composition. It is at least 2% by mass, more preferably at least 3% by mass. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

  The total content of the component (A) and the component (B) is assuming that the nonvolatile component in the paste resin composition is 100% by mass from the viewpoint of lowering the viscosity of the paste resin composition and improving insulation reliability. , Preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more. The upper limit of the total content is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

<(C) Thermal conductive filler>
The paste-like resin composition contains (C) a thermally conductive filler. By containing the component (C), a cured product (insulating layer) having high thermal conductivity can be obtained.

  Examples of the material of the component (C) include silicon carbide, boron nitride, aluminum nitride, and aluminum oxide (alumina). As the component (C), one type may be used alone, or two or more types may be used in combination. Further, two or more kinds of the same materials may be used in combination. Among them, the component (C) preferably contains silicon carbide from the viewpoint of obtaining a cured product having high thermal conductivity. In addition, the component (C) preferably contains at least one selected from silicon carbide, boron nitride, aluminum nitride, and aluminum oxide from the viewpoint of obtaining a cured product having high thermal conductivity and reducing viscosity. More preferably, it contains two or more kinds selected from silicon carbide, boron nitride, aluminum nitride, and aluminum oxide, and further preferably, it contains one or more kinds selected from boron nitride, aluminum nitride, and aluminum oxide together with silicon carbide. .

  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 further preferably 270 W / m · K or more, from the viewpoint of obtaining a cured product having high thermal conductivity. It is. The upper limit is not particularly limited, but may be 1000 W / m · K or less.

  The average particle size of silicon carbide is preferably 45 μm or less, more preferably 40 μm or less, and still more preferably 35 μm or less, from the viewpoint of obtaining a cured product having high thermal conductivity. The lower limit of the average particle size is preferably 0.1 μm or more, more preferably 0.5 μm or more, and further preferably 1 μm 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 reducing the viscosity of the paste-like resin composition. More preferably, it is 1.5 μm or less. The lower limit of the average particle size is preferably 0.01 μm or more, more preferably 0.05 μm or more, and further preferably 0.08 μm or more.

  The average particle size of the component (C) can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured on a volume basis by a laser diffraction / scattering type particle size distribution measuring apparatus, and the median diameter can be measured by setting the median diameter as the average particle diameter. As the measurement sample, one obtained by dispersing the component (C) in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba, Ltd., "SALD2200" manufactured by Shimadzu, etc. can be used.

The specific surface area of component (C), from the viewpoint of obtaining a cured product having excellent thermal conductivity, preferably 0.01 m ² / g or more, more preferably 0.025 m ² / g or more, more preferably 0.05 m ² / g or more. The upper limit is preferably 30 m ² / g or less, more preferably 25 m ² / g or less, and even more preferably 20 m ² / g or less. The specific surface area of the component (C) can be measured by a nitrogen BET method. Specifically, the measurement can be performed using an automatic specific surface area measuring device. As the automatic specific surface area measuring device, “Macsorb HM-1210” manufactured by Mountech Co., Ltd. or the like can be used.

  The aspect ratio of the component (C) is preferably 8 or less, more preferably 5 or less, even more preferably 3 or less, 2 or less, or 1.5 or less. The lower limit may be 1.0 or more. By including the component (C) having an aspect ratio in such a range in the paste-like resin composition, a cured product having excellent thermal conductivity can be obtained without increasing the viscosity. The aspect ratio indicates a value obtained by dividing the length of the long side of the powder of the component (C) by the length of the short side.

  As the component (C), a commercially available product may be used. Examples of commercially available products include “DAW-0525” and “ASFP-20” manufactured by Denka, “SSC-A01”, “SSC-A15” and “SSC-A30” manufactured by Shinano Electric Smelting and “HF” manufactured by Tokuyama. -01 "and" MBN-010T "manufactured by Mitsui Chemicals, Inc.

  The component (C) is, from the viewpoint of improving moisture resistance and dispersibility, 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, It may be treated with one or more surface treatment agents such as a titanate coupling agent. Commercially available surface treatment agents include, for example, “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu "KBE903" (3-aminopropyltriethoxysilane) manufactured by Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  The degree of the surface treatment with the surface treatment agent is, from the viewpoint of improving the dispersibility of the component (C), from 0.2 to 5 parts by mass of the surface treatment agent with respect to 100 parts by mass of the component (C). The surface treatment is preferably performed at 0.2 to 3 parts by mass, and the surface treatment is preferably performed at 0.3 to 2 parts by mass.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the component (C). Carbon content per unit surface area of the component (C), (C) from the viewpoint of improving dispersibility of the components, preferably from 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / m ² or more is more preferable. On the other hand, from the viewpoint of suppressing an increase in melt viscosity is preferably 1 mg / ^{m 2} or less, more preferably 0.8 mg / ^{m 2} or less, 0.5 mg / ^{m 2} or less is more preferable.

  The amount of carbon per unit surface area of the component (C) can be measured after the component (C) after the surface treatment is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the component (C) surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the component (C) can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. or the like can be used.

  As the component (C), it is preferable to use two types of the same material having different average particle sizes in combination. With such a configuration, a cured product having higher thermal conductivity can be obtained, and the viscosity of the paste resin composition can be further reduced. In the two same materials, when the component (C) having a small average particle size is C1 and the component (C) having a large average particle size is C2, the mass ratio (C1 / C2) is preferably 0.1. It is at least 1, more preferably at least 0.2, even more preferably at least 0.3. The upper limit is preferably 1 or less, more preferably 0.9 or less, and still more preferably 0.8 or less.

  The content of the component (C) is preferably from the viewpoint of obtaining a cured product having excellent thermal conductivity and reducing the viscosity of the paste-like resin composition, when the nonvolatile component in the paste-like resin composition is 100% by mass. Is 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more. The upper limit is preferably 95% by mass or less, more preferably 93% by mass or less, and even more preferably 90% by mass or less.

  The content of the component (C) is preferably from the viewpoint of obtaining a cured product having excellent thermal conductivity and reducing the viscosity of the paste-like resin composition, when the nonvolatile component in the paste-like resin composition is 100% by volume. Is at least 30% by volume, more preferably at least 40% by volume, still more preferably at least 50% by volume or at least 55% by volume. The upper limit is preferably 90% by volume or less, more preferably 85% by volume or less, even more preferably 80% by volume or less or 75% by volume or less.

<(D) Dispersant>
The paste-like resin composition contains (D) a dispersant. By including the component (D) together with the component (B), the fluidity of the paste-like resin composition is improved, and as a result, the viscosity of the paste-like resin composition can be reduced. The component (D) is not particularly limited as long as the viscosity of the paste-like resin composition can be reduced, and examples thereof include an oxyalkylene-containing phosphate, a titanate coupling agent, a polyacrylic acid, and a polycarboxylic acid dispersant. And the like, and an oxyalkylene-containing phosphate and a titanate-based coupling agent are preferred. As the component (D), one type may be used alone, or two or more types may be used in combination.

  Examples of the oxyalkylene-containing phosphate include polyoxyalkylene alkyl ether phosphate, polyoxyalkylene alkyl phenyl ether phosphate, and the like, and polyoxyalkylene alkyl ether phosphate is preferred.

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

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

  As the alkylene group in the poly (alkyleneoxy) moiety, an alkylene group having 2 to 4 carbon atoms is preferable. Examples of such an alkylene group include an ethylene group, a propylene group, an isopropylene group, a butylene group, and an isobutyl group.

  The alkyl group in the alkyl-oxy-poly (alkyleneoxy) group is preferably an alkyl group having 6 to 30 carbon atoms, and more preferably an alkyl group having 8 to 20 carbon atoms. Examples of such an alkyl group include 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, and the like.

  When the polyoxyalkylene alkyl ether phosphate has a plurality of alkyl-oxy-poly (alkyleneoxy) groups, the plurality of alkyl groups and the alkylene group in the poly (alkyleneoxy) moiety are different. But may be the same. In addition, the oxyalkylene-containing phosphate may be a mixture with an amine or the like.

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

  Commercially available oxyalkylene-containing phosphate esters may be used. Examples of commercially available products include HIPLAAD series (for example, “ED152”, “ED153”, “ED154”, “ED118”, “ED174”, ED251 ").

  Examples of titanate-based coupling agents include isopropyl tristearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl pyrophosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra Isopropyl bis (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 tridecylbenzenesulfonyl titanate, isopropyl tri (dioctylphosphine) Tol) titanate, isopropyl dimethacryl isostearyl titanate, isopropyl isostearyl diacryl titanate, isopropyl tricumyl phenyl titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate, and the like, and tetra (2,2-diallyloxy) Methyl-1-butyl) bis (ditridecyl) phosphite titanate is preferred.

  Commercially available titanate-based coupling agents may be used, and examples of commercially available products include “Preneact 55”, “Preneact TTS”, and “Preneact 46B” manufactured by Ajinomoto Fine-Techno.

  The content of the component (D) is preferably 0.1% by mass or more, when the total amount of the nonvolatile components in the paste-like resin composition is 100% by mass, from the viewpoint of reducing the viscosity of the paste-like resin composition. It is preferably at least 0.3% by mass, more preferably at least 0.5% by mass. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less.

<(E) Curing accelerator>
In one embodiment, the paste-like resin composition may contain (E) a curing accelerator. Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, and a metal-based curing accelerator. A curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are preferable, and from the viewpoint of lowering the viscosity of the paste-like resin composition and improving the adhesion of the cured product of the paste-like resin composition, phosphorus-based curing acceleration Agents are preferred.

  Examples of the phosphorus-based curing accelerator include triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoic acid, tetrabutylphosphonium decanoate, (4-methyl (Phenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine, tetrabutylphosphonium decanoic acid and salts thereof are preferable.

  Examples of the amine-based 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 are preferable, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

  Examples of the imidazole-based curing accelerator include, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 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-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (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-triazine isocyanuric acid adduct, 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 Imidazole compounds such as -3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline; and adducts of imidazole compounds and epoxy resins; 2-ethyl-4-methylimidazole, 1-benzyl-2- Phenylimidazole is preferred.

  As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-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-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  Examples of the metal-based curing accelerator include an organic metal complex or an organic metal salt of a metal such as cobalt, copper, zinc, iron, nickel, manganese, and tin. 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 zinc (II) acetylacetonate. And the like, an organic iron complex such as iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

  When the paste-like resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.01% by mass or more, when the entire non-volatile component in the paste-like resin composition is 100% by mass, It is preferably at least 0.05% by mass, more preferably at least 0.1% by mass. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less. By setting the content of the curing accelerator in such a range, the viscosity can be reduced and the adhesion of the cured product can be improved.

<(F) Flame retardant>
In one embodiment, the paste-like resin composition may contain (F) a flame retardant. Examples of the flame retardant include organic phosphorus-based flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone-based flame retardants, metal hydroxides, and the like. The flame retardants may be used alone or in combination of two or more.

  As the flame retardant, commercially available products may be used, for example, “HCA-HQ” manufactured by Sanko, “PX-200” manufactured by Daihachi Chemical Industry, and the like. As the flame retardant, those which are not easily hydrolyzed are preferable, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

  When the paste-like resin composition contains a flame retardant, the content of the flame retardant is not particularly limited. When the nonvolatile component in the paste-like resin composition is 100% by mass, preferably 0.5% by mass to 20% by mass. % By mass, more preferably 0.5% by mass to 15% by mass, still more preferably 0.5% by mass to 10% by mass.

<(G) Optional additives>
The resin composition may further contain other additives as necessary. Examples of such other additives include a thermoplastic resin and an inorganic filler (however, corresponding to the component (C)). ), Organic fillers, organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds, as well as binders, thickeners, defoamers, leveling agents, adhesion promoters, colorants, etc. And the like.

<Physical properties and applications of paste-like resin composition>
The content of the organic solvent contained in the paste-like resin composition is preferably less than 1.0% by mass, more preferably 0.8% by mass or less, further preferably, based on the total mass of the paste-like resin composition. It is 0.5% by mass or less and 0.1% by mass or less. The lower limit is not particularly limited, but is 0.001% by mass or more, or is not contained. The viscosity of the paste-like resin composition of the present invention can be reduced without containing an organic solvent. Since the amount of the organic solvent is small in this manner, the generation of voids due to the volatilization of the organic solvent can be suppressed, so that the adhesion to an electronic member such as a circuit board can be improved, and as a result, the electronic member Heat radiation efficiency can be improved. Here, the organic solvent means a component that does not have a function of curing the component (A) and is liquid at 25 ° C.

  The viscosity of the paste-like resin composition at 25 ° C. is preferably 350 Pa · s or less, more preferably 330 Pa · s or less, and further preferably 310 Pa · s or less. The lower limit is not particularly limited, but may be 1 Pa · s or more, 10 Pa · s or more, or the like. The viscosity can be measured according to the description of [Measurement of viscosity] described later. By setting the viscosity of the paste-like resin composition within such a range, the fluidity of the paste-like resin composition is increased, and the adhesion is also improved.

  A cured product of a paste-like resin composition (for example, a cured product obtained by thermally curing a paste-like resin composition at 150 ° C. for 60 minutes, or a cured product of a paste-like resin composition thermally cured at 120 ° C. for 60 minutes) A cured product obtained by thermally curing a cured product or a paste-like resin composition at 150 ° C. for 60 minutes and then thermally curing at 180 ° C. for 60 minutes) exhibits excellent thermal conductivity. That is, an insulating layer having high thermal conductivity is provided. The thermal conductivity is 1.0 W / m · K or more, preferably 2.0 W / m · K or more, more preferably 3.0 W / m · K or more, and still more preferably 5.0 W / m · K or more. is there. The upper limit of the thermal conductivity is not particularly limited, but may be 10 W / m · K or less. The evaluation of the thermal conductivity can be measured according to the method described in [Measurement of thermal conductivity] described later.

  A cured product obtained by thermally curing the paste-like resin composition at 150 ° C. for 60 minutes shows excellent adhesion. That is, an insulating layer having excellent adhesion is provided. The die shear strength of the cured product is preferably 10 N or more, more preferably 20 N or more. The upper limit is not particularly limited, but may be 200 N or less. The evaluation of adhesion can be measured according to the method described in [Evaluation of Adhesion] described later. Since the cured product exhibits excellent adhesiveness and excellent thermal conductivity, the heat radiation efficiency to an electronic member or the like which comes into contact with the cured product can be increased.

  Since the paste-like resin composition is a paste having high fluidity, for example, the paste-like resin composition is injected with a syringe, and the paste-like resin composition is pressed and spread so as to have a uniform thickness. Can be formed. For this reason, as described in JP-A-2012-77123, a resin varnish is prepared using an organic solvent, the resin varnish is dried to remove the organic solvent, and formed into a film (resin composition layer). Need not be formed). Since it is not necessary to prepare a resin varnish using an organic solvent in the paste-like resin composition, the presence of the organic solvent does not reduce the heat radiation efficiency of the electronic member.

  The paste-like resin composition of the present invention can provide an insulating layer having high thermal conductivity and high adhesion. Therefore, the paste-like resin composition of the present invention is used for forming a paste-like resin composition for bonding a heat sink to an electronic component (paste-like resin composition for bonding a heat sink) and for forming an insulating layer of a semiconductor chip package. Paste resin composition (paste resin composition for insulating layer of semiconductor chip package), paste resin composition for forming insulating layer of circuit board (including printed wiring board) (paste for insulating layer of circuit board) Resin composition), and a paste-like resin composition for forming an interlayer insulating layer on which a conductive layer is formed by plating (an interlayer of a circuit board on which a conductive layer is formed by plating). (Past resin composition for insulating layer). Further, a paste-like resin composition for sealing a semiconductor chip (a paste-like resin composition for sealing a semiconductor chip) and a paste-like resin composition for forming a wiring on a semiconductor chip (a paste-like resin composition for forming a semiconductor chip wiring). Resin composition).

[Circuit board]
The circuit board of the present invention includes an insulating layer formed of a cured product of the paste resin composition of the present invention.
The method for manufacturing a circuit board of the present invention includes:
(1) a step of preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate;
(2) a step of applying the paste-like resin composition on a substrate with a wiring layer so as to bury the wiring layer, and thermally curing to form an insulating layer;
And (3) a step of connecting the wiring layers between layers. Further, the method for manufacturing a circuit board may include the step of (4) removing the base material.

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

<Step (1)>
Step (1) is a step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material. Usually, the substrate with a wiring layer has a first metal layer and a second metal layer, which are part of the substrate, on both surfaces of the substrate, respectively, and the second metal layer has a surface opposite to the surface of the substrate on the substrate side. It has a wiring layer on the surface. Specifically, a dry film (photosensitive resist film) is laminated on a substrate, and is exposed and developed under a predetermined condition using a photomask to form a pattern dry film. After forming a wiring layer by electrolytic plating using the developed pattern dry film as a plating mask, the pattern dry film is peeled off.

  Examples of the substrate include substrates such as a glass epoxy substrate, a metal substrate (such as stainless steel and a cold-rolled steel plate (SPCC)), a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. A metal layer such as a copper foil may be formed on the surface. In addition, a metal layer such as a first metal layer and a second metal layer (for example, an ultra-thin copper foil with a carrier copper foil manufactured by Mitsui Mining & Smelting Co., trade name “Micro Thin”) formed on the surface is formed. Is also good.

  The dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition. For example, a dry film such as a novolak resin or an acrylic resin can be used. A commercially available dry film may be used.

  The lamination of the substrate and the dry film may be performed by a vacuum lamination method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in a range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098MPa to 1.77MPa, more preferably 0mm. .29 MPa to 1.47 MPa, and the heat-compression bonding time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably performed under a reduced pressure condition of a pressure of 13 hPa or less.

  After laminating the dry film on the substrate, exposure and development are performed under predetermined conditions using a photomask in order to form a desired pattern on the dry film.

  The ratio of the line (circuit width) / space (width between circuits) of the wiring layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 10/100 μm or less, and still more preferably 5/20 μm or less. It is 5 μm or less, more preferably 1/1 μm or less, particularly preferably 0.5 / 0.5 μm or more. The pitch need not 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 forming the pattern of the dry film, a wiring layer is formed, and the dry film is peeled off. Here, the wiring layer can be formed by a plating method using a dry film on which a desired pattern is formed as a plating mask.

  The conductor material used for the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Including metal. The wiring layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper Nickel alloy and copper / titanium alloy). Among them, from the viewpoint of versatility of wiring layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper A nickel alloy or an alloy layer of copper-titanium alloy is preferable, 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. Metal layers are more preferred.

  The thickness of the wiring layer depends on the desired design of the wiring board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 to 20 μm, or 15 to 20 μm. In the step (3), when the step of polishing or grinding the insulating layer to expose the wiring layer and connect the wiring layers to each other is adopted, it is preferable that the thickness of the wiring to be connected between layers and the thickness of the wiring not to be connected are different. . The thickness of the wiring layer can be adjusted by repeating the above-described pattern formation. The thickness of the thickest wiring layer (conductive pillar) among the respective wiring layers depends on a desired wiring board design, but is preferably 2 μm or more and 100 μm or less. Further, the wiring for interlayer connection may be convex.

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

<Step (2)>
The step (2) is a step of applying the paste-like resin composition on a substrate with a wiring layer so that the wiring layer is embedded, and thermally curing the same to form an insulating layer. Specifically, the paste-like resin composition is applied on the wiring layer of the substrate with the wiring layer obtained in the above-mentioned step (1), and the paste-like resin composition is thermally cured to form an insulating layer.

  The application of the wiring layer and the paste-like resin composition is performed, for example, by injecting the paste-like resin composition with a syringe and pressing the paste-like resin composition to form a resin composition layer having a uniform thickness. Can be.

  After applying the paste-like resin composition on the substrate with the wiring layer so that the wiring layer is embedded, the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions of the resin composition layer vary depending on the type of the paste-like resin composition and the like. For example, the curing temperature is in a range of 120 ° C to 240 ° C, and the curing time is in a range of 5 minutes to 120 minutes. it can. Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature.

  After the resin composition layer is thermally cured to form an insulating layer, the surface of the insulating layer may be polished. The polishing method is not particularly limited, and polishing may be performed by a known method. For example, the surface of the insulating layer can be polished using a surface grinder.

<Step (3)>
Step (3) is a step of connecting the wiring layers between layers. Specifically, this is a step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers between layers. Alternatively, this is a step of polishing or grinding the insulating layer to expose the wiring layer and connect the wiring layers to each other.

  When a step of forming a via hole in the insulating layer, forming a conductor layer and connecting the wiring layers to each other is adopted, formation of the via hole is not particularly limited, and examples include laser irradiation, etching, and mechanical drilling. It is preferably performed by: This laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide laser, a YAG laser, an excimer laser, or the like as a light source.

  The conditions for laser irradiation are not particularly limited, and the laser irradiation can be performed by any suitable process according to a conventional method according to the selected means.

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

  After the formation of the via hole, a so-called desmear step, which is a step of removing smear in the via hole, may be performed. When the formation of the conductor layer described later is performed by a plating process, the via hole may be subjected to, for example, a wet desmear process, and when the formation of the conductor layer is performed by a sputtering process, for example, a plasma treatment process or the like is performed. A dry desmear step may be performed. The desmearing step may also serve as a roughening step.

  Before forming the conductor layer, the via hole and the insulating layer may be subjected to a roughening treatment. For the roughening treatment, known procedures and conditions that are usually performed can be adopted. Examples of the dry-type roughening treatment include plasma treatment, and examples of the wet-type roughening treatment include a method of performing 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. Is mentioned.

  The surface roughness (Ra) of the insulating layer surface after the roughening treatment is preferably 350 nm or more, more preferably 400 nm or more, and further preferably 450 nm or more. The upper limit is preferably 700 nm or less, more preferably 650 nm or less, and even more preferably 600 nm or less. The surface roughness (Ra) can be measured using, for example, a non-contact type surface roughness meter.

  After forming the via holes, a conductor layer is formed. The conductor material constituting the conductor layer is not particularly limited, and the conductor layer can be formed by a conventionally known arbitrary suitable method such as plating, sputtering, and vapor deposition, and is preferably formed by plating. In a preferred embodiment, for example, a conductive layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. The conductor layer may have a single-layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are stacked.

  Specifically, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern for exposing a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. An electrolytic plating layer is formed on the exposed plating seed layer by electrolytic plating. At this time, the via may be filled by electrolytic plating to form a filled via together with the formation of the electrolytic plating layer. After forming the electrolytic plating layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like, so that a conductor layer having a desired wiring pattern can be formed. When forming the conductor layer, the dry film used for forming the mask pattern is the same as the above dry film.

  The conductor layer may include not only linear wiring but also, for example, an electrode pad (land) on which an external terminal can be mounted. Further, the conductor layer may be composed of only the electrode pads.

  Further, the conductor layer may be formed by forming an electrolytic plating layer and a filled via without using a mask pattern after forming the plating seed layer, and then performing patterning by etching.

  When a step of polishing or grinding the insulating layer and exposing the wiring layer to connect the wiring layer to each other is adopted, as a method for polishing or grinding the insulating layer, the wiring layer can be exposed, and the polished or ground surface can be used. Is not particularly limited as long as it is horizontal, and a conventionally known polishing method or grinding method can be applied. For example, a chemical mechanical polishing method using a chemical mechanical polishing apparatus, a mechanical polishing method such as a buff, and a surface grinding method using a grindstone rotation. And the like. As in the step of forming a via hole in the insulating layer, forming the conductor layer, and connecting the wiring layers to each other, a smear removing step and a step of performing a roughening treatment may be performed, or the conductor layer may be formed. Further, it is not necessary to expose all the wiring layers, and a part of the wiring layers may be exposed.

<Step (4)>
Step (4) is a step of removing the base material and forming the circuit board of the present invention. The method for removing the substrate is not particularly limited. In a preferred embodiment, the base material is separated 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. If necessary, the substrate may be peeled off with the conductor layer protected by a 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 joining a semiconductor chip to the circuit board.

  The bonding conditions are not particularly limited as long as the terminal electrodes of the semiconductor chip are connected to the circuit wiring of the circuit board by conductors, and known conditions used in flip chip mounting of the semiconductor chip may be used. Further, the semiconductor chip and the circuit board may be joined via an insulating adhesive.

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

  In another preferred embodiment, a semiconductor chip is reflowed and joined to a circuit board. Reflow conditions can be, for example, in the range of 120 ° C to 300 ° C.

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

A second embodiment of the semiconductor chip package of the present invention is, for example, a semiconductor chip package (Fan-out type WLP) as shown in FIG. A semiconductor chip package (Fan-out type WLP) 100 whose example is shown in FIG. 1 is a semiconductor chip package in which a sealing layer 120 is manufactured using the paste resin composition of the present invention. The semiconductor chip package 100 includes a semiconductor chip 110, a sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110, and rewiring formed on a surface of the semiconductor chip 110 opposite to the side covered with the sealing layer. A 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 is as follows.
(A) a step of laminating a temporary fixing film on a substrate,
(B) temporarily fixing the semiconductor chip on the temporary fixing film;
(C) a step of applying the paste-like resin composition of the present invention on a semiconductor chip and heat-curing to form a sealing layer;
(D) a step of peeling the substrate and the temporary fixing film from the semiconductor chip;
(E) a step of forming a rewiring formation layer (insulating layer) on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled off;
(F) a step of forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer); and (G) a step of forming a solder resist layer on the conductor layer.
In addition, a method of manufacturing a semiconductor chip package includes:
(H) The method may include a step of dicing the plurality of semiconductor chip packages into individual semiconductor chip packages to singulate.

<Step (A)>
Step (A) is a step of laminating a temporary fixing film on a substrate. The conditions for laminating the substrate and the temporary fixing film are the same as the conditions for laminating the substrate and the dry film in step (1) described above, and the preferred range is also the same.

  The material used for the substrate is not particularly limited. As a base material, a silicon wafer; a glass wafer; a glass substrate; a metal substrate such as copper, titanium, stainless steel, and cold rolled steel plate (SPCC); Substrates made of bismaleimide triazine resin such as BT resin.

  The material of the temporary fixing film is not particularly limited as long as it can be peeled off from the semiconductor chip in the step (D) described later and the semiconductor chip can be temporarily fixed. As the temporary fixing film, a commercially available product can be used. Commercial products include Riva Alpha manufactured by Nitto Denko Corporation.

<Step (B)>
Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. The temporary fixing of the semiconductor chip can be performed using a known device such as a flip chip bonder or a die bonder. The layout and the number of arrangements of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the number of semiconductor packages to be produced, and the like.For example, a matrix with a plurality of rows and a plurality of columns And can be temporarily fixed.

<Step (C)>
Step (C) is a step of applying the paste-like resin composition of the present invention on a semiconductor chip and thermally curing the same to form a sealing layer.

  The conditions for applying and thermosetting the paste-like resin composition are the same as the methods for applying the paste-like resin composition and the thermosetting conditions in step (2) in the above-described circuit board manufacturing method.

<Step (D)>
Step (D) is a step of peeling the substrate and the temporary fixing film from the semiconductor chip. The method of peeling can be appropriately changed depending on the material of the temporary fixing film and the like. For example, a method of heating and foaming (or expanding) the temporary fixing film and peeling, and irradiating ultraviolet rays from the substrate side, A method of reducing the adhesive strength of the temporary fixing film and peeling it off may be used.

In the method of heating, foaming (or expanding) to peel off the temporary fixing film, the heating condition is usually 100 ° C. to 250 ° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. Also, by irradiating ultraviolet rays from the substrate side, in the method for peeling to lower the adhesive strength of the temporary fixing film, dose of the ultraviolet rays is ^{usually, 10mJ / cm 2 ~1000mJ / cm} 2.

<Step (E)>
Step (E) is a step of forming a rewiring formation layer (insulating layer) on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off.

  The material for forming the rewiring formation layer (insulating layer) is not particularly limited as long as it has an insulating property at the time of forming the rewiring forming layer (insulating layer). From the viewpoint of ease of manufacturing a semiconductor chip package, Photosensitive resins and thermosetting resins are preferred.

  After forming the rewiring formation layer (insulating layer), a via hole may be formed in the rewiring forming layer (insulating layer) in order to connect the semiconductor chip and a later-described conductor layer between layers.

  In forming a via hole, if the material forming the rewiring formation layer (insulating layer) is a photosensitive resin, first, the surface of the rewiring forming layer (insulating layer) is irradiated with active energy rays through a mask pattern, and is irradiated. The part of the outermost wiring layer is light-cured.

  Examples of the active energy ray include an ultraviolet ray, a visible ray, an electron beam, an X-ray, and the like, and an ultraviolet ray is particularly preferable. The irradiation amount and irradiation time of the ultraviolet ray can be appropriately changed according to the photosensitive resin. As the exposure method, there are a contact exposure method in which a mask pattern is brought into close contact with a rewiring formation layer (insulating layer) and exposure, and a light exposure using a parallel beam without bringing the mask pattern into close contact with the rewiring formation layer (insulating layer). Any of the non-contact exposure methods described above may be used.

  Next, a via hole is formed by developing the rewiring forming layer (insulating layer) and removing an unexposed portion. As the development, both wet development and dry development are suitable. As the developer used in the wet development, a known developer can be used.

  Examples of the development method include a dip method, a paddle method, a spray method, a brushing method, a scraping method, and the like, and a paddle method is preferable from the viewpoint of resolution.

  When the material for forming the rewiring formation layer (insulating layer) is a thermosetting resin, the formation of the via hole is not particularly limited, and includes laser irradiation, etching, mechanical drilling, and the like. preferable. Laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide laser, a UV-YAG laser, an excimer laser, or the like as a light source.

  The conditions for laser irradiation are not particularly limited, and the laser irradiation can be performed by any suitable process according to a conventional method according to the selected means.

  The shape of the via hole, that is, the shape of the contour of the opening when viewed in the extending direction is not particularly limited, but is generally circular (substantially circular). The top diameter of the via hole (the diameter of the opening on the surface of the rewiring formation layer (insulating layer)) is preferably 50 μm or less, more preferably 30 μm or less, and still more preferably 20 μm or less. The lower limit is not particularly limited, but is preferably 10 μm or more, more preferably 15 μm or more, and further preferably 20 μm 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 the conductor layer on the rewiring formation layer (insulating layer) is the same as the method of forming the conductor layer after forming the via holes in the insulating layer in step (3) of the circuit board manufacturing method, and is preferable. The same applies to the range. The steps (E) and (F) may be repeated to alternately build up (build up) the conductor layers (rewiring layers) and the rewiring formation layers (insulating layers).

<Step (G)>
Step (G) is a step of forming a solder resist layer on the conductor layer.

  The material for forming the solder resist layer is not particularly limited as long as it has an insulating property at the time of forming the solder resist layer. From the viewpoint of ease of manufacturing a semiconductor chip package, a photosensitive resin and a thermosetting resin are preferable. .

  In the step (G), bumping processing for forming a bump may be performed as necessary. The bumping process can be performed by a known method such as solder ball or solder plating. The formation of via holes in the bumping process can be performed in the same manner as in the step (E).

<Step (H)>
The method for manufacturing a semiconductor chip package may include a step (H) in addition to the steps (A) to (G). The step (H) is a step of dicing the plurality of semiconductor chip packages into individual semiconductor chip packages to singulate them.

  The method of dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited, and a known method can be used.

  In a third embodiment of the semiconductor chip package of the present invention, for example, a rewiring forming layer (insulating layer) 130 and a solder resist layer 150 in a semiconductor chip package (Fan-out type WLP) as shown in FIG. It is a semiconductor chip package manufactured with the paste-like resin composition of the present invention.

[Semiconductor device]
Examples of the semiconductor device on which the semiconductor chip package of the present invention is mounted include electric products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, and televisions) and vehicles ( For example, various semiconductor devices provided for motorcycles, automobiles, trains, ships, aircrafts, and the like) can be mentioned.

[Electronic materials]
The electronic member of the present invention has a heat sink, a cured product of the paste resin composition of the present invention provided on the heat sink, and an electronic component mounted on the cured product. Since the cured product of the paste-like resin composition has excellent thermal conductivity and adhesiveness, for example, the cured product of the paste-like resin composition is provided on a heat sink so as to adhere to the heat sink, and the electronic component is placed on the cured product. By mounting the electronic component, the heat radiation efficiency of the electronic component to the heat sink is increased. The method of forming the cured product can be performed in the same manner as in the step (C) described above.

  Examples of the electronic component include a semiconductor chip, a power semiconductor, and an LED-PKG. Examples of the electronic member include a circuit board, a semiconductor chip package, and a semiconductor device.

  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In the following description, “parts” and “%” representing amounts mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.

[Preparation of Paste Resin Composition]
<Example 1>
17 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type) and 17 parts of liquid dispersant (“ED152” manufactured by Kusumoto Chemicals) , An alkylene oxide-containing phosphoric acid ester) was added thereto, and the mixture was stirred uniformly using Awatori Neritaro manufactured by Shinky Corporation to obtain an epoxy resin composition. Next, 14 parts of a liquid curing agent (“TMTP” manufactured by Yodo Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional) and curing acceleration were added to the obtained epoxy resin composition. 0.14 parts of an agent ("TBP-DA", manufactured by Hokuko Chemical Co., Ltd., tetrabutylphosphonium decanoic acid) was added and stirred to prepare a base resin composition.
69 parts of a thermally conductive filler (spherical alumina powder, “DAW-0525” manufactured by Denka, average particle size 5.3 μm, specific surface area: 0.4 m ² / g, aspect ratio 1.0) was added to the base resin composition. The mixture was further kneaded to obtain a paste-like resin composition 1. The organic solvent content of the paste-form resin composition 1 was 0% by mass based on the total mass of the paste-form resin composition 1.

<Example 2>
In Example 1, the thermally conductive filler: the (spherical alumina powder, Denka Co. "DAW-0525", average particle diameter 5.3 .mu.m, specific surface area 0.4 m ² / g, an aspect ratio of 1.0) 69 parts, Thermal conductive filler (spherical silicon carbide powder, “SSC-A01” manufactured by Shinano Electric Smelting Co., Ltd., average particle size 1.4 μm, specific surface area: 5.0 m ² / g, aspect ratio 1.25) was changed to 64 parts. . Except for the above, a paste-like resin composition 2 was obtained in the same manner as in Example 1.

<Example 3>
In Example 1, the thermally conductive filler: the (spherical alumina powder, Denka Co. "DAW-0525", average particle diameter 5.3 .mu.m, specific surface area 0.4 m ² / g, an aspect ratio of 1.0) 69 parts, The heat conductive filler (spherical silicon carbide powder, “SSC-A15” manufactured by Shinano Electric Smelting Co., Ltd., average particle size 18.6 μm, specific surface area: 0.3 m ² / g, aspect ratio 1.25) was changed to 64 parts. . Except for the above, a paste-like resin composition 3 was obtained in the same manner as in Example 1.

<Example 4>
In Example 1, 69 parts of a thermally conductive filler (spherical alumina powder, “DAW-0525” manufactured by Denka Co., average particle size 5.3 μm, specific surface area: 0.4 m ² / g, aspect ratio 1.0) was used. Thermal conductive filler (Spherical aluminum nitride powder of “HF-01” manufactured by Tokuyama Co., Ltd., surface-treated with phenylaminosilane at Admatechs Co., Ltd., average particle size 0.9 μm to 1.4 μm, specific surface area: 2.3 m ² / g to 2.9 m ² / g, aspect ratio 1.0 to 1.1) 65 parts. Except for the above, a paste-like resin composition 4 was obtained in the same manner as in Example 1.

<Example 5>
3 parts of bisphenol-type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type), and 1,4-cyclohexanedimethanol diglycidyl ether type 3 parts of an epoxy resin (“ZX1658GS”, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent: 130-140 g / eq) is weighed in a metal container, and a tetramethylbiphenol-type solid epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy 1 part of an equivalent (187-197 g / eq) was weighed. Then, it melt | dissolved using the IH heater.
After cooling, 4 parts of a dispersant ("ED152" manufactured by Kusumoto Kasei Co., Ltd., alkylene oxide-containing phosphoric acid ester) was added, and the mixture was stirred uniformly to obtain an epoxy resin composition.
Next, 6 parts of a liquid curing agent (“TMTP” manufactured by Yodo Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional), and a curing accelerator are added to the obtained epoxy resin composition. 0.14 parts ("TBP-DA", manufactured by Hokuko Chemical Co., Ltd., tetrabutylphosphonium decanoic acid) was added and stirred to prepare a base resin composition.
Based thermally conductive filler in the resin composition (alumina powder, Denka Co. "ASFP-20", average particle diameter 0.2Myuemu～0.5Myuemu, specific surface ^{area: 12m 2 / g~18m 2 / g} , an aspect ratio of 1. 0) 13 parts, heat conductive filler (alumina powder, “DAW-0525” manufactured by Denka Co., Ltd., average particle size 5.3 μm, specific surface area: 0.4 m ² / g, aspect ratio 1.0) 19 parts, heat conduction 13 parts of a conductive filler (spherical silicon carbide powder, “SSC-A01” manufactured by Shinano Electric Smelting Co., Ltd., average particle size 1.4 μm, specific surface area: 5.0 m ² / g, aspect ratio 1.25), and thermal conductivity 38 parts of a filler (spherical silicon carbide powder, “SSC-A15” manufactured by Shinano Electric Smelting Co., Ltd., average particle size: 18.6 μm, specific surface area: 0.3 m ² / g, aspect ratio: 1.25) are added and stirred. Paste resin composition 5 was obtained .

<Example 6>
In Example 5,
1) The amount of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type) was changed from 3 parts to 4 parts,
2) The amount of the tetramethylbiphenol-type solid epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 187-197 g / eq) was changed from 1 part to 2 parts,
3) A liquid curing agent ("MEH-8000H" manufactured by Meiwa Kasei Co., Ltd.) was mixed with 6 parts of a liquid curing agent ("TMTP" manufactured by Yodo Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional). ), 2-allylphenol-formaldehyde polycondensate, OH equivalent 139-143 g / eq) to 8 parts,
4) The amount of the dispersant (“ED152” manufactured by Kusumoto Kasei Co., Ltd., alkylene oxide-containing phosphate ester) was changed from 4 parts to 1 part.
Except for the above, a paste-like resin composition 6 was obtained in the same manner as in Example 5.

<Example 7>
In Example 5, 4 parts of a dispersant (“ED152” manufactured by Kusumoto Kasei Co., Ltd., a phosphoric acid ester containing an alkylene oxide) was added to a dispersant (“Plenact 55” manufactured by Ajinomoto Fine-Techno Co., Ltd.), a titanate coupling agent, (tetra (2 , 2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate)). Except for the above, a paste-like resin composition 7 was obtained in the same manner as in Example 5.

<Example 8>
In Example 5, a thermally conductive filler (spherical silicon carbide powder, “SSC-A01” manufactured by Shinano Electric Smelting Co., Ltd., average particle size 1.4 μm, specific surface area: 5.0 m ² / g, aspect ratio 1.25) Thirteen parts were obtained by subjecting spherical aluminum nitride powder of a thermally conductive filler ("HF-01" manufactured by Tokuyama Corporation) to surface treatment with phenylaminosilane at Admatechs Co., Ltd., average particle diameter 0.9 μm to 1.4 μm, specific surface area: 2 .3m ² /g~2.9m ² / g, it was changed to the aspect ratio 1.0 to 1.1) 13 parts. Except for the above, a paste-like resin composition 8 was obtained in the same manner as in Example 5.

<Example 9>
In Example 5, the thermally conductive filler (spherical silicon carbide powder, Shinano Electric smelting Co. "SSC-A01", average particle size 1.4 [mu] m, specific surface area: 5.0 m ² / g, the aspect ratio 1.25) 13 parts of a thermally conductive filler (boron nitride powder, “MBN-010T” manufactured by Mitsui Chemicals, Inc., average particle size 0.9 μm to 1.0 μm, specific surface area: 13.0 m ² / g, aspect ratio 5.0) Changed to 13 parts. Except for the above, a paste-like resin composition 9 was obtained in the same manner as in Example 5.

<Example 10>
2 parts of bisphenol-type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type), and 1,4-cyclohexanedimethanol diglycidyl ether type Two parts of an epoxy resin (“ZX1658GS”, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent: 130-140 g / eq) are weighed in a metal container, and a tetramethylbiphenol-type solid epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy 1 part of an equivalent (187-197 g / eq) was weighed. Then, it melt | dissolved using the IH heater.
After cooling, 3 parts of a dispersant ("ED152" manufactured by Kusumoto Kasei Co., Ltd., phosphoric acid ester containing alkylene oxide) was added, and the mixture was stirred uniformly to obtain an epoxy resin composition.
Next, 4 parts of a liquid curing agent (“TMTP” manufactured by Yodo Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional), and a curing accelerator are added to the obtained epoxy resin composition. (TBP-DA, manufactured by Hokuko Chemical Co., Ltd., tetrabutylphosphonium decanoic acid) (0.09 part) was added and stirred to prepare a base resin composition.
Based thermally conductive filler in the resin composition (alumina powder, Denka Co. "ASFP-20", average particle diameter 0.2Myuemu～0.5Myuemu, specific surface ^{area: 12m 2 / g~18m 2 / g} , an aspect ratio of 1. 0) 14 parts, 19 parts of heat conductive filler (alumina powder, “DAW-0525” manufactured by Denka Co., average particle size 5.3 μm, specific surface area: 0.4 m ² / g, aspect ratio 1.0), heat conduction 14 parts of conductive filler (spherical silicon carbide powder, “SSC-A01” manufactured by Shinano Electric Smelting Co., Ltd., average particle size 1.4 μm, specific surface area: 5.0 m ² / g, aspect ratio 1.25), and thermal conductivity 41 parts of a filler (spherical silicon carbide powder, “SSC-A15” manufactured by Shinano Electric Smelting Co., Ltd., average particle size: 18.6 μm, specific surface area: 0.3 m ² / g, aspect ratio: 1.25) are added and stirred. Paste resin composition 10 It was.

<Example 11>
In Example 10, a thermally conductive filler (spherical silicon carbide powder, “SSC-A15” manufactured by Shinano Electric Smelting Co., Ltd., average particle size: 18.6 μm, specific surface area: 0.3 m ² / g, aspect ratio: 1.25) 41 parts of a thermally conductive filler (spherical silicon carbide powder, “SSC-A30” manufactured by Shinano Electric Smelting Co., Ltd., average particle diameter 34.4 μm, specific surface area: 0.1 m ² / g, aspect ratio 1.25) 41 Changed to the department. Except for the above, a paste-like resin composition 11 was obtained in the same manner as in Example 10.

<Example 12>
In Example 11, 4 parts of a liquid curing agent ("TMTP" manufactured by Yodo Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional) was added to a liquid curing agent (manufactured by Showa Denko KK). PE-1 ", 4 parts of pentaerythritol tetrakis (3-mercaptobutyrate). Except for the above, a paste-like resin composition 12 was obtained in the same manner as in Example 11.

<Example 13>
In Example 12, the amount of the liquid curing agent ("PE-1" manufactured by Showa Denko KK, pentaerythritol tetrakis (3-mercaptobutyrate)) was changed from 4 parts to 3 parts, and the liquid curing agent (manufactured by Meiwa Kasei Co., Ltd.) "MEH-8000H", 1 part of 2-allylphenol-formaldehyde polycondensate, OH equivalent 139-143 g / eq) were added. Except for the above, a paste-like resin composition 13 was obtained in the same manner as in Example 12.

<Comparative Example 1>
In Example 5,
1) The amount of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type) was changed from 3 parts to 4 parts,
2) 6 parts of a liquid curing agent (“TMTP” manufactured by Yodo Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional) was added to a solid curing agent (phenol novolak resin, Aika SDK Phenol). "BRG-557", OH equivalent 103-107 g / eq)
3) The amount of the curing accelerator ("TBP-DA" manufactured by Hokuko Chemical Co., Ltd., tetrabutylphosphonium decanoic acid) was changed from 0.14 part to 0.16 part.
Except for the above, a paste-like resin composition 11 was obtained in the same manner as in Example 5.

<Comparative Example 2>
In Example 5,
1) The amount of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type) was changed from 3 parts to 4 parts,
2) The amount of 1,4-cyclohexane dimethanol diglycidyl ether type epoxy resin (“ZX1658GS”, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 130-140 g / eq) was changed from 3 parts to 4 parts,
3) The amount of the tetramethyl biphenol type solid epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 187-197 g / eq) was changed from 1 part to 2 parts,
4) The amount of the liquid curing agent (“TMTP” manufactured by Yodo Chemical Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional) was changed from 6 parts to 8 parts,
5) The amount of the curing accelerator ("TBP-DA" manufactured by Hokuko Chemical Co., Ltd., tetrabutylphosphonium decanoic acid) was changed from 0.14 part to 0.19 part,
6) No dispersant ("ED152" manufactured by Kusumoto Chemicals, a phosphate ester containing alkylene oxide) was added.
Except for the above, a paste-like resin composition 12 was obtained in the same manner as in Example 5.

[Measurement of viscosity]
The temperature of the paste-like resin composition of each Example and each Comparative Example was kept at 25 ± 2 ° C., and an E-type viscometer (“RE-80U” manufactured by Toki Sangyo Co., Ltd., 1 ° 34 ′ × R24 cone, rotation speed was 1 rpm).

[Measurement of thermal conductivity]
Each of the paste-like resin compositions of Examples 1 to 4 was placed in a predetermined container, and thermally cured in a heat-circulating oven at 120 ° C. for 60 minutes to produce a cylindrical cured product having a thickness of 10 mm and a diameter of 36 mm. The thermal conductivity of the obtained cylindrical cured product was measured by a hot disk method using “TPS-2500” manufactured by Kyoto Electronics Manufacturing Co., Ltd. in a constant temperature environment of a measurement temperature of 25 ° C. and 40% RH.
The conditions for thermally curing the paste-like resin compositions of Examples 5, 7 to 10 and Comparative Example 2 in a heat-circulating oven were from 120 ° C. for 60 minutes to 150 ° C. for 60 minutes. Except for the above, the thermal conductivity was measured in the same manner as in Example 1.
The paste resin compositions of Example 6 and Comparative Example 1 were heat-cured in a heat-circulating oven from 120 ° C. for 60 minutes to 150 ° C. for 60 minutes, and then to 180 ° C. for 60 minutes. Except for the above, the thermal conductivity was measured in the same manner as in Example 1.

[Measurement of adhesion]
A paste-like resin composition was applied on a nickel-plated substrate, and a capacitor chip was mounted thereon. The paste-like resin composition protruding from the capacitor chip was removed so that the bonded area of the capacitor chip became 1.2 mm × 2.0 mm, and a test piece was obtained.
Next, the paste-like 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 Example 1 were 150 ° C. for 60 minutes. After curing, the temperature was further set to 180 ° C. for 60 minutes.
Die shear strength of a paste-like resin composition cured by scratching a capacitor chip on a cured paste-like resin composition at a speed of 200 μm / s in an environment of 25 ° C. using a Daiji Series 4000 Was measured. This operation was performed three times and the average value was obtained. The adhesion was evaluated according to the following criteria.
◎: Die shear strength is 20N or more ○: Die shear strength is 10N or more and less than 20N △: Die shear strength is less than 10N

The components used in the preparation of the paste-like resin compositions 1 to 12 and the amounts thereof (parts by mass of non-volatile components) are shown in the following table. The abbreviations and the like in the table below are as follows.
Content of component (C) (% by mass): Content of component (C) when nonvolatile component in paste-form resin composition is 100% by mass Content of component (C) (% by volume): Paste-like Content of component (C) when non-volatile component in resin composition is 100% by volume

It can be seen that Examples 1 to 13 have low viscosity and high thermal conductivity. Further, it can be seen that each of the examples is excellent in adhesion because of high die shear strength.
On the other hand, Comparative Example 1 not containing the component (B) and Comparative Example 2 not containing the component (D) have a viscosity exceeding 1000 Pa · s, and can be applied to a metal foil such as a copper foil or an aluminum foil. It could not be used as a paste-like resin composition.

  In Examples 1 to 13, it was confirmed that even when the component (E) was not contained, the results were similar to those in the above examples, although the degree was different.

Claims (16)

(A) epoxy resin,
(B) a liquid curing agent,
A paste-like resin composition containing (C) a thermally conductive filler, and (D) a dispersant.   The paste-like resin composition according to claim 1, wherein the content of the organic solvent contained in the paste-like resin composition is less than 1.0% by mass based on the total mass of the paste-like resin composition.   The paste-like resin composition according to claim 1 or 2, wherein the cured product of the paste-like resin composition has a thermal conductivity of 2.0 W / mK or more.   The paste resin composition according to any one of claims 1 to 3, wherein the component (D) contains an oxyalkylene-containing phosphate.   The paste resin composition according to any one of claims 1 to 4, wherein the component (C) includes at least one selected from silicon carbide, boron nitride, aluminum nitride, and aluminum oxide.   The paste resin composition according to any one of claims 1 to 5, wherein the component (C) includes silicon carbide.   The paste-like resin composition according to claim 6, wherein the average particle size of the silicon carbide is 1 µm or more and 30 µm or less.   The paste-like resin composition according to claim 6, wherein the component (C) further contains at least one selected from boron nitride, aluminum nitride, and aluminum oxide.   The content of the component (C) is 60% by mass or more and 95% by mass or less when the nonvolatile component in the paste-like resin composition is 100% by mass, according to any one of claims 1 to 8. Paste resin composition.   The paste resin composition according to any one of claims 1 to 9, wherein the component (B) includes at least one selected from a polythiol compound and a liquid phenol resin.   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, octyl thioglycolate, 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-mercaptobutyryloxy) (Siethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethanetris (3-mercaptobutyrate), One or more polythiol compounds selected from 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril and 4,4′-isopropylidenebis [(3-mercaptopropoxy) benzene], and an alkenyl group-containing novolak The paste-like resin composition according to any one of claims 1 to 10, comprising at least one selected from liquid phenolic resins selected from type phenolic resins.   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.   A circuit board comprising an insulating layer formed from a cured product of the pasty resin composition according to claim 1.   A semiconductor chip package comprising the circuit board according to claim 13 and a semiconductor chip mounted on the circuit board.   A semiconductor chip package including a semiconductor chip sealed with the paste-like resin composition according to claim 1.   An electronic member comprising: a heat sink; a cured product of the paste-like resin composition according to claim 1 provided on the heat sink; and an electronic component mounted on the cured product.

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