JP7413678B2 - resin composition - Google Patents

Description

The present invention relates to a resin composition containing an epoxy resin. Furthermore, the present invention relates to a cured product, a resin sheet, a circuit board, a semiconductor chip package, and a semiconductor device obtained using the resin composition.

In recent years, the demand for small, high-performance electronic devices such as smartphones and tablet devices has increased, and along with this, the encapsulating materials for semiconductor chip packages used in these small electronic devices are also required to have even higher functionality. ing. As such a sealing material, one formed by curing a resin composition is known (Patent Document 1).

Furthermore, epoxy resin compositions using thiol curing agents have been known (Patent Documents 2 and 3).

Japanese Patent Application Publication No. 2017-008312 Japanese Patent Application Publication No. 2013-129775 Japanese Patent Application Publication No. 2013-253194

Particularly in recent years, there has been a demand for encapsulating materials used in semiconductor chip packages that can be encapsulated at low temperatures in order to improve manufacturing efficiency. Furthermore, from the viewpoint of package reliability, the sealing material is required to have high copper adhesion. Therefore, an object of the present invention is to provide a resin composition from which a cured product having excellent low-temperature moldability and copper adhesion can be obtained.

In order to achieve the objects of the present invention, the present inventors have made extensive studies and found that by using a resin composition that contains a thiol-based curing agent and satisfies predetermined conditions, curing with excellent low-temperature moldability and copper adhesion can be achieved. The inventors have discovered that it is possible to obtain a product, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition comprising (A) an epoxy resin, (B) an inorganic filler, (C) a thiol curing agent, and (D) a curing accelerator,
The content of component (B) is 70% by mass or more when the nonvolatile components in the resin composition are 100% by mass,
A resin composition in which the component (D) contains at least one selected from the group consisting of a phosphorus-based curing accelerator, a urea-based curing accelerator, a guanidine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator. .
[2] The resin composition according to [1] above, wherein component (D) contains at least one selected from the group consisting of a phosphorus-based curing accelerator, an imidazole-based curing accelerator, and a urea-based curing accelerator.
[3] The resin composition according to [1] or [2] above, which has a reaction initiation temperature of 70° C. or higher based on differential scanning calorimetry.
[4] The resin composition according to any one of [1] to [3] above, which has a reaction peak temperature of 130° C. or lower based on differential scanning calorimetry.
[5] The resin composition according to any one of [1] to [4] above, wherein component (A) contains a glycidylamine type epoxy resin.
[6] The resin according to any one of [1] to [5] above, wherein the content of component (B) is 80% by mass or more when the nonvolatile components in the resin composition are 100% by mass. Composition.
[7] Component (C) is a hydrocarbon type thiol type hardening agent, an ether type thiol type hardening agent, a thioether type thiol type hardening agent, an amine type thiol type hardening agent, an alcohol type thiol type hardening agent, an alkyl isocyanurate type thiol The resin composition according to any one of [1] to [6] above, which is at least one selected from the group consisting of an alkyl glycoluril type curing agent and an alkyl glycoluril type thiol type curing agent.
[8] The resin composition according to any one of [1] to [7] above, wherein component (C) contains a thiol curing agent that is liquid at 25°C.
[9] The resin composition according to any one of [1] to [8] above, wherein the imidazole curing accelerator has a molecular weight of 1,000 or less.
[10] A resin composition comprising (A) an epoxy resin, (B) an inorganic filler, (C) a thiol curing agent, and (D) a curing accelerator,
The content of component (B) is 70% by mass or more when the nonvolatile components in the resin composition are 100% by mass,
The reaction initiation temperature based on differential scanning calorimetry is 70°C or higher,
A resin composition having a reaction peak temperature of 130°C or less based on differential scanning calorimetry.
[11] The resin composition according to any one of [1] to [10] above, wherein the cured product of the resin composition has a glass transition temperature (Tg) of 80° C. or higher.
[12] The resin composition according to any one of [1] to [11] above, for forming an insulating layer of a semiconductor chip package.
[13] The resin composition according to any one of [1] to [11] above, for forming an insulating layer of a circuit board.
[14] The resin composition according to any one of [1] to [11] above for sealing a semiconductor chip of a semiconductor chip package.
[15] A cured product of the resin composition according to any one of [1] to [14] above.
[16] A resin sheet comprising a support and a resin composition layer containing the resin composition according to any one of [1] to [14] above, provided on the support.
[17] A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [14] above.
[18] A semiconductor chip package including the circuit board according to [17] above and a semiconductor chip mounted on the circuit board.
[19] A semiconductor chip package comprising a semiconductor chip and a cured product of the resin composition according to any one of [1] to [14] above, which seals the semiconductor chip.
[20] A semiconductor device comprising the semiconductor chip package according to [18] or [19] above.

According to the present invention, it is possible to provide a resin composition from which a cured product with excellent low-temperature moldability and copper adhesion can be obtained. In particular, it is possible to provide a resin composition that can yield a cured product with excellent copper adhesion against tension in the vertical direction.

Hereinafter, the present invention will be explained in detail based on its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and may be implemented with arbitrary changes within the scope of the claims of the present invention and equivalents thereof.

<Resin composition>
The resin composition of the present invention includes (A) an epoxy resin, (B) an inorganic filler, (C) a thiol curing agent, and (D) a curing accelerator, and the content of the (B) component is determined in the resin composition. When the nonvolatile components in the product are 100% by mass, it is 70% by mass or more, and further falls under either the first embodiment or the second embodiment below.

In the first embodiment, component (D) is selected from the group consisting of a phosphorus-based curing accelerator, a urea-based curing accelerator, a guanidine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator. Contains at least one species. In the second embodiment, the reaction initiation temperature of the resin composition based on differential scanning calorimetry is 70°C or higher and the reaction peak temperature is 130°C or lower, and as long as the reaction initiation temperature and the reaction peak temperature are within the above ranges. Component (D) is not limited. It is known that the reaction initiation temperature and reaction peak temperature based on differential scanning calorimetry can be easily adjusted by those skilled in the art by adjusting the components of the resin composition and their contents.

A cured product of such a resin composition has excellent low-temperature moldability and copper adhesion. In particular, it has excellent adhesion to copper against tension in the vertical direction. Further, a cured product of such a resin composition preferably has excellent storage stability and/or heat resistance.

In addition to (A) an epoxy resin, (B) an inorganic filler, (C) a thiol curing agent, and (D) a curing accelerator, the resin composition of the present invention further contains (E) other additives, and (F) It may contain an organic solvent. Each component contained in the resin composition will be explained in detail below.

<(A) Epoxy resin>
The resin composition of the present invention includes (A) an epoxy resin. (A) Epoxy resin means a resin having an epoxy group.

(A) Epoxy resins include, 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, and trisphenol type epoxy resin. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac 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 novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane Examples include dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, and isocyanurate type epoxy resin. (A) The epoxy resin preferably contains a glycidylamine type epoxy resin from the viewpoint of further improving the heat resistance and copper adhesion of the cured product. (A) Epoxy resins may be used alone or in combination of two or more.

It is preferable that the resin composition contains, as the epoxy resin (A), an epoxy resin having two or more epoxy groups in one molecule. (A) The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably is 70% by mass or more.

Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). ). The resin composition of the present invention may contain only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin. However, it is preferable that only liquid epoxy resin is included.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

Liquid epoxy resins include 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, and ester skeleton. Preferred are alicyclic epoxy resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, and epoxy resins having a butadiene structure.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "828EL", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation. ", "Epicote 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical; Mitsubishi Chemical's "630", "630LSD", "604" (glycidylamine type epoxy resin); ADEKA's "ED-523T" (glycyol type epoxy resin); ADEKA's "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (bisphenol A type epoxy resin and bisphenol F type epoxy resin); mixture of epoxy resins); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel; "PB-3600", Nippon Soda Co., Ltd.'s "JP-100", "JP-200" (epoxy resin with butadiene structure); Nippon Steel & Sumikin Chemical Co., Ltd.'s "ZX1658", "ZX1658GS" (liquid 1,4- glycidylcyclohexane type epoxy resin), etc. These may be used alone or in combination of two or more.

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.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl. Preferred examples include a type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, and a tetraphenylethane type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; “N-690” (cresol novolak type epoxy resin) manufactured by DIC; “N-695” (cresol novolac type epoxy resin) manufactured by DIC; “HP-7200”, “HP-7200HH”, “HP” manufactured by DIC -7200H" (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" ( naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical; "ESN485" (naphthol novolac) manufactured by Nippon Steel & Sumikin Chemical type epoxy resin); “YX4000H”, “YX4000”, “YL6121” manufactured by Mitsubishi Chemical Company (biphenyl type epoxy resin); “YX4000HK” manufactured by Mitsubishi Chemical Company (bixylenol type epoxy resin); manufactured by Mitsubishi Chemical Company “ "YX8800" (anthracene type epoxy resin); "YX7700" (xylene structure-containing novolac type epoxy resin) manufactured by Mitsubishi Chemical; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical; "YL7760" (bisphenol AF type epoxy resin); "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; jER1031S" (tetraphenylethane type epoxy resin). These may be used alone or in combination of two or more.

(A) The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ～5,000g/eq. , more preferably 50g/eq. ～2,000g/eq. , more preferably 80g/eq. ～1,000g/eq. , even more preferably 80 g/eq. ～500g/eq. It is. Epoxy equivalent is the mass of resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin (A) is preferably 100 to 5,000, more preferably 200 to 3,000, even more preferably 250 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

The content of the epoxy resin (A) is not particularly limited, but is preferably 10% by mass or more, more preferably The content is 20% by mass or more, more preferably 30% by mass or more, particularly preferably 40% by mass or more. (A) The upper limit of the content of the epoxy resin is not particularly limited, but is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less, particularly preferably 80% by mass. It is as follows.

<(B) Inorganic filler>
The resin composition of the present invention contains (B) an inorganic filler.

(B) The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate , titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, among which silica and alumina are particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as the silica, spherical silica is preferable. (B) The inorganic fillers may be used alone or in combination of two or more.

(B) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Kagaku Kogyo Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials; “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C”; “UFP-30” manufactured by Denka; “Silfill NSS-3N”, “Silfill NSS-4N”, “Silfill NSS-” manufactured by Tokuyama Examples include "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatex; "DAW-03" and "FB-105FD" manufactured by Denka.

(B) The average particle size of the inorganic filler is not particularly limited, but is preferably 40 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less, even more preferably 15 μm or less, particularly preferably 10 μm or less. It is. The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.5 μm or more, even more preferably 1 μm or more, and More preferably, it is 3 μm or more, particularly preferably 5 μm or more. The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, it can be measured by creating the particle size distribution of the inorganic filler on a volume basis using a laser diffraction scattering type particle size distribution measuring device, and using the median diameter as the average particle size. The measurement sample can be obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them using ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction particle size distribution measuring device using a light source wavelength of blue and red, and the volume-based particle size distribution of the inorganic filler was measured using a flow cell method. The average particle size was calculated as the median diameter. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

(B) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.01 m ² /g or more, more preferably 0.1 m ² /g or more, particularly preferably 0.2 m ² /g. That's all. Although there is no particular restriction on the upper limit, it is preferably 50 m ² /g or less, more preferably 20 m ² /g or less, 10 m ² /g or less, or 5 m ² /g or less. The specific surface area of the inorganic filler is determined by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multipoint method. You can get it by doing that.

(B) Inorganic fillers include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, titanate coupling agents, from the viewpoint of improving moisture resistance and dispersibility. Preferably, the surface treatment agent is treated with one or more surface treatment agents such as a surface treatment 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. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Kagaku Kogyo, "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical, "SZ-31" manufactured by Shin-Etsu Chemical ( hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical, "KBM-4803" (long chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical, "KBM-" manufactured by Shin-Etsu Chemical 7103" (3,3,3-trifluoropropyltrimethoxysilane), "KBM503" (3-methacryloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical, and "KBM5783" manufactured by Shin-Etsu Chemical.

The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% by mass to 5% by mass, and preferably 0.2% by mass to 3% by mass. The surface treatment is preferably from 0.3% by mass to 2% by mass.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in sheet form, the amount is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and 0.5 mg/m ² The following are more preferred.

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

(B) The content of the inorganic filler is 70% by mass or more, preferably 75% by mass or more, when all nonvolatile components in the resin composition are 100% by mass, which further improves heat resistance. From this point of view, the content is more preferably 80% by mass or more, particularly preferably 83% by mass or more. (B) The upper limit of the content of the inorganic filler is not particularly limited, but may be, for example, 98% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less.

<(C) Thiol curing agent>
The resin composition of the present invention contains (C) a thiol-based curing agent.

(C) Thiol curing agent means a thiol compound capable of curing the epoxy resin (A), and is usually a difunctional or higher functional thiol compound, and from the viewpoint of further improving the crosslinking density, a trifunctional or higher functional thiol compound. It is preferable that it is a thiol compound. Moreover, such a thiol compound is preferably a primary and/or secondary thiol compound, and from the viewpoint of increasing reactivity, a primary thiol compound is more preferable.

(C) Examples of the thiol curing agent include hydrocarbon type thiol curing agent, ether type thiol curing agent, thioether type thiol curing agent, amine type thiol curing agent, alcohol type thiol curing agent, carboxylic acid type curing agent Examples include ester-type thiol-based hardeners, alkyl isocyanurate-type thiol-based hardeners, carboxylic acid ester isocyanurate-type thiol-based hardeners, and alkyl glycoluril-type thiol-based hardeners. Among these, from the viewpoint of further improving heat resistance, thiol-based curing agents that do not contain a carboxylic acid ester structure, such as hydrocarbon-type thiol-based curing agents, ether-type thiol-based curing agents, thioether-type thiol-based curing agents, and amine-type thiols. Preferred are alcohol-type thiol-based hardeners, alcohol-type thiol-based hardeners, alkyl isocyanurate-type thiol-based hardeners, and alkyl glycoluril-type thiol-based hardeners, and particularly preferred are ether-type thiol-based hardeners and alkyl isocyanurate-type thiol-based hardeners.

Hydrocarbon-type thiol curing agent means a compound in which two or more hydrogen atoms bonded to the same or different non-aromatic carbon atoms of a hydrocarbon are substituted with mercapto groups, such as 1,4-butanedithiol. , 1,6-hexanedithiol, 1,8-octanedithiol, 1,10-decanedithiol, 2,2-dimethylpropane-1,3-dithiol, 1,4-cyclohexanedithiol, 1,2-cyclohexanedithiol, p - Bifunctional hydrocarbon type thiol curing agent such as xylene-α,α'-dithiol; 2-mercaptomethyl-1,3-propanedithiol, 2-ethyl-2-(mercaptomethyl)-1,3-propane Trifunctional hydrocarbon type thiol curing agents such as dithiol, 2-mercaptomethyl-1,4-butanedithiol, 1,2,3-propane trithiol; tetrakis(mercaptomethyl)methane, 2,2-bis(mercaptomethyl) Examples include tetrafunctional hydrocarbon type thiol curing agents such as methyl)-1,3-propanedithiol.

An ether type thiol curing agent is one in which two or more hydrogen atoms bonded to the same or different non-aromatic carbon atoms of a hydrocarbon are substituted with a mercapto group, and one or more CH ₂ (secondary means a compound in which carbon) is replaced with O, such as 3,6-dioxa-1,8-octanedithiol, 3,4-dimethoxybutane-1,2-dithiol, 2,3-dimercaptopropyl methyl ether, Bifunctional ether-type thiol curing agents such as bis(2-mercaptoethyl) ether; (2-mercaptoethyl)(2,3-dimercaptopropyl)ether, trimethylolpropane tris(2-mercaptoethyl)ether, trimethylolpropane; Methylolethane tris(2-mercaptoethyl) ether, trimethylolpropane tris(3-mercaptopropyl) ether, trimethylolethane tris(3-mercaptopropyl) ether, trimethylolpropane tris(4-mercaptobutyl) ether, trimethylolethane Tris(4-mercaptobutyl) ether, glycerin tris(3-mercaptopropyl) ether, glycerin tris(4-mercaptobutyl) ether, trimethylolpropane tris(2-mercaptopropyl) ether, trimethylolethane tris(2-mercaptopropyl) ) ether, trimethylolpropane tris(3-mercaptobutyl) ether, trimethylolethane tris(3-mercaptobutyl) ether, glycerin tris(2-mercaptopropyl) ether, glycerin tris(3-mercaptobutyl) ether, etc. Ether type thiol curing agent; bis(2,3-dimercaptopropyl) ether, pentaerythritol tetrakis (2-mercaptoethyl) ether, pentaerythritol tetrakis (3-mercaptopropyl) ether, pentaerythritol tetrakis (4-mercaptobutyl) ) ether, tetrafunctional ether type thiol curing agents such as pentaerythritol tetrakis (2-mercaptopropyl) ether, pentaerythritol tetrakis (3-mercaptobutyl) ether; dipentaerythritol hexakis (3-mercaptopropyl) ether, dipentaerythritol hexakis (3-mercaptopropyl) ether, Examples include pentaerythritol hexakis(2-mercaptopropyl) ether and other polyfunctional ether-type thiol curing agents having five or more functional groups.

A thioether type thiol curing agent is one in which two or more hydrogen atoms bonded to the same or different non-aromatic carbon atoms of a hydrocarbon are substituted with a mercapto group, and one or more CH ₂ (secondary It refers to a compound in which carbon) is replaced with S, and one or more CH ₂ (secondary carbon) in the molecule may be replaced with O, for example, 3,6-dithia-1,8-octane. Examples include difunctional thioether type thiol curing agents such as dithiol.

An amine-type thiol curing agent is one in which two or more hydrogen atoms bonded to the same or different non-aromatic carbon atoms of a hydrocarbon are substituted with a mercapto group, and one or more CH ₂ (secondary refers to a compound in which carbon) and/or CH (tertiary carbon) is replaced with NH and/or N, and in which _CH2 (secondary carbon) at one or more locations within the molecule is replaced with O and/or S. For example, bis[4-(3-phenoxy-2-mercaptopropylamino)phenyl]methane, bis{4-[3-(4-methylphenoxy)-2-mercaptopropylamino]phenyl}methane, Examples include difunctional amine type thiol curing agents such as 1,4-bis(3-phenoxy-2-mercaptopropylamino)benzene.

An alcohol-type thiol curing agent refers to a compound in which two or more hydrogen atoms bonded to the same or different non-aromatic carbon atoms of a hydrocarbon are substituted with a mercapto group, and one or more hydrogen atoms are substituted with a hydroxy group. , further, one or more CH ₂ (secondary carbon) in the molecule becomes O and/or S, and one or more CH ₂ (secondary carbon) and/or CH (tertiary carbon) becomes NH and / or may be substituted with N, for example, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 2,2-bis(mercaptomethyl)-1,3-propanediol, etc. Bifunctional alcohol type thiol curing agent; trifunctional alcohol type thiol curing agent such as pentaerythritol tris(3-mercaptopropyl)ether, 3-mercapto-2,2-bis(mercaptomethyl)-1-propanol, etc. can be mentioned.

A carboxylic acid ester type thiol curing agent is one in which two or more hydrogen atoms bonded to the same or different non-aromatic carbon atoms of a hydrocarbon are substituted with a mercapto group, and at least one CH ₂ ( Refers to a compound in which CH 2 (secondary carbon) is replaced with C(=O)-O, and one or more CH ₂ (secondary carbon) in the molecule is replaced with O and/or S, and one or more CH 2 (secondary carbon) is replaced with O and/or S. ₂ (secondary carbon) and/or CH (tertiary carbon) may be replaced with NH and/or N, for example, bis(2-mercaptoethyl) succinate, bis(2-mercaptoethyl phthalate). ), bis(3-mercaptopropyl) phthalate, bis(4-mercaptobutyl) phthalate, ethylene glycol bis(mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(4-mercapto) butyrate), propylene glycol bis(3-mercaptopropionate), propylene glycol bis(4-mercaptobutyrate), diethylene glycol bis(3-mercaptopropionate), diethylene glycol bis(4-mercaptobutyrate), tetraethylene Glycol bis(3-mercaptopropionate), 1,4-butanediol bis(mercaptoacetate), 1,4-butanediol bis(3-mercaptopropionate), 1,4-butanediol bis(4- mercaptobutyrate), 1,8-octanediol bis(3-mercaptopropionate), 1,8-octanediol bis(4-mercaptobutyrate), bis(1-mercaptoethyl) phthalate, bis phthalate ( 2-mercaptopropyl), bis(3-mercaptobutyl) phthalate, ethylene glycol bis(2-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(2-mercaptopropionate) , propylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(2-mercaptopropionate), diethylene glycol bis(3-mercaptobutyrate), tetraethylene glycol bis(2-mercaptopropionate), 1,4- Butanediol bis(2-mercaptopropionate), 1,4-butanediol bis(3-mercaptobutyrate), 1,8-octanediol bis(2-mercaptopropionate), 1,8-octanediol bis Bifunctional carboxylic acid ester type thiol curing agent such as (3-mercaptobutyrate); bis(2-mercaptoethyl) thiomalate, trimethylolpropane tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate) , trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptopropionate), trimethylolpropane tris (4-mercaptobutyrate), trimethylolethane tris (4-mercaptobutyrate) , glycerin tris (3-mercaptopropionate), glycerin tris (4-mercaptobutyrate), trimethylolpropane tris (2-mercaptopropionate), trimethylolethane tris (2-mercaptopropionate), trimethylol Trifunctional carboxylic acid esters such as propane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), glycerin tris (2-mercaptopropionate), and glycerin tris (3-mercaptobutyrate) type thiol curing agent; 2,3-dimercaptosuccinate bis(2-mercaptoethyl), pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (4-mercapto tetrafunctional carboxylic acid ester type thiol curing agents such as pentaerythritol tetrakis (2-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate); dipentaerythritol hexakis (3-mercaptopropionate); Examples include polyfunctional carboxylic acid ester type thiol-based curing agents having five or more functional groups, such as dipentaerythritol hexakis (2-mercaptopropionate) and dipentaerythritol hexakis (2-mercaptopropionate).

The alkyl isocyanurate type thiol curing agent refers to the nitrogen atoms at the 1, 3, and 5 positions of isocyanuric acid (i.e., 1,3,5-triazine-2,4,6(1H,3H,5H)-trione). Refers to a compound in which an alkyl group is bonded and has two or more mercapto groups, such as tris(3-mercaptopropyl)isocyanurate, tris(2-mercaptopropyl)isocyanurate, tris(2-mercaptoethyl)isocyanurate Examples include trifunctional alkyl isocyanurate type thiol curing agents such as.

A carboxylic acid ester isocyanurate type thiol curing agent is one in which an alkyl group is bonded to each of the 1st, 3rd, and 5th positions of isocyanuric acid, has two or more mercapto groups, and has at least one mercapto group in the alkyl group. It means a compound in which CH ₂ (secondary carbon) is replaced with C(=O)-O, such as tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tris[2-(4-mercaptopropionyloxy)ethyl] Trifunctional carboxylic acid ester isocyanurate such as butyryloxy)ethyl]isocyanurate, tris[2-(2-mercaptopropionyloxy)ethyl]isocyanurate, tris[2-(3-mercaptobutyryloxy)ethyl]isocyanurate, etc. Examples include nurate type thiol curing agents.

The alkyl glycoluril type thiol curing agent refers to the 1, 3, 4, 6, 3a, and 6a positions of glycoluril (i.e., tetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione). It refers to a compound having an alkyl group bonded to at least one of them and two or more mercapto groups, such as 1,3-bis(2-mercaptoethyl)glycoluril, 1,3-bis(3-mercapto propyl) glycoluril, 1,4-bis(2-mercaptoethyl) glycoluril, 1,4-bis(3-mercaptopropyl) glycoluril, 1,6-bis(2-mercaptoethyl) glycoluril, 1,6 - Bifunctional alkyl glycoluril type thiol curing agent such as bis(3-mercaptopropyl) glycoluril; 1,3,4-tris(2-mercaptoethyl) glycoluril, 1,3,4-tris(3- trifunctional alkyl glycoluril type thiol curing agent such as 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril; Examples include tetrafunctional alkyl glycoluril type thiol curing agents such as propyl glycoluril.

(C) The thiol-based curing agent preferably contains a thiol-based curing agent that is liquid at 25°C.

The molecular weight of the thiol curing agent (C) is not particularly limited, but is preferably 200 or more, more preferably 250 or more, even more preferably 300 or more, particularly preferably 350 or more. (C) The upper limit of the molecular weight of the thiol curing agent is not particularly limited, but is preferably 1,500 or less, more preferably 1,000 or less, even more preferably 800 or less, particularly preferably 700 or less. .

The thiol equivalent of the thiol curing agent (C) is not particularly limited, but is preferably 50 to 1,000 g/eq. , more preferably 50 to 500 g/eq. , more preferably 50 to 300 g/eq. , particularly preferably 50 to 200 g/eq. It is. The thiol equivalent is the mass of the thiol curing agent per equivalent of thiol group.

The content of the thiol curing agent (C) is not particularly limited, but when the nonvolatile components other than the component (B) in the resin composition are 100% by mass, the content of the thiol curing agent is preferably 5% by mass or more, and more. The content is preferably 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more. (C) The upper limit of the content of the thiol curing agent is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 55% by mass or less, and particularly preferably 50% by mass or less. % by mass or less.

<(D) Curing accelerator>
The resin composition of the present invention contains (D) a curing accelerator. (D) The curing accelerator has the function of accelerating the curing of the (A) epoxy resin.

In the first embodiment, (D) the curing accelerator is selected from the group consisting of a phosphorus-based curing accelerator, a urea-based curing accelerator, a guanidine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator. It preferably contains at least one selected from the group consisting of phosphorus-based curing accelerators, imidazole-based curing accelerators, and urea-based curing accelerators.

Examples of the phosphorus curing accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, and tetrabutylphosphonium hydro Aliphatic phosphonium salts such as denhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenyl Phosphonium tetraphenylborate, tetraphenylphosphonium tetrap-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4 - Aromatic phosphonium salts such as methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; Aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone Aromatic phosphine/quinone addition reaction products such as addition reaction products; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl- Aliphatic phosphine such as 2-butenyl)phosphine, tricyclohexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o -Tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butyl) phenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris( 3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4- methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis( Examples include aromatic phosphines such as diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether. It will be done.

Examples of the urea-based curing accelerator include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl) )-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4- methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4- methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3- [4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea] etc.

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] Dec-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-(o-tolyl) biguanide and the like.

Examples of imidazole-based curing accelerators include 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'-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-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-3-benzylimidazolium chloride, 2-methylimidazoline , imidazole compounds such as 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins.

The molecular weight of the imidazole curing accelerator is not particularly limited, but from the viewpoint of improving workability (fluidity) and suppressing undissolved residue during hot molding, it is preferably 1,000 or less, more preferably It is 600 or less, more preferably 400 or less, particularly preferably 300 or less.

Examples of the metal hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes 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. Examples include organic zinc complexes such as , organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

In the second embodiment, the curing accelerator (D) is not limited as long as a resin composition having a reaction initiation temperature of 70° C. or higher and a reaction peak temperature of 130° C. or lower based on differential scanning calorimetry can be obtained. It is preferable to contain at least one selected from the group consisting of a phosphorus-based curing accelerator, a urea-based curing accelerator, a guanidine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator; It may also contain an agent.

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

The content of the curing accelerator (D) is not particularly limited, but when the nonvolatile components other than the component (B) in the resin composition are 100% by mass, it is preferably 0.001% by mass or more, The content is more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more. (D) The upper limit of the content of the curing accelerator is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 4% by mass or less, particularly preferably 3% by mass. % or less.

<(E) Other additives>
The resin composition of the present invention may further contain arbitrary additives as nonvolatile components. Examples of such additives include phenolic curing agents, naphthol curing agents, acid anhydride curing agents, active ester curing agents, benzoxazine curing agents, cyanate ester curing agents, carbodiimide curing agents, Curing agents other than thiol curing agents such as imidazole curing agents; Organic fillers such as rubber particles, polyamide fine particles, silicone particles; phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyether sulfone resins, polyphenylene ether resins , thermoplastic resins such as polycarbonate resins, polyetheretherketone resins, and polyester resins; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet Coloring agents such as , titanium oxide, and carbon black; Polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; Leveling agents such as siloxane; Thickeners such as bentone and montmorillonite; Silicone antifoaming agents and acrylic antifoaming agents , fluorine-based antifoaming agents, vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; silane coupling agents, triazole-based adhesion agents , adhesion-imparting agents such as tetrazole-based adhesion-imparting agents and triazine-based adhesion-imparting agents; antioxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants; fluorescent brighteners such as stilbene derivatives; fluorine Surfactants such as surfactants and silicone surfactants; phosphorus flame retardants (e.g. phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen flame retardants (e.g. melamine sulfate), halogen-based flame retardants Flame retardants, inorganic flame retardants (e.g. antimony trioxide), etc.; borate ester compounds, titanate ester compounds, aluminate compounds, zirconate compounds, isocyanate compounds, carboxylic acids, acid anhydrides, mercapto organic acids, etc. Stabilizers include: One type of additive may be used alone, or two or more types may be used in combination in any ratio. (E) The content of other additives can be determined as appropriate by those skilled in the art.

<(F) Organic solvent>
The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the above-mentioned nonvolatile components. (F) As the organic solvent, any known organic solvent can be used as long as it can dissolve at least a portion of the nonvolatile components, and its type is not particularly limited. (F) Organic solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, γ- Ester solvents such as butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol; Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate; methyl lactate, ethyl lactate, 2-hydroxyisobutyric acid Ester alcohol solvents such as methyl; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); N,N-dimethylformamide, Amide solvents such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone; Sulfoxide solvents such as dimethyl sulfoxide; Nitrile solvents such as acetonitrile and propionitrile; Hexane, cyclopentane, cyclohexane, methylcyclohexane, etc. Aliphatic hydrocarbon solvents include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (F) The organic solvents may be used alone or in combination of two or more in any ratio.

<Method for manufacturing resin composition>
The resin composition of the present invention can be prepared, for example, in any reaction vessel by adding (A) an epoxy resin, (B) an inorganic filler, (C) a thiol curing agent, (D) a curing accelerator, and optionally (E) It can be produced by adding and mixing other additives and (F) an organic solvent as necessary in any order and/or some or all at the same time. Further, in the process of adding and mixing each component, the temperature can be set appropriately, and heating and/or cooling may be performed temporarily or throughout the process. Further, in the process of adding and mixing each component, stirring or shaking may be performed. Further, during or after addition and mixing, the resin composition may be stirred using a stirring device such as a mixer to uniformly disperse the resin composition.

<Characteristics of resin composition>
The resin composition of the present invention includes (A) an epoxy resin, (B) an inorganic filler, (C) a thiol curing agent, and (D) a curing accelerator, and the content of the (B) component is determined in the resin composition. When the non-volatile components in the product are 100% by mass, it is 70% by mass or more and falls under either the first embodiment or the second embodiment below, so low-temperature moldability and copper adhesion A cured product with excellent properties can be obtained. In particular, a cured product with excellent copper adhesion against tension in the vertical direction can be obtained. Moreover, the cured product of the resin composition of the present invention preferably has excellent storage stability and/or heat resistance.

In the first embodiment, component (D) is selected from the group consisting of a phosphorus-based curing accelerator, a urea-based curing accelerator, a guanidine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator. Contains at least one species. In this embodiment, the reaction initiation temperature of the resin composition based on differential scanning calorimetry (DSC) is preferably 50°C or higher, more preferably 60°C or higher, even more preferably 65°C or higher, particularly preferably 70°C or higher. be. In addition, from the viewpoint of achieving better low-temperature moldability, the reaction peak temperature of the resin composition based on differential scanning calorimetry is preferably 160°C or lower, more preferably 150°C or lower, still more preferably 140°C or lower, especially Preferably it is 130°C or lower.

In the second embodiment, the reaction start temperature of the resin composition based on differential scanning calorimetry is 70° C. or higher and the reaction peak temperature is 130° C. or lower, and as long as the conditions are satisfied, the component (D) is not limited.

Here, the reaction initiation temperature based on differential scanning calorimetry is the differential scanning calorimetry curve (DSC curve) obtained when performing differential scanning calorimetry at a heating rate of 5°C/min and in the temperature range of 25°C to 280°C. ) means the temperature at the intersection of the tangent line and the baseline at the inflection point. The reaction peak temperature is the temperature indicating the peak top located on the lowest temperature side.

Since the cured product of the resin composition of the present invention has excellent storage stability, for example, in an environment of 25° C./60% humidity, it is preferably for 12 hours or more, more preferably for 24 hours or more, and particularly preferably for 48 hours or more. It may exhibit fluidity even if it is left standing for more than an hour.

Since the cured product of the resin composition of the present invention has excellent low-temperature moldability, it is preferably compressed at a mold temperature of less than 140°C, more preferably less than 130°C, further preferably less than 120°C, particularly preferably less than 110°C. By molding (pressure: 6 MPa, curing time: 5 minutes), a cured product without tackiness can be obtained.

Since the cured product of the resin composition of the present invention may have excellent heat resistance, for example, the glass transition temperature (Tg) may be preferably 60°C or higher, more preferably 80°C or higher, and particularly preferably 100°C or higher. . The glass transition temperature (Tg) here is based on JIS K 7121, and the DSC curve shows a step-like change when performing differential scanning calorimetry at a heating rate of 5°C/min and a measurement temperature range of 25°C to 280°C. This is the midpoint of the section shown.

Since the cured product of the resin composition of the present invention has excellent copper adhesion, it is, for example, compression molded (pressure: 6 MPa, cure time: 5 minutes) on the shiny surface of a copper foil, and then heated at 130°C for 90 minutes. The adhesive strength of ^the cured product measured in a vertical tensile test (test speed ^0.1 Kg/sec) when cured by cm ² or more, particularly preferably 100 Kgf/cm ² or more.

<Applications of resin composition>
Due to the above-mentioned advantages, the cured product of the resin composition of the present invention is particularly useful for semiconductor sealing layers and insulating layers. Therefore, this resin composition can be used as a resin composition for semiconductor encapsulation or an insulating layer.

For example, the resin composition of the present invention can be used as a resin composition for forming an insulating layer of a semiconductor chip package (a resin composition for an insulating layer of a semiconductor chip package), and a circuit board (including a printed wiring board). It can be suitably used as a resin composition for forming an insulating layer (resin composition for an insulating layer of a circuit board).

Further, for example, the resin composition of the present invention can be suitably used as a resin composition for sealing a semiconductor chip in a semiconductor chip package (resin composition for semiconductor chip sealing).

Semiconductor chip packages to which the sealing layer or insulating layer formed of the cured product of the resin composition of the present invention can be applied include, for example, FC-CSP, MIS-BGA package, ETS-BGA package, and fan-out type WLP ( Fan-in type WLP, Fan-out type PLP (Panel Level Package), and Fan-in type PLP.

Further, the resin composition of the present invention may be used as an underfill material, for example, as a material for MUF (Molding Under Filling) used after connecting a semiconductor chip to a substrate.

Furthermore, the resin composition of the present invention can be used for resin sheets, sheet-like laminated materials such as prepreg, liquid materials such as resin inks for solder resists, die bonding materials, hole filling resins, component embedding resins, etc. Can be used for a wide range of applications.

<Resin sheet>
The resin sheet of the present invention includes a support and a resin composition layer provided on the support. The resin composition layer is a layer containing the resin composition of the present invention, and is usually formed of the resin composition.

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 600 μm or less, more preferably 500 μm or less. The lower limit of the thickness of the resin composition layer is preferably 1 μm or more, 5 μm or more, more preferably 10 μm or more, even more preferably 50 μm or more, and particularly preferably 100 μm or more.

Moreover, the thickness of the cured product obtained by curing the resin composition layer is preferably 600 μm or less, more preferably 500 μm or less. The lower limit of the thickness of the cured product is preferably 1 μm or more, 5 μm or more, more preferably 10 μm or more, even more preferably 50 μm or more, particularly preferably 100 μm or more.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferred.

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ); polycarbonate (hereinafter sometimes abbreviated as "PC"); acrylic polymers such as polymethyl methacrylate (hereinafter sometimes abbreviated as "PMMA"); cyclic polyolefins; triacetylcellulose (hereinafter sometimes abbreviated as "PMMA"); ); polyether sulfide (hereinafter sometimes abbreviated as "PES"); polyether ketone; polyimide; and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When using metal foil as a support, examples of the metal foil include copper foil, aluminum foil, and the like. Among them, copper foil is preferred. As the copper foil, a foil made of a single metal such as copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. May be used.

The surface of the support to be bonded to the resin composition layer may be subjected to treatments such as matte treatment, corona treatment, and antistatic treatment.

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . Examples of commercially available mold release agents include "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, which are alkyd resin mold release agents. Examples of the support with a release layer include "Lumirror T60" manufactured by Toray Industries, Inc.; "Purex" manufactured by Teijin; and "Unipeel" manufactured by Unitika.

The thickness of the support is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. In addition, when using the support body with a mold release layer, it is preferable that the thickness of the whole support body with a mold release layer is in the said range.

A resin sheet can be manufactured, for example, by applying a resin composition onto a support using a coating device such as a die coater. Further, if necessary, a resin sheet may be manufactured by dissolving the resin composition in an organic solvent to prepare a resin varnish, and applying this resin varnish. By using an organic solvent, the viscosity can be adjusted and the coating properties can be improved. When a resin composition or resin varnish containing an organic solvent is used, the resin composition or resin varnish is usually dried after coating to form a resin composition layer.

Drying may be performed by a known method such as heating or blowing hot air. The drying conditions are such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when using a resin composition or resin varnish containing 30% by mass to 60% by mass of organic solvent, the temperature is 50°C to 150°C for 3 minutes to 10 minutes. By drying for minutes, a resin composition layer can be formed.

The resin sheet may contain any layer other than the support and the resin composition layer, if necessary. For example, in the resin sheet, a protective film similar to the support may be provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent dust from adhering to the surface of the resin composition layer and from scratches. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. Further, the resin sheet can be wound up into a roll and stored.

The resin sheet can be suitably used for forming an insulating layer in the manufacture of a semiconductor chip package (insulating resin sheet for a semiconductor chip package). For example, the resin sheet can be used to form an insulating layer of a circuit board (resin sheet for an insulating layer of a circuit board). Examples of packages using such a substrate include FC-CSP, MIS-BGA package, and ETS-BGA package.

Further, the resin sheet can be suitably used for encapsulating a semiconductor chip (semiconductor chip encapsulation resin sheet). Applicable semiconductor chip packages include, for example, Fan-out type WLP, Fan-in type WLP, Fan-out type PLP, Fan-in type PLP, and the like.

Further, the resin sheet may be used as a material for the MUF used after the semiconductor chip is connected to the substrate.

Additionally, resin sheets can be used in a wide range of other applications where high insulation reliability is required. For example, a resin sheet can be suitably used to form an insulating layer of a circuit board such as a printed wiring board.

<Circuit board>
The circuit board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention. This circuit board can be manufactured, for example, by a manufacturing method including the following steps (1) and (2).
(1) Step of forming a resin composition layer on a base material.
(2) A step of thermosetting the resin composition layer to form an insulating layer.

In step (1), a base material is prepared. Examples of the base material include substrates such as a glass epoxy substrate, a metal substrate (stainless steel, cold rolled steel plate (SPCC), etc.), a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. Further, the base material may have a metal layer such as copper foil on the surface as a part of the base material. For example, a substrate having a releasable first metal layer and a second metal layer on both surfaces may be used. When such a base material is used, a conductor layer as a wiring layer that can function as circuit wiring is usually formed on the surface of the second metal layer opposite to the first metal layer. An example of a base material having such a metal layer is "Micro Thin", an ultra-thin copper foil with carrier copper foil manufactured by Mitsui Mining & Mining Co., Ltd.

Further, a conductor layer may be formed on one or both surfaces of the base material. In the following description, a member including a base material and a conductor layer formed on the surface of this base material may be appropriately referred to as a "base material with a wiring layer." The conductor material included in the conductor layer is, for example, one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Examples include materials containing the above metals. As the conductor material, a single metal or an alloy may be used. Examples of the alloy include alloys of two or more metals selected from the above group (eg, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among these, from the viewpoint of versatility in forming conductor layers, cost, and ease of patterning, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as single metals; and nickel-chromium alloys as alloys , copper/nickel alloy, copper/titanium alloy; are preferred. Among these, single metals such as chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and nickel-chromium alloys are more preferred, and single metals such as copper are particularly preferred.

The conductor layer may be patterned, for example, in order to function as a wiring layer. At this time, the line (circuit width)/space (width between circuits) ratio of the conductor layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 10/10 μm or less, and Preferably it is 5/5 μm or less, even 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 conductor layer. The minimum pitch of the conductor layer may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

The thickness of the conductor layer depends on the design of the circuit board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, even more preferably 10 μm to 20 μm, particularly preferably 15 μm to 20 μm.

The conductor layer can be formed, for example, by laminating a dry film (photosensitive resist film) on a base material, or by exposing and developing the dry film under predetermined conditions using a photomask to form a pattern. It can be formed by a method including a step of obtaining a film, a step of forming a conductor layer by a plating method such as an electrolytic plating method using a developed patterned dry film as a plating mask, and a step of peeling off the patterned dry film. As the dry film, a photosensitive dry film made of a photoresist composition can be used, and for example, a dry film formed of a resin such as a novolac resin or an acrylic resin can be used. The conditions for laminating the base material and the dry film may be the same as the conditions for laminating the base material and the resin sheet, which will be described later. Peeling of the dry film can be carried out using, for example, an alkaline stripping solution such as a sodium hydroxide solution.

After preparing the base material, a resin composition layer is formed on the base material. When a conductor layer is formed on the surface of the base material, the resin composition layer is preferably formed such that the conductor layer is embedded in the resin composition layer.

Formation of the resin composition layer is performed, for example, by laminating a resin sheet and a base material. This lamination can be performed, for example, by bonding the resin composition layer to the base material by heat-pressing the resin sheet to the base material from the support side. Examples of the member for heat-pressing the resin sheet to the base material (hereinafter sometimes referred to as "heat-pressing member") include a heated metal plate (SUS mirror plate, etc.) or a metal roll (SUS roll, etc.). It will be done. Note that, instead of pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the base material.

The base material and the resin sheet may be laminated by, for example, a vacuum lamination method. In the vacuum lamination method, the heat-pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C. The heating pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa. The heat-pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 13 hPa or less.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same as the conditions for the heat-pressing of the lamination described above. Note that the lamination and smoothing treatment may be performed continuously using a vacuum laminator.

Further, the resin composition layer can be formed by, for example, a compression molding method. The molding conditions may be similar to the method for forming a resin composition layer in the step of forming a sealing layer of a semiconductor chip package, which will be described later.

After forming the resin composition layer on the base material, the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions for the resin composition layer vary depending on the type of resin composition, but the curing temperature is usually in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably in the range of 170°C to 200°C). ), and the curing time is in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before thermally curing the resin composition layer, the resin composition layer may be subjected to a preliminary heating treatment in which the resin composition layer is heated at a temperature lower than the curing temperature. For example, before thermosetting the resin composition layer, the resin composition layer is usually heated at a temperature of 50°C or higher and lower than 120°C (preferably 60°C or higher and 110°C or lower, more preferably 70°C or higher and 100°C or lower). may be preheated for usually 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

In the manner described above, a circuit board having an insulating layer can be manufactured. Further, the method for manufacturing a circuit board may further include an arbitrary step.
For example, when a circuit board is manufactured using a resin sheet, the method for manufacturing the circuit board may include a step of peeling off the support of the resin sheet. The support may be peeled off before thermal curing of the resin composition layer, or may be peeled off after thermal curing of the resin composition layer.

The method for manufacturing a circuit board may include, for example, a step of polishing the surface of the insulating layer after forming the insulating layer. The polishing method is not particularly limited. For example, the surface of the insulating layer can be polished using a surface grinder.

The method for manufacturing a circuit board may include, for example, a step (3) of interlayer connecting conductor layers, for example, a step of drilling holes in an insulating layer. Thereby, holes such as via holes and through holes can be formed in the insulating layer. Examples of methods for forming via holes include laser irradiation, etching, mechanical drilling, and the like. The dimensions and shape of the via hole may be determined as appropriate depending on the design of the circuit board. Note that in step (3), the interlayer connection may be performed by polishing or grinding the insulating layer.

After forming the via hole, it is preferable to perform a step of removing smear within the via hole. This process is sometimes called a desmear process. For example, when a conductor layer is formed on an insulating layer by a plating process, a wet desmear process may be performed on the via hole. Further, when forming a conductor layer on an insulating layer by a sputtering process, a dry desmear process such as a plasma treatment process may be performed. Furthermore, the insulating layer may be roughened by a desmear process.

Furthermore, before forming the conductor layer on the insulating layer, the insulating layer may be subjected to a roughening treatment. According to this roughening treatment, the surface of the insulating layer including the inside of the via hole is usually roughened. As the roughening treatment, either dry or wet roughening treatment may be performed. Examples of dry roughening treatment include plasma treatment and the like. Furthermore, an example of the wet roughening treatment includes a method in which a swelling treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing liquid are performed in this order.

After forming the via hole, a conductor layer may be formed on the insulating layer. By forming a conductor layer at the position where the via hole is formed, the newly formed conductor layer and the conductor layer on the surface of the base material are electrically connected, and an interlayer connection is performed. Examples of methods for forming the conductor layer include plating, sputtering, and vapor deposition, with plating being preferred. In a preferred embodiment, a conductive layer having a desired wiring pattern is formed by plating the surface of the insulating layer by an appropriate method such as a semi-additive method or a fully additive method. Further, when the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by a subtractive method. The material of the conductor layer to be formed may be a single metal or an alloy. Further, this conductor layer may have a single layer structure or a multilayer structure including two or more layers of different types of materials.

Here, an example of an embodiment in which a conductor layer is formed on an insulating layer will be described in detail. A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer, corresponding to a desired wiring pattern. After forming an electrolytic plating layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layers are removed by a process such as etching to form a conductor layer having a desired wiring pattern. Note that when forming the conductor layer, the dry film used to form the mask pattern is the same as the dry film described above.

The method for manufacturing a circuit board may include a step (4) of removing the base material. By removing the base material, a circuit board having an insulating layer and a conductor layer embedded in this insulating layer is obtained. This step (4) can be performed, for example, when a base material having a peelable metal layer is used.

<Semiconductor chip package>
The semiconductor chip package according to the first embodiment of the present invention includes the above-described circuit board and a semiconductor chip mounted on this circuit board. This semiconductor chip package can be manufactured by bonding a semiconductor chip to a circuit board.

As the bonding conditions between the circuit board and the semiconductor chip, any conditions can be adopted that allow conductive connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board. For example, conditions used in flip-chip mounting of semiconductor chips can be adopted. Furthermore, for example, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

An example of the bonding method is a method of press-bonding a semiconductor chip to a circuit board. As for the crimping conditions, the crimping temperature is usually in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and the crimping time is usually in the range of 1 second to 60 seconds. (preferably 5 seconds to 30 seconds).

Another example of the bonding method is a method of bonding a semiconductor chip to a circuit board by reflowing it. The reflow conditions may be in the range of 120°C to 300°C.

After bonding the semiconductor chip to the circuit board, the semiconductor chip may be filled with a mold underfill material. As this mold underfill material, the above-mentioned resin composition may be used, or the above-mentioned resin sheet may be used.

A semiconductor chip package according to a second embodiment of the present invention includes a semiconductor chip and a cured product of the resin composition for sealing the semiconductor chip. In such semiconductor chip packages, the cured product of the resin composition usually functions as a sealing layer. An example of the semiconductor chip package according to the second embodiment is a fan-out type WLP.

The manufacturing method for such a semiconductor chip package is as follows:
(A) Step of laminating a temporary fixing film on the base material,
(B) Temporarily fixing the semiconductor chip on the temporary fixing film,
(C) forming a sealing layer on the semiconductor chip;
(D) Peeling the base material and temporary fixing film from the semiconductor chip,
(E) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled;
(F) a step of forming a rewiring layer as a conductor layer on the rewiring formation layer, and
(G) forming a solder resist layer on the rewiring layer;
including. Further, the method for manufacturing the semiconductor chip package described above includes:
(H) The method may include the step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces.

(Process (A))
Step (A) is a step of laminating a temporary fixing film on the base material. The conditions for laminating the base material and the temporary fixing film may be the same as the conditions for laminating the base material and the resin sheet in the method for manufacturing a circuit board.

Examples of base materials include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold rolled steel plate (SPCC); glass fibers such as FR-4 substrates impregnated with epoxy resin, etc. Examples include a thermosetting substrate; a substrate made of bismaleimide triazine resin such as BT resin; and the like.

The temporary fixing film can be made of any material that can be peeled off from the semiconductor chip and can temporarily fix the semiconductor chip. Commercially available products include "Riva Alpha" manufactured by Nitto Denko Corporation.

(Process (B))
Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. The semiconductor chip can be temporarily fixed using a device such as a flip chip bonder or a die bonder. The layout and number of semiconductor chips can be appropriately set depending on the shape and size of the temporary fixing film, the desired number of semiconductor chip packages to be produced, and the like. For example, semiconductor chips may be temporarily fixed by arranging them in a matrix of multiple rows and columns.

(Step (C))
Step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer is formed from a cured product of the resin composition described above. The sealing layer is usually formed by a method that includes the steps of forming a resin composition layer on the semiconductor chip and thermally curing the resin composition layer to form the sealing layer.

The resin composition layer is preferably formed by compression molding. In the compression molding method, a semiconductor chip and a resin composition are usually placed in a mold, and pressure and, if necessary, heat are applied to the resin composition within the mold to form a resin composition layer covering the semiconductor chip.

The specific operation of the compression molding method can be performed as follows, for example. An upper mold and a lower mold are prepared as molds for compression molding. Further, a resin composition is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip coated with the resin composition is attached to the lower mold together with the base material and the temporary fixing film. Thereafter, the upper mold and the lower mold are clamped together, heat and pressure are applied to the resin composition, and compression molding is performed.

Moreover, the specific operation of the compression molding method may be performed as follows, for example. An upper mold and a lower mold are prepared as molds for compression molding. A resin composition is placed on the lower mold. Further, the semiconductor chip is attached to the upper mold together with the base material and the temporary fixing film. Thereafter, the upper mold and the lower mold are clamped so that the resin composition placed on the lower mold contacts the semiconductor chip attached to the upper mold, and compression molding is performed by applying heat and pressure.

Molding conditions vary depending on the composition of the resin composition, and appropriate conditions can be adopted to achieve good sealing. For example, the temperature of the mold during molding is preferably 70°C or higher, more preferably 80°C or higher, particularly preferably 90°C or higher, and preferably 200°C or lower, more preferably 170°C or lower, particularly preferably 150°C. It is as follows. Further, the pressure applied during molding is preferably 1 MPa or more, more preferably 3 MPa or more, particularly preferably 5 MPa or more, and preferably 50 MPa or less, more preferably 30 MPa or less, particularly preferably 20 MPa or less. The curing time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 3 minutes or more, and preferably 60 minutes or less, more preferably 30 minutes or less, particularly preferably 20 minutes or less. Usually, the mold is removed after forming the resin composition layer. The mold may be removed before or after thermosetting the resin composition layer.

The resin composition layer may be formed by laminating a resin sheet and a semiconductor chip. For example, the resin composition layer can be formed on the semiconductor chip by heat-pressing the resin composition layer of the resin sheet and the semiconductor chip. Lamination of a resin sheet and a semiconductor chip can be performed in the same manner as the lamination of a resin sheet and a base material in a method for manufacturing a circuit board, usually using a semiconductor chip instead of a base material.

After forming the resin composition layer on the semiconductor chip, this resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor chip. Thereby, the semiconductor chip is sealed with the cured product of the resin composition. The thermosetting conditions for the resin composition layer may be the same as those for the resin composition layer in the method for manufacturing a circuit board. Furthermore, before thermally curing the resin composition layer, the resin composition layer may be subjected to a preliminary heat treatment in which the resin composition layer is heated at a temperature lower than the curing temperature. The processing conditions for this preheating treatment may be the same as those for the preheating treatment in the circuit board manufacturing method.

(Process (D))
Step (D) is a step of peeling the base material and the temporary fixing film from the semiconductor chip. As for the peeling method, it is desirable to adopt an appropriate method depending on the material of the temporary fixing film. Examples of the peeling method include a method of heating, foaming, or expanding the temporarily fixed film and peeling it off. Moreover, as a peeling method, for example, a method of irradiating the temporary fixing film with ultraviolet rays through the base material to reduce the adhesive strength of the temporary fixing film and peeling it off can be mentioned.

In the method of peeling off the temporarily fixed film by heating, foaming or expanding, the heating conditions are usually 100° C. to 250° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in a method in which the temporary fixing film is peeled off by irradiation with ultraviolet rays to reduce its adhesive strength, the amount of ultraviolet ray irradiation is usually 10 mJ/cm ² to 1000 mJ/cm ² .

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

Any insulating material can be used as the material for the rewiring formation layer. Among these, photosensitive resins and thermosetting resins are preferred from the viewpoint of ease of manufacturing semiconductor chip packages. Moreover, the resin composition of the present invention may be used as this thermosetting resin.

After forming the rewiring formation layer, via holes may be formed in the rewiring formation layer in order to connect the semiconductor chip and the rewiring layer between layers.

In the method of forming via holes when the material of the redistribution layer is photosensitive resin, the surface of the redistribution layer is usually irradiated with active energy rays through a mask pattern, and the irradiated areas of the redistribution layer are exposed to light. Let it harden. Examples of active energy rays include ultraviolet rays, visible rays, electron beams, and X-rays, with ultraviolet rays being particularly preferred. The irradiation amount and irradiation time of ultraviolet rays can be appropriately set depending on the photosensitive resin. Examples of the exposure method include a contact exposure method in which the mask pattern is exposed to the rewiring formation layer in close contact with the rewiring formation layer, a non-contact exposure method in which parallel light is used to expose the mask pattern without the mask pattern in close contact with the rewiring formation layer, etc. can be mentioned.

After the rewiring formation layer is photocured, the rewiring formation layer is developed and unexposed areas are removed to form via holes. Development may be performed by either wet development or dry development. Examples of the developing method include a dip method, a paddle method, a spray method, a brushing method, a scraping method, etc., and the paddle method is preferable from the viewpoint of resolution.

When the material of the rewiring formation layer is a thermosetting resin, examples of methods for forming via holes include laser irradiation, etching, mechanical drilling, and the like. Among these, laser irradiation is preferred. Laser irradiation can be performed using an appropriate laser processing machine using a light source such as a carbon dioxide laser, UV-YAG laser, or excimer laser.

Although the shape of the via hole is not particularly limited, it is generally circular (substantially circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less. Here, the top diameter of the via hole refers to the diameter of the opening of the via hole on the surface of the rewiring formation layer.

(Process (F))
Step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring forming layer. A method for forming a rewiring layer on the rewiring formation layer may be the same as a method for forming a conductor layer on an insulating layer in a method for manufacturing a circuit board. Alternatively, the steps (E) and (F) may be repeated to alternately stack up the rewiring layers and the rewiring forming layers (build-up).

(Process (G))
Step (G) is a step of forming a solder resist layer on the rewiring layer. Any material having insulation properties can be used as the material of the solder resist layer. Among these, photosensitive resins and thermosetting resins are preferred from the viewpoint of ease of manufacturing semiconductor chip packages. Furthermore, the resin composition of the present invention may be used as the thermosetting resin.

Moreover, in step (G), bumping processing to form bumps may be performed as necessary. The bumping process can be performed using methods such as solder balls and solder plating. Furthermore, via holes can be formed in the bumping process in the same manner as in step (E).

(Step (H))
The method for manufacturing a semiconductor chip package may include a step (H) in addition to steps (A) to (G). Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces. The method of dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited.

<Semiconductor device>
The semiconductor device includes a semiconductor chip package. Semiconductor devices include, for example, electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, etc.). and aircraft, etc.).

Hereinafter, the present invention will be specifically explained with reference to Examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass," respectively, unless otherwise specified.

<Example 1>
Glycidylamine type epoxy resin (ADEKA "EP3950L", epoxy equivalent 95 g/eq.) 10 parts, thiol curing agent (Ajinomoto Fine Techno "TMPIC", tris (3-mercaptopropyl) isocyanurate, thiol equivalent 117 g /eq.) 10 parts, spherical silica (average particle size 6.0 μm, maximum cut diameter 20 μm, specific surface area 4.8 m ² /g, KBM573 (manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) ) and 0.4 parts of a urea-based curing accelerator ("U-CAT3512T" manufactured by Sun-Apro Co., Ltd., aromatic dimethyl urea) were uniformly dispersed using a mixer to form a resin composition. Obtained.

<Example 2>
Instead of 0.4 part of urea-based curing accelerator ("U-CAT3512T", manufactured by Sun-Apro Co., Ltd., aromatic dimethyl urea), 0.2 part of phosphorus-based curing accelerator ("TPP", manufactured by Hokko Chemical Co., Ltd., triphenylphosphine) A resin composition was obtained in the same manner as in Example 1 except that .

<Example 3>
Instead of 0.4 part of a urea-based curing accelerator ("U-CAT3512T" manufactured by Sun-Apro Co., Ltd., aromatic dimethyl urea), a phosphorus-based curing accelerator ("TBP-3S" manufactured by Hokko Chemical Co., Ltd., tetrabutylphosphonium hydrogen hexane) was used. A resin composition was obtained in the same manner as in Example 1, except for using 0.36 parts of hydrophthalate.

<Example 4>
Instead of 0.4 part of a urea-based curing accelerator ("U-CAT3512T" manufactured by Sun-Apro Co., Ltd., aromatic dimethyl urea), a phosphorus-based curing accelerator ("TBP-3PC" manufactured by Hokko Chemical Co., Ltd., tetrabutylphosphonium-2, A resin composition was obtained in the same manner as in Example 1, except that 0.46 part of 6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate) was used.

<Example 5>
6 parts of glycidylamine type epoxy resin ("EP3950L" manufactured by ADEKA, epoxy equivalent: 95 g/eq.), 3 parts of glycidylamine type epoxy resin ("604", manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 120 g/eq.), lycidylamine type epoxy 1 part of resin ("EP3980S" manufactured by ADEKA, epoxy equivalent 115 g/eq.), thiol curing agent ("TMPIC" manufactured by Ajinomoto Fine Techno, tris (3-mercaptopropyl) isocyanurate, thiol equivalent 117 g/eq.) 10 parts, spherical silica (average particle size 6.0 μm, maximum cut diameter 20 μm, specific surface area 4.8 m ² /g, treated with KBM573 (manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) A resin composition was obtained by uniformly dispersing 100 parts of urea-based curing accelerator ("U-CAT3512T" manufactured by San-Apro Co., Ltd., aromatic dimethylurea) using a mixer.

<Example 6>
Glycidylamine type epoxy resin (ADEKA "EP3950L", epoxy equivalent: 95 g/eq.) 6 parts, bisphenol A type epoxy resin (Mitsubishi Chemical "828EL", epoxy equivalent: 189 g/eq.) 10 parts, thiol-based curing 5 parts of agent (“TMPIC” manufactured by Ajinomoto Fine-Techno, tris(3-mercaptopropyl) isocyanurate, thiol equivalent 117 g/eq.), spherical silica (average particle size 6.0 μm, maximum cut diameter 20 μm, specific surface area 4. 8 m ² /g, 80 parts of KBM573 (treated with N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), urea-based curing accelerator (“U-CAT3512T”, manufactured by San-Apro Co., Ltd., aromatic A resin composition was obtained by uniformly dispersing 0.4 part of dimethylurea (dimethylurea) using a mixer.

<Example 7>
Example 1 except that the amount of the thiol curing agent (“TMPIC” manufactured by Ajinomoto Fine Techno, tris (3-mercaptopropyl) isocyanurate, thiol equivalent: 117 g/eq.) was changed from 10 parts to 8 parts. A resin composition was obtained in the same manner as above.

<Example 8>
The amount of thiol-based curing agent (“TMPIC” manufactured by Ajinomoto Fine-Techno, Inc., tris(3-mercaptopropyl) isocyanurate, thiol equivalent: 117 g/eq.) was changed from 10 parts to 6 parts, and the amount of spherical silica (average particle Diameter 6.0 μm, maximum cut diameter 20 μm, specific surface area 4.8 m ² /g, amount of KBM573 (manufactured by Shin-Etsu Chemical Co., Ltd., treated with N-phenyl-3-aminopropyltrimethoxysilane) used was 100 μm. A resin composition was obtained in the same manner as in Example 1, except that the amount was changed from 90 parts to 90 parts.

<Example 9>
The amount of thiol curing agent ("TMPIC" manufactured by Ajinomoto Fine-Techno, Inc., tris(3-mercaptopropyl) isocyanurate, thiol equivalent 117 g/eq.) was changed from 10 parts to 4 parts, and the amount of spherical silica (average particle Diameter 6.0 μm, maximum cut diameter 20 μm, specific surface area 4.8 m ² /g, amount of KBM573 (manufactured by Shin-Etsu Chemical Co., Ltd., treated with N-phenyl-3-aminopropyltrimethoxysilane) used was 100 μm. Implemented except that the usage amount of the urea curing accelerator ("U-CAT3512T" manufactured by Sun-Apro Co., Ltd., aromatic dimethyl urea) was changed from 0.4 parts to 0.2 parts. A resin composition was obtained in the same manner as in Example 1.

<Example 10>
Instead of 10 parts of a thiol-based curing agent ("TMPIC" manufactured by Ajinomoto Fine Techno, tris (3-mercaptopropyl) isocyanurate, thiol equivalent 117 g/eq.), a thiol-based curing agent ("PEMP" manufactured by SC Organic Chemical Co., Ltd.) was used. A resin composition was obtained in the same manner as in Example 1, except that 10 parts of pentaerythritol tetrakis (3-mercaptopropionate) and thiol equivalent (122 g/eq.) were used.

<Example 11>
Instead of 10 parts of a thiol-based curing agent (“TMPIC” manufactured by Ajinomoto Fine-Techno Co., Ltd., tris(3-mercaptopropyl) isocyanurate, thiol equivalent 117 g/eq.), a thiol-based curing agent (pentaerythritol tetrakis manufactured by SC Organic Chemical Co., Ltd.) was used. A resin composition was obtained in the same manner as in Example 9, except that 4 parts of (3-mercaptopropyl)ether, thiol equivalent: 119 g/eq.) were used.

<Example 12>
Instead of 0.4 part of a urea-based curing accelerator ("U-CAT3512T" manufactured by Sun-Apro Co., Ltd., aromatic dimethyl urea), an imidazole-based curing accelerator ("2MZA-PW" manufactured by Shikoku Kasei Kogyo Co., Ltd., 2,4-diamino A resin composition was obtained in the same manner as in Example 1, except that 0.2 part of -6-[2'-methylimidazolyl-(1')]-ethyl-S-triazine) was used.

<Comparative example 1>
Instead of 0.4 part of urea-based curing accelerator ("U-CAT3512T", manufactured by San-Apro, aromatic dimethyl urea), 0.22 part of amine-based curing accelerator ("SA-102", manufactured by San-Apro, DBU salt) A resin composition was obtained in the same manner as in Example 1 except that .

<Comparative example 2>
Glycidylamine type epoxy resin (ADEKA "EP3950L", epoxy equivalent: 95 g/eq.) 10 parts, acid anhydride curing agent (Shin Nippon Rika Co., Ltd. "HNA-100", acid anhydride equivalent: 179 g/eq.) 15 part, spherical silica (average particle size 6.0 μm, maximum cut diameter 20 μm, specific surface area 4.8 m ² /g, treated with KBM573 (manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) A resin composition was obtained by uniformly dispersing 130 parts of a urea-based curing accelerator ("U-CAT3512T" manufactured by Sun-Apro Co., Ltd., aromatic dimethylurea) using a mixer.

<Test Example 1: Differential Scanning Calorimetry (DSC)>
10 mg of the resin compositions produced in Examples and Comparative Examples were weighed into sample containers. Put a lid on the sample container, attach it to a differential scanning calorimeter, and measure at a heating rate of 5°C/min in the range of 25°C to 280°C to obtain a differential scanning calorimetry curve (DSC curve) on the time axis. Ta. The temperature at the intersection of the tangent at the inflection point of the obtained DSC curve and the baseline was defined as the curing start temperature. Moreover, the temperature showing the peak top located on the lowest temperature side was defined as the reaction peak temperature.

<Test Example 2: Evaluation of storage stability>
Approximately 5 g of the resin compositions produced in Examples and Comparative Examples were sealed in a plastic container and left in a constant temperature room at a temperature of 25°C and humidity of 60% for a predetermined period of time, and then opened and stirred with a spatula to cause fluidization. I confirmed the gender. "×" means that it became impossible to stir for less than 12 hours, "△" means that it became impossible to stir for more than 12 hours and less than 24 hours, and "〇" means that it became impossible to stir for more than 24 hours but less than 48 hours. , Those that showed fluidity even after 48 hours or more were rated "◎".

<Test Example 3: Evaluation of low temperature moldability>
The resin compositions produced in the examples and comparative examples were compression molded onto a 12-inch SUS plate using a compression molding device (pressure: 6 MPa, cure time: 5 minutes) to form a resin composition with a thickness of 300 μm. Obtained. "◎" indicates that a cured product with no tackiness was obtained at a mold temperature of less than 110°C; "○" indicates that a cured product without tackiness was obtained at a mold temperature of 110°C or higher and less than 120°C; mold temperature: 120°C Those in which a cured product with no tackiness was not obtained at °C were rated "×".

<Test Example 4: Evaluation of heat resistance>
The resin composition obtained in Test Example 3 was further heated at 130° C. for 2 hours to completely cure the resin composition. The glass transition temperature (Tg) of the obtained cured product was measured in a nitrogen atmosphere using a differential scanning calorimeter (DSC). The temperature increase rate was 5°C/min, and the measurement temperature range was 25°C to 280°C. Based on the method described in JIS K 7121, the midpoint of the part where the DSC curve shows a step-like change was defined as the Tg of the cured product (Tg before standing). Those with a Tg of 100°C or higher were marked as "◎", those with Tg of 80°C or higher and lower than 100°C were marked as "○", those with Tg of 60°C or higher and lower than 80°C were marked as "△", and those with a Tg of lower than 60°C as "x".

<Test Example 5: Evaluation of copper adhesion>
The resin compositions produced in Examples and Comparative Examples were placed on the shiny surface of copper foil and compression molded onto a 12-inch SUS plate using a compression molding device (pressure: 6 MPa, cure time: 5 minutes). A resin composition with a copper foil having a thickness of 300 μm was formed. Note that the conditions listed in Table 1 below were used for the mold temperature. Thereafter, the resin composition was thermally cured by heating at 130° C. for 2 hours. In Comparative Example 2, the compression mold was cured for 15 minutes, and then heated at 180° C. for 90 minutes to cure the resin composition. The obtained cured product of the resin composition with copper foil was cut into 1 cm square pieces, and a φ5.8 mm stud pin with adhesive was erected perpendicularly to the copper foil matte surface of the obtained cured product plate with copper foil. Further, a backing plate with an adhesive was placed on the cured side of the same cured product plate and heated at 150° C. for 60 minutes to create a test piece in which the stud pin, the cured product plate with copper foil, and the backing plate were adhered. The obtained test piece was subjected to a vertical tensile test at a test speed of 0.1 kg/sec using a vertical tensile tester ROMULUS manufactured by QUAD GROUP. Measurements were performed on five test pieces, and the average value was calculated. Those whose adhesive strength was 100 Kgf/cm ² or more were rated “〇”, and those whose adhesive strength was less than 100 Kgf/cm ² were rated “x”.

Table 1 below shows the nonvolatile components and their usage amounts in the resin compositions of Examples and Comparative Examples, as well as the evaluation results of Test Examples.

From the above results, when a thiol-based curing agent is used as a component of the resin composition and a specific curing accelerator is used, or when the reaction initiation temperature is set to 70°C or higher and the reaction peak temperature is set to 130°C or lower, It was found to have excellent low-temperature formability and copper adhesion.

Claims (18)

A resin composition comprising (A) an epoxy resin, (B) an inorganic filler, (C) a thiol curing agent, and (D) a curing accelerator,
(A) component contains a glycidylamine type epoxy resin,
(B) component contains silica,
The content of component (B) is 70% by mass or more when the nonvolatile components in the resin composition are 100% by mass,
(D) component contains at least one selected from the group consisting of a phosphorus-based curing accelerator, a urea-based curing accelerator, a guanidine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator;
A resin composition in which the imidazole curing accelerator has a molecular weight of 1,000 or less. The resin composition according to claim 1, wherein component (D) contains at least one selected from the group consisting of a phosphorus-based curing accelerator, an imidazole-based curing accelerator, and a urea-based curing accelerator. The resin composition according to claim 1 or 2, wherein the reaction initiation temperature based on differential scanning calorimetry is 70°C or higher. The resin composition according to any one of claims 1 to 3, which has a reaction peak temperature of 130° C. or lower based on differential scanning calorimetry. The resin composition according to any one of claims 1 to 4, wherein the content of component (B) is 80% by mass or more when the nonvolatile components in the resin composition are 100% by mass. Component (C) is a hydrocarbon type thiol type hardening agent, an ether type thiol type hardening agent, a thioether type thiol type hardening agent, an amine type thiol type hardening agent, an alcohol type thiol type hardening agent, an alkyl isocyanurate type thiol type hardening agent The resin composition according to any one of claims 1 to 5, which is at least one selected from the group consisting of , and alkyl glycoluril type thiol curing agents. The resin composition according to any one of claims 1 to 6, wherein component (C) contains a thiol-based curing agent that is liquid at 25°C. A resin composition comprising (A) an epoxy resin, (B) an inorganic filler, (C) a thiol curing agent, and (D) a curing accelerator,
(A) component contains a glycidylamine type epoxy resin,
(B) component contains silica,
The content of component (B) is 70% by mass or more when the nonvolatile components in the resin composition is 100% by mass,
(D) component contains at least one selected from the group consisting of a phosphorus-based curing accelerator, a urea-based curing accelerator, a guanidine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator;
The imidazole curing accelerator has a molecular weight of 1,000 or less,
The reaction initiation temperature based on differential scanning calorimetry is 70°C or higher,
A resin composition having a reaction peak temperature of 130°C or less based on differential scanning calorimetry. The resin composition according to any one of claims 1 to 8, wherein the cured product of the resin composition has a glass transition temperature (Tg) of 80°C or higher. The resin composition according to any one of claims 1 to 9, for forming an insulating layer of a semiconductor chip package. The resin composition according to any one of claims 1 to 9, for forming an insulating layer of a circuit board. The resin composition according to any one of claims 1 to 9, for sealing a semiconductor chip in a semiconductor chip package. A cured product of the resin composition according to any one of claims 1 to 12. A resin sheet comprising a support and a resin composition layer containing the resin composition according to any one of claims 1 to 12 provided on the support. A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 12. A semiconductor chip package comprising the circuit board according to claim 15 and a semiconductor chip mounted on the circuit board. A semiconductor chip package comprising a semiconductor chip and a cured product of the resin composition according to any one of claims 1 to 12, which seals the semiconductor chip. A semiconductor device comprising the semiconductor chip package according to claim 16 or 17.