TWI804489B - resin composition - Google Patents

Abstract

[Problem] The present invention provides an insulating layer capable of suppressing warpage that occurs when the insulating layer is formed, and also provides an insulating layer having excellent thermal expansion coefficient, thermal conductivity, and adhesion strength to copper plating. The resin composition of the insulating layer with physical properties such as surface roughness, etc.; and the resin sheet, circuit board, and semiconductor chip package obtained by using the resin composition. [Solution] A resin composition containing (A) epoxy resin, (B) inorganic filler, (C) hardener, and (D) amphiphilic polyether block copolymer.

Description

resin composition

The present invention is an invention related to a resin composition. Also, it relates to a resin sheet, a circuit board, and a semiconductor chip package obtained by using the resin composition.

In recent years, with the miniaturization and high performance of electronic equipment, there is a need for multi-layer stacking, miniaturization and high-density wiring in semiconductor packaging substrates. In addition, with the popularization of smartphones and tablet PCs, thin packaging substrates such as thinning, thinning core materials, and even core-free structures are strongly required. Along with this point, there is a need for a substrate capable of suppressing warpage that occurs when an insulating layer is formed.

For example, Patent Document 1 discloses a resin composition capable of reducing warpage due to cure shrinkage and having excellent flexibility. However, in response to the demand for higher performance in recent years, a resin composition with higher performance is still required. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese National Publication No. 2000-64960

[Problem to be solved by the invention]

The present invention is to provide a resin composition suitable for forming an insulating layer in a stacked layer of a high-density, thinned, or denuclearized wiring board, a wafer-level chip size package, and the like. Specifically, for example, it provides A resin composition that can suppress the warpage that occurs when the insulating layer is formed, and even has excellent thermal expansion coefficient, thermal conductivity, adhesion strength with copper plating, surface roughness and other physical properties; use Resin sheets, circuit substrates, and semiconductor chip packages obtained from the resin composition. [How to solve the problem]

The inventors of the present invention, as a result of in-depth research on the above problems, found that when the resin composition contains epoxy resin, inorganic filler, hardener, and amphiphilic polyether block copolymer, the formation of the insulating layer can be suppressed. warping that actually occurs, thus completing the present invention.

骨架之酚系硬化劑，及活性酯系硬化劑所選出之1種以上者。 　　[10] 如[1]～[9]中任一項所記載的樹脂組成物，其中，(A)成份為，含有含縮合環構造之環氧樹脂。 　　[11] 如[1]～[10]中任一項所記載的樹脂組成物，其中，樹脂組成物經180℃、90分鐘熱硬化後之硬化物的硬化收縮率為0.27%以下。 　　[12] 如[1]～[11]中任一項所記載的樹脂組成物，其中，樹脂組成物經180℃、90分鐘熱硬化後之硬化物的25℃～150℃間之線性熱膨脹係數為3ppm/℃以上、30ppm/℃以下。 　　[13] 如[1]～[12]中任一項所記載的樹脂組成物，其為半導體晶片封裝之絕緣層用樹脂組成物。 　　[14] 如[1]～[13]中任一項所記載的樹脂組成物，其為使用半加成法(Semi-Additive Process)製程而形成線路的線路基板之絕緣層用樹脂組成物。 　　[15] 一種樹脂薄片，其特徵為，具有包含支撐體，與設置於該支撐體上的[1]～[14]中任一項所記載的樹脂組成物之樹脂組成物層。 　　[16] 一種線路基板，其特徵為，包含[1]～[14]中任一項所記載的樹脂組成物的硬化物所形成的絕緣層。 　　[17] 一種半導體晶片封裝，其特徵為，包含[16]所記載之線路基板，與搭載於前述線路基板上的半導體晶片。 　　[18] 一種半導體晶片封裝，其特徵為，包含[1]～[14]中任一項所記載的樹脂組成物或[15]所記載之樹脂薄片所密封的半導體晶片。 [發明之效果]That is, the present invention includes the following: [1] A resin composition characterized by comprising: (A) epoxy resin, (B) inorganic filler, (C) hardener, and (D) amphiphilic Polyether block copolymers. [2] The resin composition as described in [1], wherein the content of the component (B) is not less than 50% by mass and not more than 95% by mass when the non-volatile content in the resin composition is 100% by mass. [3] The resin composition as described in [1] or [2], wherein the component (B) is treated with a silane coupling agent containing a nitrogen atom. [4] The resin composition according to any one of [1] to [3], wherein the content of component (D) is 0.3% by mass when the non-volatile content in the resin composition is 100% by mass % or more and 15% by mass or less. [5] The resin composition as described in any one of [1] to [4], wherein component (D) contains at least one epoxy resin-mixable polyether block segment, and at least one epoxy resin composition Resin is a block copolymer of non-mixed polyether block segments. [6] The resin composition as described in [5], wherein the epoxy resin mixed polyether block segment is composed of polyethylene oxide block, polypropylene oxide block, poly(ethylene oxide block) Alkane-co-propylene oxide) block, poly(ethylene oxide-ran-propylene oxide) block, and a mixture of these selected more than one polyalkylene oxide block; epoxy resin is not The mixed polyether block segment is a polycyclic polycyclic compound selected from polybutylene oxide block, polyhexylene oxide block, polydodecane oxide block, and mixtures thereof. oxane block. [7] The resin composition according to any one of [1] to [6], which further contains (E) a carbodiimide compound. [8] The resin composition according to any one of [1] to [7], which further contains (F) a thermoplastic resin. [9] The resin composition according to any one of [1] to [8], wherein component (C) is composed of three

One or more selected phenolic hardeners and active ester hardeners. [10] The resin composition according to any one of [1] to [9], wherein the component (A) is an epoxy resin containing a condensed ring structure. [11] The resin composition according to any one of [1] to [10], wherein the cure shrinkage of the cured product after the resin composition is thermally cured at 180° C. for 90 minutes is 0.27% or less. [12] The resin composition according to any one of [1] to [11], wherein the linear thermal expansion coefficient of the cured product after thermal curing at 180°C for 90 minutes is between 25°C and 150°C It is 3 ppm/°C or more and 30 ppm/°C or less. [13] The resin composition according to any one of [1] to [12], which is a resin composition for an insulating layer of a semiconductor chip package. [14] The resin composition according to any one of [1] to [13], which is a resin composition for an insulating layer of a wiring board formed by a semi-additive process. [15] A resin sheet characterized by having a resin composition layer comprising a support and the resin composition described in any one of [1] to [14] provided on the support. [16] A circuit board characterized by comprising an insulating layer formed of a cured product of the resin composition described in any one of [1] to [14]. [17] A semiconductor chip package comprising the circuit board described in [16], and a semiconductor chip mounted on the circuit board. [18] A semiconductor chip package comprising a semiconductor chip sealed with the resin composition described in any one of [1] to [14] or the resin sheet described in [15]. [Effect of Invention]

The content of the present invention is to provide a material that can suppress the warpage that occurs when the insulating layer is formed, and has excellent thermal expansion coefficient, thermal conductivity, adhesion strength with copper plating, surface roughness, etc. A resin composition for an insulating layer; a resin sheet, a circuit substrate, and a semiconductor chip package obtained by using the resin composition.

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

[Resin composition] The resin composition of the present invention contains: (A) epoxy resin, (B) inorganic filler, (C) hardener, and (D) amphiphilic polyether block copolymer.

When the resin composition contains (A) component, (B) component, (C) component, and (D) component, an insulating layer capable of suppressing warpage can be obtained. The resin composition may further contain (E) carbodiimide compound, (F) thermoplastic resin, (G) polybutadiene structure, polysiloxane structure, poly(methyl) Acrylic structure, polyalkane structure, polyalkoxy structure, polyisoprene structure, polyisobutylene structure, and resin with one or more structures selected from polycarbonate structure, (H) rubber particles, (I) cured accelerator, (J) flame retardant.

The "resin component" in this specification refers to a component other than (B) inorganic filler among the non-volatile components constituting the resin composition. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) epoxy resin> The resin composition contains (A) epoxy resin. Epoxy resins are not particularly limited as long as the resin composition of the present invention can be thermally cured, for example, naphthalene-type epoxy resins, naphthalene-type 4-functional epoxy resins, naphthol-type epoxy resins, perylene Ether-type epoxy resin, anthracene-type epoxy resin, dicyclopentadiene-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type 4-functional epoxy resin, naphthol-type epoxy resin, pernaphthylether-type epoxy resin , dicyclopentadiene type epoxy resin and other epoxy resins with condensed ring structure; bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol S type epoxy resin; bisphenol AF type ring Oxygen resin; Trisphenol-type epoxy resin; Novolac-type epoxy resin; Naphthol-Novolac-type epoxy resin; Phenol-Novolac-type epoxy resin; Tert-butyl-catechol-type epoxy resin; shrinkage Glycerylamine-type epoxy resins; glycidyl ester-type epoxy resins; cresol-novolak-type epoxy resins; biphenyl-type epoxy resins; linear aliphatic epoxy resins; epoxy resins with a butadiene structure; Cyclic epoxy resins; heterocyclic epoxy resins; epoxy resins containing spiro rings; cyclohexanedimethanol epoxy resins; trimethylol epoxy resins; tetraphenylethane epoxy resins, etc. . For epoxy resins, these may be used alone or in combination of two or more. The component (A) is preferably at least one selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, and epoxy resin having a condensed ring structure. Among them, component (A) can obtain an insulating layer with excellent physical properties such as low thermal expansion coefficient, thermal conductivity, adhesion strength with copper plating, and surface roughness. Resin is preferred. Epoxy resins with a condensed ring structure, in the above examples, naphthalene-type epoxy resins, naphthalene-type 4-functional epoxy resins, naphthol-type epoxy resins, pernaphthalene-type epoxy resins, anthracene-type epoxy resins , Dicyclopentadiene type epoxy resin is preferred, and naphthalene type epoxy resin and naphthol type epoxy resin are particularly preferred.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. Also, the epoxy resin preferably has an aromatic structure, and when two or more epoxy resins are used, at least one of them preferably has an aromatic structure. When the non-volatile content of the epoxy resin is 100% by mass, at least 50% by mass is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, it also contains: epoxy resin having two or more epoxy groups in one molecule, and liquid epoxy resin at a temperature of 20°C (hereinafter, also referred to as "liquid epoxy resin"), and epoxy resin having two or more epoxy groups in one molecule It is preferable to have more than 3 epoxy groups and a solid epoxy resin at a temperature of 20°C (hereinafter also referred to as "solid epoxy resin"). Epoxy resin, when liquid epoxy resin and solid epoxy resin are used together, a resin composition with excellent flexibility can be obtained. In addition, the fracture strength of the cured product of the resin composition can also be increased. The aromatic structure is generally defined as a chemical structure that is aromatic, and also includes polycyclic aromatics and aromatic heterocycles.

Liquid epoxy resins, such as 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-novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and butadiene structure epoxy resin Epoxy resins are preferred, and glycidylamine epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol AF epoxy resins and naphthalene epoxy resins are more preferred. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation, "828US" and "jER828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation. epoxy resin), "jER807" (bisphenol F epoxy resin), "jER152" (phenol-novolac epoxy resin), "630", "630LSD" (glycidylamine epoxy resin), Xinri "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Tetsumikin Chemical Co., Ltd. "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemical Co., Ltd., "CELLOXIDE 2021P" manufactured by DAICEL (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), "ZX1658" manufactured by Nippon Steel & Sumikin Chemicals, "ZX1658GS" (liquid 1,4-glycidylcyclohexane), "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA Corporation Oxygen resin), etc. These may be used individually by 1 type, and may use it in combination of 2 or more types.

Solid epoxy resins, such as novolak type epoxy resins, naphthalene type 4-functional epoxy resins, cresol-novolac type epoxy resins, dicyclopentadiene type epoxy resins, triphenol type epoxy resins, Naphthol-type epoxy resin, biphenyl-type epoxy resin, pernaphthyl ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, tetraphenylethane-type epoxy resin are preferred, and phenolic Varnish-type epoxy resins, naphthalene-type four-functional epoxy resins, naphthol-type epoxy resins, and biphenyl-type epoxy resins are preferred. Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin) and "N-690" manufactured by DIC Corporation. (cresol-novolak type epoxy resin), "N-695" (cresol-novolak type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH ", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (Phenyl ether type epoxy resin) , "EPPN-502H" (triphenol type epoxy resin), "NC7000L" (naphthol-novolak type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" manufactured by Nippon Kayaku Co., Ltd. "(biphenyl type epoxy resin), "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "ESN485" (naphthol-novolak type epoxy resin), "ESN475V" manufactured by Mitsubishi Chemical Corporation YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100" manufactured by Osaka Gas Chemical Co., Ltd. ", "CG-500", "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YL7800" (stilbene type epoxy resin), "jER1010" manufactured by Mitsubishi Chemical Corporation (solid bisphenol A-type epoxy resin), "jER1031S" (tetraphenylethane-type epoxy resin), "157S70" (novolac-type epoxy resin), etc. These may be used individually by 1 type, and may use it in combination of 2 or more types.

Epoxy resin, when liquid epoxy resin and solid epoxy resin are used together, the ratio of these (liquid epoxy resin: solid epoxy resin) is 1:0.1 based on the mass ratio The range of ~1:15 is better. When the ratio of the liquid epoxy resin to the solid epoxy resin is within this range, i) when used in the form of a resin sheet, it has appropriate adhesiveness, and ii) when used in the form of a resin sheet, it can be Sufficient flexibility is obtained to improve handleability, and iii) effects such as that a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of the above i) to iii), the quantitative ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is based on a mass ratio of 1 : The range of 0.3-1:10 is better, and the range of 1:0.6-1:8 is more preferable.

The content of the epoxy resin in the resin composition is preferably 1 mass % when the non-volatile content in the resin composition is 100 mass % from the viewpoint of obtaining an insulating layer with good mechanical strength and insulation reliability. % or more, more preferably at least 2% by mass, and particularly preferably at least 5% by mass. The upper limit of the epoxy resin content is not particularly limited as long as the effect of the present invention can be achieved, but it is preferably 20% by mass or less, more preferably 15% by mass or less, and most preferably 10% by mass or less.

The epoxy equivalent of the epoxy resin is preferably 50-5000, more preferably 50-3000, particularly preferably 80-2000, most preferably 110-1000. Within this range, the cured product can have sufficient crosslink density, and an insulating layer with low surface roughness can be obtained. In addition, the epoxy equivalent is measured according to the regulation of JIS K7236, and means the mass of the resin containing 1 equivalent of epoxy groups.

The weight average molecular weight of the epoxy resin is preferably 100-5000, more preferably 250-3000, and most preferably 400-1500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) method.

The number average molecular weight of the epoxy resin is preferably not more than 5000, more preferably not more than 4000, particularly preferably not more than 3000. The lower limit is preferably at least 100, more preferably at least 300, and most preferably at least 500. The number average molecular weight (Mn) is the number average molecular weight of polystyrene conversion measured using GPC (gel permeation chromatography).

The glass transition temperature (Tg) of the epoxy resin is preferably higher than 25°C, more preferably higher than 30°C, particularly preferably higher than 35°C. The upper limit is preferably at most 500°C, more preferably at most 400°C, particularly preferably at most 300°C.

<(B) Inorganic filler> The resin composition contains (B) inorganic filler. The material of the inorganic filler is not particularly limited, for example, silicon dioxide, alumina, glass, cordierite, silicate, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, water Aluminum stone, 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 titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silicon dioxide is suitable. Moreover, spherical silica is preferable as silica. As the inorganic filler, one type may be used alone, or two or more types may be used in combination.

The average particle size of the inorganic filler is preferably not more than 12 μm, more preferably not more than 10 μm, more preferably not more than 8 μm, more preferably not more than 5.0 μm, more preferably 2.5 μm or less, particularly preferably 2.2 μm or less, more preferably 2 μm or less. The lower limit of the average particle size is not particularly limited, but is preferably at least 0.01 μm, more preferably at least 0.05 μm, and particularly preferably at least 0.1 μm. Commercially available inorganic fillers having these average particle diameters include, for example, "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by ADMATECHS, "UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd., "SILFILE NSS-3N", "SILFILE NSS-4N", "SILFILE NSS-5N" manufactured by Tokuyama Corporation, "SC2500SQ" manufactured by ADMATECHS Corporation, "SO-C6", "SO-C4", "SO-C2", "SO-C1", "DAW-03" manufactured by Denka Corporation, "FB-105FD", etc.

The average particle size of inorganic fillers can be measured using the laser diffraction and scattering method based on the Mie scattering theory. Specifically, for example, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction-scattering particle size distribution measuring device, and the median of the diameters is measured as the average particle size. It is better to use ultrasonic waves to disperse inorganic fillers in water for measuring samples. As a laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba Manufacturing Co., Ltd., etc. can be used.

Inorganic fillers, from the viewpoint of improving wettability with the base resin, more than one aminosilane coupling agent, epoxy silane coupling agent, mercaptosilane coupling agent, silane coupling agent, alkoxy Surface treatment agents such as base silane compounds, organic silazane compounds, titanate-based coupling agents, etc. Commercially available surface treatment agents, for example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyl Trimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxy base silane), Shin-Etsu Chemical Co., Ltd. "KBM5783" (N-phenyl-3-aminooctyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy-type silane coupling agent), etc. Among them, the N-phenyl-3-aminoalkyltrimethoxysilane starting with N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminooctyltrimethoxysilane Nitrogen-containing silane coupling agents such as silanes are preferred, and aminosilane-based coupling agents containing phenyl groups are preferred, and N-phenyl-3-aminopropyltrimethoxysilane is more preferred.

The content of the inorganic filler in the resin composition is preferably at least 50% by mass when the non-volatile content in the resin composition is 100% by mass, and more preferably 60% by mass or more, especially preferably 65% by mass or more. The upper limit is preferably at most 95% by mass, more preferably at most 93% by mass, particularly preferably at most 90% by mass, from the viewpoint of the mechanical strength of the insulating layer, especially the tensile strength.

系硬化劑，及氰酸酯酯系硬化劑等。硬化劑可單獨使用1種亦可，或將2種以上合併使用亦可。(C)成份，以由酚系硬化劑、萘酚系硬化劑、活性酯系硬化劑及氰酸酯酯系硬化劑所選出之1種以上為佳，以由酚系硬化劑，及活性酯系硬化劑所選出之1種以上為佳，其中之一態樣，又以由酚系硬化劑及活性酯系硬化劑所選出之1種以上為更佳。<(C) Curing agent> The resin composition contains (C) curing agent. (C) The curing agent is not particularly limited as long as it has the function of curing resin such as component (A), for example, phenolic curing agent, naphthol-based curing agent, active ester-based curing agent, benzo evil

Hardeners and cyanate ester hardeners. A hardening agent may be used individually by 1 type, or may use it in combination of 2 or more types. Component (C) is preferably at least one selected from phenolic hardeners, naphthol hardeners, active ester hardeners, and cyanate ester hardeners. One or more types of curing agents are preferred, and one or more types of them are more preferably selected from phenol-based curing agents and active ester-based curing agents.

骨架之酚系硬化劑為較佳。The phenolic hardener and the naphthol hardener are preferably phenolic hardeners having a novolac structure or naphthol hardeners with a novolac structure from the viewpoint of giving sufficient strength to the hardened product. Also, from the point of view of adhesion to the conductor layer, nitrogen-containing phenolic hardeners are preferred, and those containing three

Skeleton phenolic hardener is preferred.

Specific examples of phenolic hardeners and naphthol hardeners include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN" and "CBN" manufactured by Nippon Kayaku Co., Ltd. , "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", "SN395" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "SN395" manufactured by DIC Corporation TD2090", "TD2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC- 9500", "KA-1160", "KA-1163", "KA-1165", "GDP-6115L", "GDP-6115H", "ELPC75" manufactured by Qunying Chemical Co., Ltd., etc.

Active ester-based hardeners are not particularly limited, and generally use phenolic esters, thiophenolic esters, N-hydroxylamine esters, esters of heterocyclic hydroxyl compounds, etc. Active ester-based compounds are preferred. The active ester hardening agent is preferably prepared by condensation reaction of carboxylic acid compound and/or thiocarboxylic acid compound and hydroxyl compound and/or thiol compound. In particular, from the viewpoint of improving heat resistance, active ester hardeners made of carboxylic acid compounds and hydroxyl compounds are preferred, active ester hardeners made of carboxylic acid compounds and phenolic compounds and/or naphthol compounds is better. Carboxylic acid compounds such as benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. Phenol compounds or naphthol compounds such as hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 ,6-Dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, glucinol, dicyclopentadiene-type diphenol compounds, phenol-phenolic novolac Varnish etc. Here, the "dicyclopentadiene-type diphenol compound" means a diphenol compound obtained by condensing one molecule of dicyclopentadiene and two molecules of phenol.

Specifically, for example, active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing acetylated phenol-novolaks, phenol-novolak-containing phenol Active ester compounds of formyl compounds are preferred, among which active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" means a divalent structure formed from phenylene-dicyclopentyl-phenylene.

Among the commercially available active ester-based hardeners, active ester compounds containing dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H ", "HPC-8000-65T", "EXB-8000L" (manufactured by DIC Corporation), active ester compounds containing a naphthalene structure such as "EXB9416-70BK" (manufactured by DIC Corporation), acetylated compounds containing phenol-novolac Active ester compounds such as "DC808" (manufactured by Mitsubishi Chemical Corporation), active ester compounds containing phenol-novolak benzoyl compounds such as "YLH1026" (manufactured by Mitsubishi Chemical Corporation), active ester compounds of phenol-novolac acetyl compounds Hardeners such as "DC808" (manufactured by Mitsubishi Chemical Corporation), active ester hardeners of benzoyl compounds of phenol-novolac such as "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation) and the like.

系硬化劑之具體例如，昭和高分子公司製之「HFB2006M」、四國化成工業公司製之「P-d」、「F-a」等。Benzox

Specific examples of the curing agent include "HFB2006M" manufactured by Showa High Polymer Co., Ltd., "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd., and the like.

化而得之預聚物等。氰酸酯酯系硬化劑之具體例如，LONZAJAPAN公司製之「PT30」及「PT60」(任一者皆為酚-酚醛清漆型多官能氰酸酯酯樹脂)、「BA230」、「BA230S75」(雙酚A二氰酸酯的一部份或全部經三

化而形成三聚物的預聚物)等。Cyanate ester-based hardeners, such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'- Methyl bis(2,6-xylyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4- cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-xylyl)methane, 1,3-bis(4- Bifunctional cyanate esters of cyanate phenyl-1-(methylethylene)benzene, bis(4-cyanate phenyl)sulfide, and bis(4-cyanate phenyl)ether Polyfunctional cyanate resins derived from resins, phenol-novolaks and cresol-novolacs, etc., and these cyanate resins are partially three

The resulting prepolymers, etc. Specific examples of cyanate ester-based hardeners include "PT30" and "PT60" (both of which are phenol-novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" ( Part or all of bisphenol A dicyanate

to form prepolymers of terpolymers) and the like.

The content of the component (C) is preferably at most 30% by mass, more preferably at most 20% by mass, most preferably at most 15% by mass, when the resin component in the resin composition is 100% by mass. Also, the lower limit is preferably at least 1% by mass, more preferably at least 3% by mass, and particularly preferably at least 5% by mass. When the content of the component (C) is within this range, the warpage that occurs when the insulating layer is formed can be suppressed, and it can be obtained with excellent thermal expansion coefficient, thermal conductivity, adhesion strength with copper plating, surface roughness, etc. physical insulating layer.

<(D) Amphiphilic polyether block copolymer> The resin composition contains (D) amphiphilic polyether block copolymer. In this specification, the amphiphilic polyether block copolymer refers to a block copolymer comprising at least one epoxy resin mixed polyether block segment and at least one epoxy resin non-mixed polyether block segment The meaning of things. When component (D) is contained, the toughness of the resin composition can be improved, and the stress relaxation performance can be improved, thereby reducing the warpage of the cured product of the resin composition.

Epoxy resin hybrid polyether block segments, such as epoxy resin hybrid polyether block segments derived from alkylene oxide, etc. Epoxy resin hybrid polyether block segments derived from alkylene oxide, for example, to contain polyethylene oxide blocks, polypropylene oxide blocks, poly(ethylene oxide-co-propylene oxide ) block, poly(ethylene oxide-ran-propylene oxide) block, and more than one polyalkylene oxide block selected from the mixture of these is preferred, and the polyethylene oxide block is better.

The epoxy resin immiscible block segment, for example, at least one epoxy resin immiscible polyether block segment derived from alkylene oxide, and the like. At least one epoxy resin immiscible polyether block segment derived from alkylene oxide, for example, polybutylene oxide block, 1,2-epoxyhexane derived polyhexene oxide block segment, polydodecane oxide block derived from 1,2-epoxydodecane, and a mixture of these, preferably one or more polyalkylene oxides, with polybutylene oxide block is better.

The amphiphilic polyether block copolymer used in the present invention is preferably with more than one epoxy resin mixed block chain segment, and preferably with two or more epoxy resin mixed block chain segments. better. Similarly, it is preferable to have one or more types of epoxy resin immiscible block segments, and it is more preferable to have two or more types of epoxy resin immiscible block segments. Therefore, the (D) component, for example, is formed by having diblock, linear triblock, linear tetrablock, high-order multi-block structure, branched block structure, star block structure, and combinations thereof. The epoxy resin mixed block segment selected by the group, or the epoxy resin non-mixed block segment is preferred.

The amphiphilic polyether block copolymer can contain other segments in the molecule within the scope of not impairing its effect. Other segments such as polyvinylpropylene (PEP), polybutadiene, polyisoprene, polydimethylsiloxane, polybutylene oxide, polyhexene oxide, polyethylhexyl Polyalkylmethacrylates such as methacrylates, mixtures thereof, and the like.

The number average molecular weight of the amphiphilic polyether block copolymer is preferably 3,000-20,000. The number average molecular weight is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) method.

Amphiphilic polyether block copolymers, for example, poly(ethylene oxide)-b-poly(butylene oxide) (PEO-PBO); poly(ethylene oxide)-b-poly(butylene oxide) Alkane)-b-poly(ethylene oxide) (PEO-PBO-PEO) and other amphiphilic polyether triblock copolymers, etc. As the amphiphilic block copolymer, commercially available items can be used. Commercially available items include "Fortegra 100" manufactured by The Dow Chemical Company and the like.

The content of the component (D) is preferably at least 0.3% by mass, more preferably at least 0.4% by mass, especially from the standpoint of improving crack resistance when the non-volatile content in the resin composition is 100% by mass. Preferably 0.5% by mass above. The upper limit is not particularly limited as long as the effect of the present invention can be achieved, but it is preferably 15% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass or less.

<(E) Carbodiimide compound>

The resin composition of the present invention is component (E), which may contain a carbodiimide compound. A carbodiimide compound is a compound having one or more carbodiimide groups (-N=C=N-) in one molecule. When the component (E) is contained, it can be obtained with excellent adhesion to the conductor layer. Coated insulating layer. The carbodiimide compound is preferably a compound having two or more carbodiimide groups in one molecule. The carbodiimide compound may be used alone or in combination of two or more.

In one embodiment, the carbodiimide compound contained in the resin composition of the present invention has a structure represented by the following formula (1).

(In the formula, X represents an alkylene group, a ring alkylene group, or an arylylene group, and these may have substituents. p represents an integer of 1 to 5. When there are multiple Xs, these may be the same or different Yes. * indicates a bonded key).

The number of carbon atoms in the alkylene group represented by X is preferably 1-20, more preferably 1-10, particularly preferably 1-6, 1-4, or 1-3. The number of carbon atoms is the number of carbon atoms excluding substituents. Preferable examples of the alkylene group include, for example, a methylene group, an ethylene group, a propylidene group, and a butylene group.

The number of carbon atoms in the cycloalkylene group represented by X is preferably 3-20, more preferably 3-12, particularly preferably 3-6. The number of carbon atoms is the number of carbon atoms excluding substituents. Preferable examples of the cycloalkylene group include, for example, cyclopropyl, cyclobutylene, cyclopentylene, and cyclohexylene.

The aryl extended group represented by X is a group obtained by removing two hydrogen atoms from the aromatic ring of an aromatic hydrocarbon; the number of carbon atoms in the aryl extended group is preferably 6-24, more preferably 6-18, Particularly preferred is 6-14, most preferably 6-10. The number of carbon atoms is the number of carbon atoms excluding substituents. Preferable examples of the arylylene group include, for example, phenylene group, naphthylene group, and anthracenyl group.

The alkylene group, cycloalkylene group or aryl group represented by X may have a substituent. The substituent is not particularly limited, for example, a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, an aryloxy group, an acyl group and an acyloxy group. Halogen atoms used as substituents include, for example, fluorine atom, chlorine atom, bromine atom, iodine atom and the like. The alkyl and alkoxy groups used as substituents may be either linear or branched, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, particularly preferably 1~6, 1~4, or 1~3. The number of carbon atoms of the cycloalkyl group and cycloalkoxy group used as the substituent is preferably 3-20, more preferably 3-12, particularly preferably 3-6. The aryl group used as a substituent is a group obtained by removing one hydrogen atom from the aromatic ring of an aromatic hydrocarbon, and the number of carbon atoms is preferably 6-24, more preferably 6-18, particularly preferably 6. ~14, preferably 6~10. The number of carbon atoms of the aryloxy group used as a substituent is preferably 6-24, more preferably 6-18, particularly preferably 6-14, most preferably 6-10. The acyl group used as a substituent is a group represented by the formula: -C(=O)-R ¹ (wherein R ¹ represents an alkyl or aryl group). The alkyl group represented by ^R1 may be either linear or branched, and the number of carbon atoms is preferably 1-20, more preferably 1-10, particularly preferably 1-6, 1~4, or 1~3. The number of carbon atoms of the aryl group represented by R ¹ is preferably 6-24, more preferably 6-18, particularly preferably 6-14, most preferably 6-10. The acyloxy group used as a substituent is a group represented by the formula: -OC(=O)-R ¹ (in the formula, R ¹ represents the same meaning as described above). Among them, the substituents, for example, are preferably alkyl, alkoxy, and acyloxy, more preferably alkyl.

In formula (1), p represents the integer of 1-5. From the viewpoint of realizing an insulating layer having better heat resistance, laser hole reliability, and adhesion to the conductor layer, p is preferably 1-4, more preferably 2-4, particularly preferably 2 or 3 .

In formula (1), when there are a plurality of Xs, these may be the same or different. In a preferred embodiment, at least one X is an alkylene group or a cycloalkylene group, and these may have a substituent.

In a preferred embodiment, the carbodiimide compound preferably contains 50% by mass or more, more preferably 60% by mass when the mass of the entire molecule of the carbodiimide compound is 100% by mass. Above, it is particularly preferable to contain 70% by mass or more, most preferably 80% by mass or more, or 90% by mass or more of the structure represented by the formula (1). The carbodiimide compound can be substantially formed by the structure represented by formula (1) in addition to the terminal structure. The terminal structure of the carbodiimide compound is not particularly limited, for example, an alkyl group, a cycloalkyl group, and an aryl group, etc., which may have substituents. The alkyl group, cycloalkyl group and aryl group used in the terminal structure may be the same as the alkyl group, cycloalkyl group and aryl group described in the substituents that the group represented by X may have. Moreover, the substituent which the group used as a terminal structure may have may be the same as the substituent which the group represented by X may have.

When the resin composition hardens, from the viewpoint of suppressing outgassing (outgass), the weight average molecular weight of the carbodiimide compound is preferably at least 500, more preferably at least 600, particularly preferably at least 700, and most preferably at least 700. Above 800, preferably above 900 or above 1000. Also, from the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the carbodiimide compound is preferably 5,000 or less, more preferably 4,500 or less, particularly preferably 4,000 or less, most preferably 3,500 or less, and most preferably 5,000 or less. Below 3000. The weight average molecular weight of a carbodiimide compound can be measured, for example using the gel permeation chromatography (GPC) method (polystyrene conversion).

Also, when the carbodiimide compound contains an isocyanate group (-N=C=O) in the molecule caused by the production method. From the viewpoint of obtaining a resin composition with good storage stability and realizing an insulating layer with desired characteristics, the content of isocyanate groups in carbodiimide compounds (also called "NCO content") , preferably less than 5% by mass, more preferably less than 4% by mass, particularly preferably less than 3% by mass, most preferably less than 2% by mass, most preferably less than 1% by mass or less than 0.5% by mass.

As a carbodiimide compound, a commercial item can also be used. Commercially available carbodiimide compounds, for example, Carbodilite (registered trademark) V-02B, V-03, V-04K, V-07 and V-09 manufactured by Nisshinbo Chemical Co., Ltd., Stabaxol (registered trademark) manufactured by Wright Chemical Co., Ltd. Trademark) P, P400, and Hycanine510 etc.

When the resin composition contains (E) component, the content of (E) component can simultaneously obtain an insulating layer with any characteristic of excellent heat resistance, laser hole reliability, and adhesion to the conductor layer From the standpoint, when the resin content is 100% by mass, it is preferably at least 0.1% by mass, more preferably at least 0.3% by mass, and more preferably at least 0.5% by mass. The upper limit of the content of the carbodiimide compound is not particularly limited, but it is preferably not more than 10% by mass, more preferably not more than 8% by mass, and more preferably not more than 5% by mass.

<(F) Thermoplastic resin> The resin composition contains a thermoplastic resin. Thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyimide resins, polyamideimide resins, polyetherimide resins, polyetherimide resins, polyetherimide resins, Polyphenylene ether resin, polyether ether ketone resin, polyester resin, etc.

The polystyrene-equivalent weight average molecular weight of the phenoxy resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of a phenoxy resin is what was measured using the gel permeation chromatography (GPC) method. Specifically, for example, the polystyrene-equivalent weight average molecular weight of the phenoxy resin can be measured using LC-9A/RID-6A manufactured by Shimadzu Corporation, and Shodex K-800P manufactured by Showa Denko Co., Ltd. as a column. /K-804L/K-804L, using chloroform as the mobile phase, measured at a column temperature of 40°C, and calculated using the standard polystyrene calibration curve. Similarly, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, more preferably in the range of 20,000 to 60,000.

Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both of which are phenoxy resins containing a bisphenol A structure), "YX8100" (phenoxy resins containing a bisphenol S skeleton) Base resin), and "YX6954" (phenoxy resin containing bisphenol acetophenone structure), others, such as "FX280" and "FX293" manufactured by Nippon Steel and Sumikin Chemical Co., Ltd., "YX7180" manufactured by Mitsubishi Chemical Corporation ", "YX6954", "YX7553", "YX7553BH30", "YL7769", "YL6794", "YL7213", "YL7290", "YL7891" and "YL7482". Among them, phenoxy resins having a polyalkoxy structure are preferable, and specific examples include "YX-7180" and "YX7553BH30" manufactured by Mitsubishi Chemical Corporation.

Specific examples of polyvinyl acetal resins include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C" and "Denka Butyral 6000-C" manufactured by Denki Kagaku Kogyo Co., Ltd. Butyraldehyde 6000-EP", Sekisui Chemical Co., Ltd.'s S-LEC BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series, etc.

Specific examples of the polyimide resin include "Rika-Coad SN20" and "Rika-Coad PN20" manufactured by Nippon Chemical Co., Ltd.

Specific examples of the polyamideimide resin include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd., "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd., and the like.

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. and the like.

Specific examples of the polyethylene resin include polyethylene "P1700" and "P3500" manufactured by Solvay Advanced Polymer Co., Ltd., and the like.

When the resin composition contains the component (F), the content of the component (F) is preferably 1% by mass or more, more preferably 3% by mass, when the resin component is 100% by mass, from the viewpoint of imparting flexibility. Above, especially preferably at least 5% by mass, most preferably at least 50% by mass, at least 55% by mass, and at least 60% by mass. The upper limit is preferably at most 85 mass %, more preferably at most 80 mass %, particularly preferably at most 75 mass %, at most 20 mass %, at most 15 mass %, or at most 10 mass %.

<(G) The molecule has a polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkane structure, polyalkoxy structure, polyisoprene structure, polyisobutylene structure, and Resin with one or more structures selected from the polycarbonate structure> The (G) component in the resin composition may contain polybutadiene structure, polysiloxane structure, poly Resin with one or more structures selected from (meth)acrylate structure, polyalkane structure, polyalkoxy structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure. (G) Component is a resin different from (F) thermoplastic resin. (G) The component has one or more selected from polybutadiene structure, poly(meth)acrylate structure, polyalkoxy structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure Two or more structures are preferred, and one or more structures selected from polybutadiene structures and polycarbonate structures is preferred. When the resin composition contains (G) component, the insulating layer has low elasticity, and has excellent connection strength, fracture bending deformation, and crack resistance, and can suppress the occurrence of warpage. In addition, "(meth)acrylate" means methacrylate and acrylate. These structures may be included in the main chain or may be included in the side chain.

The component (G) preferably has a high molecular weight from the viewpoint of reducing warpage when the resin composition hardens. The number average molecular weight (Mn) is preferably at least 1,000, more preferably at least 1,500, particularly preferably at least 3,000, and at least 5,000. The upper limit is preferably at most 1,000,000, more preferably at most 900,000. The number average molecular weight (Mn) is the number average molecular weight of polystyrene conversion measured using GPC (gel permeation chromatography).

Component (G) preferably has a functional group capable of reacting with component (A) from the viewpoint of improving the mechanical strength of the cured product. Moreover, the functional group which can react with (A) component also includes the functional group which appears by heating, for example.

In a preferred embodiment, the functional groups that can react with component (A) are, for example, those formed from hydroxyl groups, carboxyl groups, acid anhydride groups, phenolic hydroxyl groups, epoxy groups, isocyanate groups, and urethane groups. More than one functional group selected from the group; among them, the functional group is preferably, for example, hydroxyl group, acid anhydride group, phenolic hydroxyl group, epoxy group, isocyanate group and carbamate group, and hydroxyl group, acid anhydride group Groups, phenolic hydroxyl groups, and epoxy groups are preferred, and phenolic hydroxyl groups are particularly preferred. However, when the functional group includes an epoxy group, the number average molecular weight (Mn) is preferably 5,000 or more.

A preferred embodiment of the component (G) is a resin containing a polybutadiene structure, and the polybutadiene structure may be included in the main chain or in the side chain. Also, in the structure of polybutadiene, it may be partially or completely hydrogenated. Resins containing polybutadiene structures are called polybutadiene resins. Specific examples of polybutadiene resins include "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (polybutadiene containing acid anhydride groups), "GQ-1000" (polybutadiene with hydroxyl and carboxyl groups introduced) manufactured by Nippon Soda Co., Ltd., "G-1000", "G-2000", "G- 3000" (polybutadiene with hydroxyl groups at both terminals), "GI-1000", "GI-2000", "GI-3000" (hydrogenated polybutadiene with hydroxyl groups at both terminals), "FCA" manufactured by Nagase Chemical Co., Ltd. -061L" (epoxy resin with hydrogenated polybutadiene skeleton), etc. As an embodiment, for example, linear polyimides using hydroxyl-terminated polybutadiene, diisocyanate compounds, and tetrabasic anhydrides as raw materials (recorded in Japanese Patent Laid-Open No. 2006-37083 and International Publication No. 2008/153208 of polyimide), etc. In the polyimide, the content of the butadiene structure is preferably from 60% by mass to 95% by mass, more preferably from 75% by mass to 85% by mass. For details of the polyimide, reference may be made to the records in JP-A-2006-37083 and International Publication No. 2008/153208, which are also incorporated into this specification.

A preferred embodiment of the component (G) is a resin containing a poly(meth)acrylate structure. Resins containing poly(meth)acrylate structures are called poly(meth)acrylic resins. Examples of poly(meth)acrylic resins include DENSAIRENI manufactured by Nagase Chemical Co., Ltd., "ME-2000", "W-116.3", "W-197C", "KG-25", " KG-3000", etc.

A preferred embodiment of the component (G) is a resin containing a polycarbonate structure. Resins containing polycarbonate structures are called polycarbonate resins. Examples of polycarbonate resins include "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemical Co., Ltd., "C-1090", "C-2090" and "C-3090" manufactured by KURARAY Co., Ltd. (polycarbonate diol), etc. Also, as the component (G), a linear polyimide made of a hydroxyl-terminated polycarbonate, a diisocyanate compound, and a tetrabasic anhydride as a raw material can also be used. The content of the carbonate structure of the polyimide is preferably from 60% by mass to 95% by mass, more preferably from 75% by mass to 85% by mass. For details of the polyimide, reference may be made to the records in International Publication No. 2016/129541, which are also incorporated into this specification.

Also, another specific example of the component (G) is a resin containing a siloxane structure. Resins containing siloxane structures are called siloxane resins. Silicone resin, such as "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd. Polyimide (International Publication No. 2010/053185, JP-A 2002-12667, JP-A 2000-319386, etc.) and the like.

Other specific examples of the component (G) include resins containing an alkylene structure and an alkoxy structure. A resin containing an alkylene structure is called an alkyl resin, and a resin containing an alkoxy structure is called an alkoxy resin. The polyalkoxy structure is preferably a polyalkoxy structure with 2 to 15 carbon atoms, preferably a polyalkoxy structure with 3 to 10 carbon atoms, and more preferably a polyalkoxy structure with 5 to 6 carbon atoms. good. Specific examples of the alkyl resin and the alkoxy resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fiber Co., Ltd.

Another specific example of the component (G) is a resin containing an isoprene structure. Resins containing isoprene structure are called isoprene resins. Specific examples of the isoprene resin include "KL-610" and "KL613" manufactured by Kuraray Corporation.

Other specific examples of component (G) include resins with an isobutylene structure. Resins containing isobutylene structures are called isobutylene resins. Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation.

When the resin composition contains (G) component, the content of (G) component is preferably at least 1% by mass, more preferably at least 3% by mass, when the resin component is 100% by mass, from the viewpoint of imparting flexibility. Particularly preferred is at least 5% by mass, most preferably at least 50% by mass, at least 55% by mass, and at least 60% by mass. The upper limit is preferably at most 85 mass %, more preferably at most 80 mass %, particularly preferably at most 75 mass %, at most 15 mass %, at most 10 mass %, or at most 5 mass %.

＜(H) Rubber Particles＞ The resin composition contains (H) rubber particles. The rubber particles are different from the components (F) and (G), so they are not soluble in organic solvents, nor are they compatible with other components such as epoxy resin or hardener. Specific examples of rubber particles include acrylic rubber particles, polyamide microparticles, polysiloxane particles, etc. Specific examples of acrylic rubber particles, such as acrylonitrile butadiene rubber, butadiene rubber, acrylic rubber and other resins with rubber elasticity, are chemically cross-linked to form fine particles of resins that are insoluble and insoluble in organic solvents, etc. Specifically, for example, "AC3832" manufactured by Kanz Chemical Co., Ltd. and the like.

When the resin composition contains component (H), the content of component (H) is preferably at least 1% by mass, more preferably at least 3% by mass, when the resin component is 100% by mass, from the viewpoint of imparting flexibility , particularly preferably at least 5% by mass, most preferably at least 50% by mass, at least 55% by mass, and at least 60% by mass. The upper limit is preferably at most 85 mass %, more preferably at most 80 mass %, particularly preferably at most 75 mass %, at most 15 mass %, at most 10 mass %, or at most 5 mass %.

<(I) hardening accelerator> The resin composition contains (I) hardening accelerator. Hardening accelerators, such as phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, metal-based hardening accelerators, etc. , imidazole-based hardening accelerators, and metal-based hardening accelerators are preferred, and amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are more preferred. The hardening accelerator may be used alone or in combination of two or more.

Phosphorus-based hardening accelerators, for example, triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylboride, n-butylphosphonium tetraphenylboride, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, etc., and triphenylphosphine, tetrabutylphosphonium decanoic acid Salt is better.

Amine-based hardening accelerators, for example, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-para(dimethylaminomethyl)phenol , 1,8-diazabicyclo(5,4,0)-undecene, etc., and 4-dimethylaminopyridine, 1,8-diazabicyclo(5,4,0)-undeca Alkene is better.

、2,4-二胺基-6-[2’-十一烷基咪唑基-(1’)]-乙基-s-三

、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三

、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三

異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、2-苯基-4,5-二羥甲基咪唑、2-苯基-4-甲基-5-羥甲基咪唑、2,3-二氫-1H-吡咯[1,2-a]苯併咪唑、1-十二烷基-2-甲基-3-苄基咪唑鹽氯化物、2-甲基咪唑啉、2-苯基咪唑啉等的咪唑化合物及咪唑化合物與環氧樹脂之加成物等，又以2-乙基-4-甲基咪唑、1-苄基-2-苯基咪唑為佳。Imidazole-based hardening accelerators, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitic acid Esters, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-tri

, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-tri

, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-tri

, 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-tri

Isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dimethylolimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methyl Imidazole compounds such as base imidazoline, 2-phenylimidazoline and the adducts of imidazole compounds and epoxy resins, etc., and 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole better.

As the imidazole-based hardening accelerator, commercially available products such as "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc. can also be used.

Guanidine-based hardening accelerators, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethyl guanidine, 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-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc. Dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

Metal-based hardening accelerators include, for example, metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin, organometallic complexes, or organometallic salts. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetone (salt), cobalt (III) acetylacetone (salt), and copper (II) acetylacetone (salt). ) and other organic copper complexes, zinc (II) acetylacetone (salt) and other organic zinc complexes, iron (III) acetylacetone (salt) and other organic iron complexes, nickel (II) ) Organonickel complexes such as acetylacetone (salt), organomanganese complexes such as manganese (II) acetylacetone (salt), and the like. Organic metal salts are, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

When the resin composition contains (I) component, the content of (I) component, when the resin content of the resin composition is 100% by mass, is preferably 0.01% by mass to 3% by mass, more preferably 0.03% to 1.5% by mass Better, more preferably 0.05 to 1% by mass.

＜(J) Flame retardant＞ The resin composition contains (J) flame retardant. Flame retardants, for example, organic phosphorus-based flame retardants, phosphorus compounds containing organic nitrogen, nitrogen compounds, polysiloxane-based flame retardants, metal hydroxides, and the like. A flame retardant may be used individually by 1 type, or may use it in combination of 2 or more types.

As the flame retardant, commercially available products can also be used, for example, "HCA-HQ" manufactured by Sanko Co., Ltd., "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd., and the like. The flame retardant is preferably not easily hydrolyzed, for example, 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide, etc. are preferred.

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited. When the non-volatile content in the resin composition is 100% by mass, it is preferably 0.5% to 20% by mass, more preferably 0.5% by mass to 15% by mass, particularly preferably 0.5% by mass to 10% by mass.

<(K) Arbitrary additives> The resin composition may contain other additives, such as organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds, as well as binders, additives, etc., if necessary. Adhesives, defoamers, leveling agents, adhesion imparting agents, resin additives such as coloring agents, etc.

<Physical Properties of the Resin Composition> The hardened product of the resin composition of the present invention after heat curing at 180°C for 90 minutes shows the characteristic of lower curing shrinkage. That is, it is possible to obtain an insulating layer that suppresses curing shrinkage and suppresses warpage due to the shrinkage. The hardening shrinkage rate is preferably at most 0.27%, more preferably at most 0.25%, and most preferably at most 0.2%. The lower limit of the curing shrinkage rate is not particularly limited, and it may be 0.01% or more. Hardening shrinkage can be measured in accordance with the method described in <Measurement of Hardening Shrinkage> below.

The cured product of the resin composition of the present invention after thermal curing at 180°C for 30 minutes shows the property of suppressing warpage. Specifically, for example, the absolute value is preferably less than 20 mm, more preferably less than 10 mm. Warpage can be evaluated by the method described in <Warpage Test> below.

The hardened product of the resin composition of the present invention after being thermally cured at 180°C for 90 minutes shows the characteristic of lower linear thermal expansion coefficient (thermal expansion rate). That is, an insulating layer having a low coefficient of thermal expansion can be formed. The upper limit of the coefficient of linear thermal expansion between 30°C and 150°C is preferably 30ppm/°C or less, more preferably 25ppm/°C or less, more preferably 20ppm/°C or less, and more preferably 15ppm/°C or less. Below 10ppm/°C is particularly preferred. On the other hand, the lower limit of the coefficient of linear thermal expansion is not particularly limited, and is generally 3 ppm/°C or higher, 4 ppm/°C or higher, 5 ppm/°C or higher, and the like. The measurement of the coefficient of thermal expansion can be carried out according to the method described in <Measurement of Average Linear Thermal Expansion Coefficient (Thermal Expansion Coefficient)> below.

The cured product of the resin composition of the present invention after heat curing at 180°C for 30 minutes and then at 180°C for 60 minutes shows excellent peel strength with the metal layer, especially the metal layer formed by plating. characteristic. An insulating layer with excellent peel strength can be obtained. The peel strength is preferably at least 0.4 kgf/cm, more preferably at least 0.45 kgf/cm, and most preferably at least 0.5 kgf/cm. On the other hand, the upper limit of the peel strength is not particularly limited, but is generally 1.5 kgf/cm or less, 1 kgf/cm or less, and the like. The evaluation of peel strength can be carried out according to the method described in <Measurement of Tensile Peel Strength (Peel Strength) of Metal Layer and Surface Roughness (Ra) of Surface of Insulation Layer after Roughening Treatment> below. The metal layer is preferably a metal layer containing copper, more preferably a metal layer formed by plating.

The cured product of the resin composition of the present invention after thermal curing at 180°C for 90 minutes shows excellent thermal conductivity characteristics. An insulating layer with excellent thermal conductivity can be obtained. The thermal conductivity is preferably at least 0.5 W/m・K. The upper limit of thermal conductivity is 5.0W/m・K or less, 4.0W/m・K or less, or 3.5W/m・K or less. The thermal conductivity can be evaluated by the method described in <Measurement of Thermal Conductivity of Cured Material> below.

The resin composition of the present invention can produce an insulating layer that suppresses warpage that occurs when the insulating layer is formed. And it can produce an insulating layer with excellent thermal expansion coefficient, thermal conductivity, adhesion strength with copper plating, surface roughness and other physical properties. Therefore, the resin composition of the present invention is suitable for use as a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for an insulating layer of a semiconductor chip package), and a resin for forming an insulating layer of a circuit board (including a printed wiring board). The composition (resin composition for the insulating layer of the circuit board) is more suitable for use as a resin composition for forming an interlayer insulation layer on the substrate where the conductor layer is formed by plating (the interlayer insulation layer for the circuit substrate where the conductor layer is formed by plating). The resin composition for the layer, that is, the resin composition for the interlayer insulating layer of the circuit board for forming the circuit in the semi-additive process (Semi-Additive Process) is suitably used). Moreover, it is also suitably used as a resin composition for sealing a semiconductor wafer (resin composition for semiconductor wafer sealing), and a resin composition for forming wiring on a semiconductor wafer (resin composition for forming semiconductor wafer wiring).

[Resin Sheet] The resin sheet of the present invention includes a support and a resin composition layer formed of the resin composition of the present invention provided on the support.

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, particularly preferably 100 μm or less, 80 μm or less, 60 μm or less, 50 μm or less, or 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but it is usually 1 μm or more, 5 μm or more, 10 μm or more, and the like.

The support body is, for example, a film, metal foil, release paper, etc. formed of plastic materials, preferably a film or metal foil formed of plastic materials.

When the support is made of a film made of plastic material, the plastic material, for example, polyethylene terephthalate (hereinafter, also referred to as "PET"), polyethylene naphthyl ester (hereinafter, also referred to as "PEN") ), polyesters such as polycarbonate (hereinafter also referred to as "PC"), acrylates such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), poly Ether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthyl ester are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When metal foil is used as the support, the metal foil, for example, copper foil, aluminum foil, etc., is preferably copper foil. Copper foil can be made of a single metal of copper, or it can be made of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) Can.

The support body can be subjected to matting treatment, corona treatment, etc. on the surface connected with the resin composition layer.

Also, as the support body, a support body with a release layer attached to the surface connected to the resin composition layer can be used. A release agent for a release layer using a support with a release layer, for example, one selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin The above release agent, etc. The support body with the release layer can also use commercially available products, for example, "SK-1" and "SK-1" made by Linde Co., Ltd., which have a release layer mainly composed of alkyd resin release agent. AL-5", "AL-7", "LUMMIOR T60" manufactured by Toray Corporation, "PUREX" manufactured by Teijin Corporation, "YUNIPIRE" manufactured by UNITIKA Corporation, etc.

The thickness of the support body is not particularly limited, and generally it is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. Moreover, when using the support body with a release layer, it is preferable that the thickness of the support body with a release layer as a whole falls within the said range.

For resin flakes, for example, a resin composition can be dissolved in an organic solvent to obtain a resin coating, and the resin coating can be coated on a support using a slit coater or the like, and then dried to form a resin composition layer can be obtained in this way.

Organic solvents such as acetone, ketones such as methyl ethyl ketone (MEK) and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carboxylate Acetates such as benzyl acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide Amide solvents such as amine (DMAc) and N-methylpyrrolidone, etc. An organic solvent may be used individually by 1 type, and may use it in combination of 2 or more types.

Drying can be carried out using known methods such as heating and hot air blowing. The drying conditions are not particularly limited. Generally, the content of the organic solvent in the resin composition layer is dried until the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. It also varies according to the boiling point of the organic solvent in the resin coating. For example, when using a resin coating containing 30% to 60% by mass of organic solvent, it should be dried at 50°C to 150°C for 3 minutes to 10 minutes. As a result, a resin composition layer can be formed.

In the resin sheet, a protective film can be further laminated on the basis of the support on the surface not connected to the support of the resin composition layer (ie, the surface opposite to the support). The thickness of the protective film is not particularly limited, for example, 1 μm˜40 μm. When the protective film is laminated, impurities, etc. can be prevented from adhering to or damaging the surface of the resin composition layer. Resin flakes can be rolled up and stored in the form of a roll. When the resin sheet has a protective film, it can be used after peeling off the protective film.

The resin sheet is suitable for forming an insulating layer in the process of manufacturing a semiconductor chip package (resin sheet for insulation of a semiconductor chip package). For example, a resin sheet is suitable for forming an insulating layer of a circuit board (resin sheet for an insulating layer of a circuit board), and is more suitable for an interlayer insulating layer formed on a substrate to form a conductor layer by plating (conductor layer formed by plating). layer for the interlayer insulating layer of the circuit substrate). Examples of packages using these substrates include FC-CSP, MIS-BGA packages, ETS-BGA packages, and the like.

In addition, the resin sheet is suitable for sealing a semiconductor wafer (resin sheet for semiconductor wafer sealing), or for forming wiring on a semiconductor wafer (resin sheet for semiconductor wafer wiring formation), for example, it is suitable for use in a fan-out type WLP (Wafer Level Package). ), Fan-in WLP, Fan-out PLP (Panel Level Package), Fan-in PLP, etc. Moreover, MUF (Molding Under Filling) materials etc. which are used as a semiconductor chip connection board|substrate are also suitably used. In addition, the resin sheet is also suitable for use in a wide range of other applications requiring high insulation reliability, for example, it is suitable for use in forming an insulating layer of a circuit board such as a printed wiring board.

In addition to the resin sheet, a prepreg formed by impregnating a sheet-shaped fiber base material with the resin composition of the present invention can also be used.

The sheet-like fiber base material used in the prepreg is not particularly limited, and glass fiber cloth, aramid non-woven fabric, liquid crystal polymer non-woven fabric, etc., which are commonly used as base materials for prepregs, can generally be used. From the viewpoint of thinning, the thickness of the flaky fibrous substrate is preferably at most 900 μm, more preferably at most 800 μm, particularly preferably at most 700 μm, most preferably at most 600 μm. The lower limit of the thickness of the flake-shaped fibrous substrate is not particularly limited, and it is generally 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

The prepreg can be produced using known methods such as a hot melt method and a solvent method.

The thickness of the prepreg can be in the same range as that of the resin composition layer in the above-mentioned resin sheet.

[Wiring substrate] The wiring substrate of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention. The manufacturing method of the circuit board of the present invention comprises: (1) preparing a base material, and the step of the base material with the wiring layer having the wiring layer provided on at least one side of the base material, (2) The resin sheet of the present invention is laminated on the base material with the wiring layer in such a way that the wiring layer is embedded in the resin composition layer, and is thermally cured to form an insulating layer. (3) Forming the wiring layer between the layers Steps to connect. Moreover, the manufacturing method of a circuit board may also include (4) the step of removing a base material.

Step (3) is not particularly limited as long as the wiring layer can be connected between the layers, and the step of forming a through hole in the insulating layer, forming the wiring layer, and grinding or grinding the insulating layer to expose the wiring layer Preferably at least one of the steps.

<Step (1)> Step (1) is a step of preparing a substrate and a substrate with a wiring layer having a wiring layer provided on at least one side of the substrate. Usually, the base material with the wiring layer has a first metal layer and a second metal layer as part of the base material on both sides of the base material, and the side opposite to the base material side of the second metal layer A wiring layer is provided on the side surface. Specifically, a dry film (photosensitive resist film) is laminated on a base material, exposed and developed under specific conditions using a photomask, and a patterned dry film is formed. Using the developed patterned dry film as a mask, the patterned dry film is peeled off after forming a wiring layer by electroplating. Moreover, it is not necessary to have a 1st metal layer and a 2nd metal layer.

Substrates, such as glass epoxy substrates, metal substrates (stainless steel or cold-rolled steel plate (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene oxide substrates, etc., It can form a metal layer such as copper foil on the surface of the substrate. In addition, a metal layer such as a peelable first metal layer and a second metal layer (for example, ultra-thin copper foil with carrier copper foil manufactured by Mitsui Metal Mining Co., Ltd., trade name "Micro Thin") can also be formed on the surface. .

The dry film is not particularly limited as long as it is a photosensitive dry film formed of a photoresist composition. For example, a dry film of novolac resin, acrylic resin, or the like can be used. A commercial item can also be used for a dry film.

The lamination conditions of the base material and the dry film are the same as the conditions for embedding the resin sheet into the wiring layer in the step (2) described later, and the preferred range is also the same.

After the dry film is laminated on the base material, when the desired pattern is formed on the dry film, a photomask can be used to expose and develop according to specific conditions.

The line (line width)/space (width between lines) ratio of the wiring layer is not particularly limited, preferably less than 20/20μm (that is, the pitch is less than 40μm), more preferably less than 10/10μm, especially good It is less than 5/5 μm, particularly preferably less than 1/1 μm, most preferably more than 0.5/0.5 μm. It is not necessary for all the pitches to be the same in all the wiring layers. The minimum pitch of the wiring layer may be 40 μm or less, 36 μm or less, or 30 μm or less.

After the dry film pattern is formed, the wiring layer is formed and the dry film is peeled off. Among them, the formation of the wiring layer can be performed by using a dry film formed with a desired pattern as a mask, and it can be implemented by a plating method.

The conductor material used in the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer is one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. above metal. The wiring layer can be a single metal layer or an alloy layer. The alloy layer is, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-nickel alloy). Titanium alloy) formed by etc. Among them, from the viewpoint of the extensiveness, cost, and ease of pattern formation of the wiring layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or a nickel-chromium alloy , Copper-nickel alloy, copper-titanium alloy alloy layer is preferred, single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel-chromium alloy alloy layer is preferred , and a single metal layer of copper is better.

The thickness of the wiring layer is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, particularly preferably 10 to 20 μm, or 15 to 20 μm, depending on the desired wiring board design. In step (3), when using the step of grinding or grinding the insulating layer to expose the wiring layer so that the wiring layer is connected between the layers, the thickness of the wiring connected between the layers is preferably different from that of the unconnected wiring. . The thickness of the wiring layer can be adjusted by repeating the aforementioned pattern forming steps. Among the wiring layers, the thickness of the thickest wiring layer (conductive support) is preferably not less than 2 μm and not more than 100 μm, depending on the desired design of the wiring board. Moreover, the wiring connected between layers may also be in a convex shape.

After the wiring layer is formed, the dry film is peeled off. The stripping method of the dry film can be carried out by using an alkaline stripping solution such as sodium hydroxide solution, for example. If necessary, unnecessary wiring patterns can be removed by etching or the like to form desired wiring patterns. The distance between the formed wiring layers is as described above.

<Step (2)> Step (2) is to laminate the resin sheet of the present invention on the substrate with the wiring layer in such a way that the wiring layer is embedded in the resin composition layer, and heat-cure to form an insulating layer. the steps. In detail, the wiring layer of the base material with the wiring layer obtained in the above step (1) is laminated in such a manner that the resin composition layer of the resin sheet is embedded, and then the resin composition layer of the resin sheet is heated. harden to form an insulating layer.

The method of laminating the wiring layer and the resin sheet can be carried out by, for example, heating and pressing the resin sheet to the wiring layer from the support side after removing the protective film from the resin sheet. A member for heat-bonding a resin sheet to a wiring layer (hereinafter also referred to as “heat-bonding member”) is, for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller). In addition, instead of directly pressing the resin sheet with a heat pressing member, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet fully follows the surface unevenness of the wiring layer.

The lamination of the wiring layer and the resin sheet can be carried out by vacuum lamination after removing the protective film of the resin sheet. In the vacuum lamination method, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and pressing pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to In the range of 1.47 MPa, the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions with a pressure of 13 hPa or less.

After lamination, the laminated resin sheet can be smoothed under normal pressure (atmospheric pressure), for example, by pressing a heated pressing member from the support side. The pressure conditions for the smoothing treatment can be carried out under the same conditions as the above-mentioned heating and pressing conditions for lamination. In addition, the lamination and smoothing treatment can be continuously performed using the above-mentioned commercially available vacuum laminator.

After the resin composition layer is laminated on the wiring layer-embedded substrate, the resin composition layer is thermally cured to form an insulating layer. For example, the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, etc., and the general curing temperature is in the range of 120° C. to 240° C., and the curing time is in the range of 5 minutes to 120 minutes. Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature.

The support body of the resin sheet may be laminated on the substrate with the wiring layer and then peeled off after thermosetting, or the support may be peeled off before laminating the resin sheet on the substrate with the wiring layer. Moreover, before the roughening process process mentioned later, you may peel a support body.

After the resin composition layer is thermally cured to form the insulating layer, the surface of the insulating layer may also be polished. The grinding method is not particularly limited, and known methods can be used for grinding, for example, using a flat grinding disc to grind the surface of the insulating layer.

<Step (3)> Step (3) is a step of connecting the wiring layers between layers. The detailed content is a step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layer between layers. Or the step of grinding or grinding the insulating layer to expose the wiring layer so that the wiring layer is connected between layers.

When using the step of forming a via hole in the insulating layer, forming a conductor layer, and forming a connection between the wiring layer and the interlayer, the method of forming the via hole is not particularly limited, for example, laser irradiation, etching, mechanical drilling etc. It is better to use laser irradiation. This laser irradiation can be performed using any laser processing machine whose light source is a carbon dioxide laser, a YAG laser, an excimer laser, or the like. In detail, laser irradiation is performed from the support body surface side of the resin sheet to penetrate the support body and the insulating layer to expose the wiring layer and form via holes.

The conditions of the laser irradiation are not particularly limited, and the laser irradiation can be carried out using any appropriate steps according to the usual method in accordance with the selected means.

The shape of the through hole, when viewed from the extension direction, the shape of the opening is not particularly limited, and it is generally circular (slightly circular).

After the through-holes are formed, a so-called desmear step is performed as a step of removing smudges in the through-holes. In the process used for forming the conductor layer described later, wet desmear treatment can be performed on the through hole, for example, and dry desmear process such as plasma treatment process can be performed when the conductor layer is formed by the sputtering process. . In addition, in the stain removal step, the roughening treatment step may also be performed concurrently.

Before forming the conductor layer, roughening treatment may be performed on the via hole and the insulating layer. For the roughening treatment, generally known procedures and conditions can be employed. Examples of dry roughening treatment include, for example, plasma treatment, etc. Examples of wet roughening treatment, for example, sequentially use swelling treatment using a swelling solution, roughening treatment using an oxidizing agent, and intermediate treatment using a neutralizing solution. and processing methods.

The circuit board of the present invention can reduce the surface roughness (Ra) because it includes an insulating layer formed of a cured product of the resin composition of the present invention. That is, it has the property that the surface roughness (Ra) of the surface of the insulating layer after the roughening treatment is small. The surface roughness (Ra) is preferably at least 100 nm, more preferably at least 150 nm, and most preferably at least 200 nm. The upper limit is preferably at most 700 nm, more preferably at most 650 nm, particularly preferably at most 600 nm. The surface roughness (Ra) can be measured according to the description of <Measurement of the tensile peel strength (peel strength) of the metal layer and the surface roughness (Ra) of the surface of the insulating layer after roughening>>.

After the via hole is formed, the conductor layer is formed. The conductive material constituting the conductive layer is not particularly limited, and the conductive layer can be formed by any conventionally known preferred method such as plating, sputtering, and vapor deposition, and is preferably formed by plating. In a preferred embodiment, for example, using conventionally known techniques such as semi-additive process and full-additive method, plating is performed on the surface of the insulating layer to form a desired wiring pattern. conductor layer. In addition, in the resin sheet, when the support body is a metal foil, a conventionally known technique such as a subtractive process can be used to form a conductor layer having a desired wiring pattern. The conductor layer may have a single-layer structure, or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated.

Specifically, a plating seed layer is formed on the surface of the insulating layer using electroless plating. Next, on the formed plating seed layer, a mask pattern is formed by exposing a part of the plating seed layer corresponding to a desired wiring pattern. On the exposed plating seed layer, electroplating is used to form an electroplating layer. At this time, at the same time as forming the electroplating layer, through holes may be formed and embedded by electroplating to form buried holes. After the electroplating layer is formed, the mask pattern is removed. Subsequently, after the unnecessary plating seed layer is removed by etching or the like, a conductor layer having a desired wiring pattern is formed. Also, when forming the conductor layer, the dry film used for forming the mask pattern is the same as the dry film described above.

The conductor layer includes, for example, not only linear wiring but also electrode pads (lands) on which external terminals are mounted. In addition, the conductive layer may be composed only of electrode pads.

In addition, the conductor layer may be formed by forming the plating layer and the buried hole without patterning the mask after the plating seed layer is formed, and then performing patterning by etching.

When using the step of grinding or grinding the insulating layer to expose the wiring layer to form a connection between the wiring layer and the wiring layer, as long as the grinding or grinding method of the insulating layer can expose the wiring layer and make the ground or ground surface horizontal, It is not particularly limited, and conventionally known grinding methods or grinding methods can be used, for example, a chemical mechanical polishing method using a chemical mechanical polishing device, a mechanical polishing method such as a mirror surface, a plane grinding method using rotary abrasive grains, and the like. The steps of forming a through hole on the insulating layer to form a conductor layer and connecting the wiring layer between layers are the same, and can be performed on a stain removal step, a roughening treatment step, or the formation of a conductor layer. Also, it is not necessary to expose all the wiring layers, but only a part of the wiring layers may be exposed.

<Step (4)> Step (4) is a step of removing the substrate to form the circuit board of the present invention. The method of removing the substrate is not particularly limited. In a preferred embodiment, at the interface between the first and second metal layers, the circuit board is peeled off from the base material, and then the second metal layer is etched away using, for example, an aqueous copper chloride solution. If necessary, the substrate can also be peeled off in a state where the conductor layer is protected by the protective film.

In other embodiments, the circuit board can also be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as when using a resin sheet.

[Semiconductor Chip Package] A first aspect of the semiconductor chip package of the present invention is a semiconductor chip package in which a semiconductor chip is mounted on the above-mentioned circuit board. It can be used to make a semiconductor chip package by connecting it to the semiconductor chip on the above-mentioned circuit substrate.

As long as the terminal electrodes of the semiconductor chip can be electrically connected to the circuit wiring of the circuit board, the connection conditions are not particularly limited, and known conditions used in flip chips on which semiconductor chips are actually mounted can be used. In addition, the semiconductor chip and the circuit board may be connected via an insulating adhesive.

In a preferred embodiment, the semiconductor wafer is pressed against the circuit board. Pressing conditions, for example, the pressing temperature is 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 pressing time is in the range of 1 second to 60°C. The range of seconds (preferably 5 seconds to 30 seconds).

In addition, another preferred embodiment is that the semiconductor chip is connected by reflow on the circuit board. Reflow conditions, for example, range from 120°C to 300°C.

After the semiconductor chip is connected to the circuit substrate, for example, the semiconductor chip can be filled with an underfill to obtain a semiconductor chip package. The method of filling with an underfill material can be implemented using a well-known method. The resin composition or resin sheet of the present invention can also be used as an underfill material.

The second aspect of the semiconductor chip package of the present invention is, for example, the semiconductor chip package (Fan-out type WLP) shown as an example in FIG. 1 . A semiconductor chip package (Fan-out type WLP) 100 shown as an example in FIG. 1 is a semiconductor chip package using a sealing layer 120 made of the resin composition or resin sheet of the present invention. The semiconductor chip package 100 includes a sealing layer 120 formed to cover the semiconductor chip 110 and its periphery, and a rewiring formation layer ( insulating layer) 130 , conductor layer (rewiring layer) 140 , solder resist layer 150 , and bump 160 . The manufacturing method of these semiconductor chip packages includes: (A) the step of laminating the pre-fixed film on the base material, (B) the step of pre-fixing the semiconductor chip on the pre-fixed film, (C) applying the resin sheet of the present invention The resin composition layer of the present invention is laminated on the semiconductor wafer, or the resin composition of the present invention is coated on the semiconductor wafer, and it is thermally cured to form a sealing layer. (D) The base material and the pre-fixed film are made of The step of peeling off the semiconductor wafer, (E) The step of forming a rewiring formation layer (insulation layer) on the surface of the substrate and pre-fixed film from the semiconductor wafer, (F) Forming a conductor on the rewiring formation layer (insulation layer) layer (rewiring layer), and (G) a step of forming a solder resist layer on the conductor layer. In addition, the method for manufacturing a semiconductor chip package also includes (H) a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to form individual chips.

<Step (A)> Step (A) is a step of laminating a pre-fixed film on the substrate. The lamination conditions of the base material and the pre-fixed film are the same as the lamination conditions of the wiring layer and the resin sheet in step (2) of the manufacturing method of the circuit board, and the preferred range is also the same.

樹脂所形成之基板等。The material used as the substrate is not particularly limited. Substrates, for example, silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel plates (SPCC); epoxy resin infiltrated into glass fibers such as FR-4 substrates, etc., Substrate after thermal hardening treatment; bismaleimide three of BT resin

Substrates made of resin, etc.

The material of the pre-fixed film is not particularly limited as long as it can pre-fix the semiconductor wafer while peeling off the semiconductor wafer in the step (D) described later. As the pre-fixed film, commercially available ones can be used. Commercially available items include LIWA-α manufactured by Nitto Denko Co., Ltd., and the like.

<Step (B)> Step (B) is a step of pre-fixing the semiconductor wafer on the pre-fixed film. The pre-fixing method of the semiconductor wafer, for example, can be performed using known devices such as flip-chip connectors and die bonders. The arrangement and arrangement number of semiconductor chips can be appropriately set in accordance with the shape and size of the pre-fixed film, the number of target semiconductor packages produced, etc. For example, it can be arranged in a matrix of multiple rows and columns for pre-fix .

<Step (C)> Step (C) is to laminate the resin composition layer of the resin sheet of the present invention on the semiconductor wafer, or apply the resin composition of the present invention to the semiconductor wafer, and heat-cure it And the step of forming the sealing layer. In the step (C), it is preferable to laminate the resin composition layer of the resin sheet on the semiconductor wafer and heat-cure to form the sealing layer.

The lamination method of the semiconductor wafer and the resin sheet can be performed by, for example, heat-pressing the resin sheet to the semiconductor wafer from the support side after removing the protective film from the resin sheet. A member for thermally bonding a resin sheet to a semiconductor wafer (hereinafter, also referred to as “heat-pressing member”), for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller). In addition, instead of directly pressing the resin sheet with a heating and pressing member, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet can fully follow the surface irregularities of the semiconductor wafer.

In addition, the lamination method of the semiconductor wafer and the resin sheet can be carried out by vacuum lamination after the protective film is removed from the resin sheet. The lamination conditions in the vacuum lamination method are the same as the lamination conditions of the wiring layer and the resin sheet in the step (2) of the circuit board manufacturing method, and the preferred range is also the same.

The support of the resin sheet may be peeled off after the resin sheet is laminated on the semiconductor wafer and thermally cured, or the support may be peeled off before the resin sheet is laminated on the semiconductor wafer.

The coating conditions of the resin composition are the same as the coating conditions when forming the resin composition layer in the resin sheet of the present invention, and the preferred ranges are also the same.

<Step (D)> Step (D) is a step of peeling the substrate and pre-fixed film from the semiconductor wafer. The method of peeling can be appropriately changed in accordance with the material of the pre-fixed film, for example, the method of peeling off the pre-fixed film after heating, foaming (or expanding), and irradiating ultraviolet rays from the substrate side to reduce the thickness of the pre-fixed film. The method of peeling off due to the adhesive force, etc.

In the method of peeling off the pre-fixed film after heating, foaming (or expansion), the heating conditions are usually between 100° C. and 250° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in the method of irradiating ultraviolet rays from the base material side to reduce the adhesive force of the pre-fixed film and peeling off, the irradiation amount of ultraviolet rays is usually 10mJ/cm ² to 1000mJ/cm ² .

<Step (E)> Step (E) is a step of forming a rewiring forming layer (insulating layer) on the surface where the base material and pre-fixed film are peeled off from the semiconductor wafer.

The material that can form the rewiring formation layer (insulating layer) is not particularly limited as long as it has insulating properties when forming the rewiring formation layer (insulating layer). From the viewpoint of the ease of manufacturing semiconductor chip packages, Photosensitive resin and thermosetting resin are preferable. As the thermosetting resin, a resin composition having the same composition as the resin composition forming the resin sheet of the present invention can be used.

After the rewiring forming layer (insulating layer) is formed, the semiconductor wafer is connected to the conductor layer described later to form an interlayer connection, and via holes can be formed on the rewiring forming layer (insulating layer).

When forming a through hole, if the material for forming the rewiring formation layer (insulation layer) is photosensitive resin, first, the surface of the rewiring formation layer (insulation layer) can be irradiated with active energy rays through a shadow pattern, so that the surface of the irradiated part The rewiring layer is photohardened.

Active energy rays, for example, ultraviolet rays, visible light, electron rays, X-rays, etc., especially ultraviolet rays are preferred. The irradiation amount and irradiation time of ultraviolet rays can be appropriately changed according to the photosensitive resin. The exposure method can be a contact exposure method in which the mask pattern is adhered to the rewiring formation layer (insulating layer) to expose, and the mask pattern is not adhered to the rewiring formation layer (insulating layer). Any of the non-contact exposure methods for exposing with parallel rays may be used.

Next, the rewiring forming layer (insulating layer) is developed to remove the unexposed portion to form a via hole. For image development, either wet image development or dry image image may be used. As the developing solution used for wet development, a known developing solution can be used.

Developing methods include, for example, dipping, stirring, spraying, brushing, and scraping. From the viewpoint of resolution, stirring is preferred.

When the material for forming the rewiring formation layer (insulation layer) is a thermosetting resin, the method of forming the through hole is not particularly limited, for example, laser irradiation, etching, mechanical drilling, etc., and laser irradiation can be used better. Laser irradiation can be performed using any suitable laser processing machine whose light source is carbon dioxide laser, UV-YAG laser, excimer laser, or the like.

The conditions of the laser irradiation are not particularly limited, and the laser irradiation can be carried out using any appropriate steps according to the usual method in accordance with the selected means.

The shape of the through hole, when viewed from the extension direction, the shape of the opening is not particularly limited, and it is generally circular (slightly circular). The diameter of the top of the via hole (the diameter of the opening on the surface of the redistribution forming layer (insulating layer)) is preferably 50 μm or less, more preferably 30 μm or less, particularly preferably 20 μm or less. The lower limit is not particularly limited, but generally, it is preferably at least 10 μm, more preferably at least 15 μm, and most preferably at least 20 μm.

<Step (F)> Step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer). The method of forming a conductor layer on the rewiring formation layer (insulation layer) is the same as the method of forming a conductor layer after forming a through hole in the insulation layer in step (3) in the manufacturing method of the circuit board, and the preferred range is also the same. In addition, step (E) and step (F) can also be repeated, so that the conductor layer (rewiring layer) and the rewiring formation layer (insulating layer) are alternately laminated (stacked).

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

The material for forming the solder resist layer is not particularly limited as long as the solder resist layer is insulating when it is formed. From the viewpoint of ease of manufacturing semiconductor chip packages, photosensitive resins and thermosetting resins are preferred. . As the thermosetting resin, a resin composition having the same composition as the resin composition forming the resin sheet of the present invention can be used.

In addition, in the step (G), if necessary, bump processing for forming bumps may be performed. Bump processing can be performed using known methods such as solder balls and solder plating. Also, in the bump processing, the method of forming the through hole can be carried out in the same way as step (E).

<Step (H)> In the manufacturing method of a semiconductor chip package, a step (H) other than steps (A) to (G) may be included. The step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to form individual pieces.

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

The third aspect of the semiconductor chip package of the present invention is, for example, the rewiring formation layer (insulation layer) 130 and the solder resist layer 150 in the semiconductor chip package (Fan-out type WLP) shown as an example in FIG. 1 , is a semiconductor chip package made using the resin composition or resin sheet of the present invention.

[Semiconductor device] The semiconductor device actually equipped with the semiconductor chip package of the present invention is, for example, provided for use in electrical products (for example, computers, mobile phones, smart phones, tablet-type devices, wearable devices, digital devices, etc.) Various semiconductor devices such as cameras, medical equipment, and televisions, etc.) and vehicles (such as locomotives, automobiles, trains, ships, and aircraft, etc.). [Example]

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited by these examples. In addition, in the following description, "part" and "%" of "amount" mean "part by mass" and "% by mass", respectively, unless otherwise specified.

[Synthesis Example 1: Synthesis of Synthetic Resin 1] Bifunctional hydroxyl-terminated polybutadiene (G-3000, manufactured by Nippon Soda Co., Ltd., number average molecular weight=3000, hydroxyl equivalent=1800g/eq.) was made into a reaction vessel 69 g, mixed with 40 g of IPUZOURU 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Kosan Co., Ltd.) and 0.005 g of dibutyltin lauryl, and dissolved uniformly. After forming a homogeneous state, the temperature was raised to 50° C., and 8 g of isophorone diisocyanate (manufactured by Evonik Degussa Japan, IPDI, isocyanate group equivalent = 113 g/eq.) was added while stirring, and the reaction was carried out for about 3 hours. Next, the reactant was cooled to room temperature, and 23 g of cresol-novolac resin (KA-1160, manufactured by DIC Corporation, hydroxyl equivalent = 117 g/eq.) was mixed with ethyl diethylene glycol acetate (produced by DAICEL Corporation). ) 60g was added therein, the temperature was raised to 80°C while stirring, and the reaction was carried out for about 4 hours. Use FT-IR to confirm whether the NCO peak at 2250cm ^-1 disappears. When the NCO peak disappears, it is regarded as the end of the reaction. After the reactant is cooled to room temperature, it is filtered through a 100-mesh filter cloth to obtain a synthetic resin 1 with a butadiene structure and a phenolic hydroxyl group (containing a phenolic hydroxyl group) Butadiene resin: solid content 50% by mass). The number average molecular weight was 5500.

[Example 1] Epoxy resin ("ZX1059" manufactured by Nippon Steel Sumitomo Metal Chemical Co., Ltd., a 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g/eq) 10 parts, biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 269) 41 parts, amphiphilic polyether block copolymer ("Fortegra 100" manufactured by Dow Chemical Co.) 3 parts, 380 parts of spherical silica (average particle size 0.5 μm, “SO-C2” manufactured by ADMATECHS Co., Ltd.) surface-treated with an anilinosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), phenol-novolac Resin (MEK solution with a phenolic hydroxyl equivalent of 105, "TD2090-60M" manufactured by DIC Corporation with a solid content of 60% by mass) 8.3 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, cyclohexanone with a solid content of 30% by mass) : 16.6 parts of methyl ethyl ketone (MEK) 1:1 solution), 30 parts of methyl ethyl ketone, 0.3 parts of imidazole-based hardening accelerator (manufactured by Shikoku Chemicals Co., Ltd. "1B2PZ"), mix and disperse evenly with a high-speed rotary mixer , and made the resin coating 1.

[Example 2] In Example 1, 41 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 269) were changed to pernaphthyl ether type epoxy resin ("EXA" manufactured by DIC Corporation). -7311", epoxy equivalent 277) 41 parts, phenol-novolak resin (phenolic hydroxyl equivalent 105, DIC company "TD2090-60M" solid content 60 mass % MEK solution) 8.3 parts, changed to active ester compound ( "HPC-8000-65T" manufactured by DIC Co., Ltd., 7.7 parts of a toluene solution with an active group equivalent of about 223 and a solid content of 65% by mass. Resin coating 2 was prepared in the same manner as in Example 1 except for the above.

骨架之酚樹脂(DIC公司製「LA-3018-50P」羥基當量151之固形成份50質量%之丙二醇單甲醚溶液)10份。除以上事項以外，其他皆依與實施例1相同之方法製得樹脂塗料3。[Example 3] In Example 1, 41 parts of a biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 269) was changed to a novolak type epoxy resin ("157S70" manufactured by Mitsubishi Chemical Corporation) "Epoxy equivalent 200-220) 41 parts, phenol-novolak resin (phenolic hydroxyl equivalent 105, DIC company "TD2090-60M" solid content 60 mass % MEK solution) 8.3 parts, changed to contain three

10 parts of phenolic resin of the skeleton ("LA-3018-50P" manufactured by DIC Corporation, 50% by mass of propylene glycol monomethyl ether solution with a hydroxyl equivalent of 151 and a solid content of 50 mass%). Resin coating 3 was prepared in the same manner as in Example 1 except for the above.

[Example 4] In Example 2, 6 parts of a carbodiimide compound ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution with a carbodiimide equivalent of 216 and a nonvolatile content of 50% by mass) was added. Except for the above matters, the resin coating 4 was obtained by the same method as in Example 2.

骨架之酚樹脂(DIC公司製「LA-3018-50P」羥基當量151之固形成份50質量%之丙二醇單甲醚溶液)10份，變更為活性酯化合物(DIC公司製「HPC-8000-65T」活性基當量約223之固形成份65質量%之甲苯溶液)7.7份、 　　2)加入合成例1所合成之合成樹脂1 10份、 　　3)加入碳二醯亞胺化合物(日清紡化學公司製「V-03」碳二醯亞胺當量216、不揮發成份50質量%之甲苯溶液)6份、 　　4)不加入苯氧基樹脂(三菱化學公司製「YX7553BH30」、固形成份30質量%之環己酮：甲基乙酮(MEK)之1：1溶液)。 　　除以上事項以外，其他皆依與實施例3相同之方法製得樹脂塗料5。[Example 5] In Example 3, 1) will contain three

10 parts of the phenolic resin of the skeleton ("LA-3018-50P" manufactured by DIC Corporation, a 50% by mass propylene glycol monomethyl ether solution with a hydroxyl equivalent of 151 and a solid content of 151) was changed to an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation) 7.7 parts of a solid content of 65 mass % toluene solution with an active group equivalent of about 223), 2) adding 10 parts of the synthetic resin synthesized in Synthesis Example 1, 3) adding a carbodiimide compound (manufactured by Nisshinbo Chemical Co., Ltd. "V- 03" 6 parts of toluene solution with carbodiimide equivalent of 216 and non-volatile content of 50% by mass, 4) Cyclohexanone without adding phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, solid content of 30% by mass): 1:1 solution of methyl ethyl ketone (MEK). Resin coating 5 was prepared in the same manner as in Example 3 except for the above.

[Example 6] In Example 1, the amphiphilic polyether block copolymer ("Fortegra 100" manufactured by Dow Chemical Co. was changed from 3 parts to 6 parts), and the phenol-novolak resin (phenolic hydroxyl equivalent 105, DIC "TD2090-60M" manufactured by the company "MEK solution with solid content of 60% by mass") 8.3 parts, changed to an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation with an active group equivalent of about 223 Toluene solution with a solid content of 65% by mass) 7.7 parts. Except above-mentioned matter, other all make resin coating 6 according to the method identical with embodiment 1.

[Example 7] In Example 1, the amount of the amphiphilic polyether block copolymer ("Fortegra 100" manufactured by Dow Chemical Co.) was changed from 3 parts to 9 parts, and the phenol-novolac resin (phenolic hydroxyl equivalent 105. 8.3 parts of "TD2090-60M" MEK solution with solid content of 60% by mass manufactured by DIC Corporation) was changed to an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation with an active group equivalent of about 223 and a solid content of 65% by mass) Toluene solution) 7.7 parts. Except for the above matters, the resin coating 7 was obtained by the same method as in Example 1.

骨架之酚樹脂(DIC公司製「LA-3018-50P」羥基當量151之固形成份50質量%之丙二醇單甲醚溶液)10份，變更為酚-酚醛清漆樹脂(酚性羥基當量105、DIC公司製「TD2090-60M」之固形成份60質量%之MEK溶液)8.3份。除以上事項以外，其他皆依與實施例3相同之方法製得樹脂塗料8。[Example 8] In Example 3, spherical silica (average particle size 0.5 μm, ADMATECHS "SO-C2" produced by ADMATECHS Co. ) 380 parts, changed to 450 parts of alumina ("DAW-03" manufactured by Denka Corporation, average particle size 3.7 μm) surface-treated with an anilinosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), containing three

10 parts of the phenolic resin of the skeleton ("LA-3018-50P" produced by DIC Corporation, a solid content of 50% by mass of propylene glycol monomethyl ether solution with a hydroxyl equivalent of 151) was changed to a phenol-novolak resin (a phenolic hydroxyl equivalent of 105, DIC Corporation Prepare 8.3 parts of "TD2090-60M" MEK solution with a solid content of 60% by mass). Except for the above matters, the resin coating 8 was obtained by the same method as in Example 3.

[Example 9] In Example 2, 3 parts of the amphiphilic polyether block copolymer (manufactured by Dow Chemical Co. "Fortegra 100") was changed to 6 parts, and an anilinosilane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd. "KBM573") surface-treated spherical silica (average particle size: 0.5 μm, "SO-C2" manufactured by ADMATECHS Co., Ltd.) was changed from 380 parts to 300 parts. 7.7 parts of a toluene solution with an active group equivalent of about 223 and a solid content of 65% by mass) was changed to a phenol-novolak resin (a MEK solution with a solid content of 60% by mass of "TD2090-60M" manufactured by DIC Corporation with a phenolic hydroxyl equivalent of 105) 8.3 servings. Resin coating 9 was prepared in the same manner as in Example 2 except for the exception.

[Example 10] In Example 9, spherical silica (average particle size 0.5 μm, ADMATECHS "SO-C2" produced by ADMATECHS Co., Ltd.) surface-treated ) is changed from 300 to 250. Except for the exception, the resin coating 10 was obtained in the same manner as in Example 9.

[Example 11] In Example 3, 41 parts of novolak-type epoxy resin (Mitsubishi Chemical Corporation "157S70" epoxy equivalent 200-220) were changed to pernaphthylether-type epoxy resin (DIC Corporation "EXA -7311", 41 parts of epoxy equivalent 277), and 4 parts of core-shell rubber particles (manufactured by Kanz Chemical Co., Ltd. "AC3832"). Except for the above matters, the resin coating 11 was obtained by the same method as in Example 3.

[Example 12] In Example 10, spherical silica (average particle size 0.5 μm, ADMATECHS "SO-C2" produced by ADMATECHS Co., Ltd.) surface-treated ) was changed to 250 parts of fused spherical silica ("FB-105FD" manufactured by Denka Corporation with an average particle size of 11.7 μm) surface-treated with an anilinosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.). Except for the above matters, the resin coating 12 was prepared by the same method as in Example 10.

[Comparative Example 1] In Example 4, 1) no amphiphilic polyether block copolymer ("Fortegra 100" manufactured by Dow Chemical Co.), 2) a perynalyl ether type epoxy resin ("EXA -7311", 41 parts of epoxy equivalent 277), changed to 41 parts of novolac type epoxy resin ("157S70" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 200 to 220). Except above-mentioned matter, other all make resin coating 13 according to the method identical with embodiment 4.

<Measurement of curing shrinkage> (1-1) Manufacture of resin-coated polyimide film The resin coatings obtained in Examples and Comparative Examples were used so that the thickness of the resin composition layer after drying was 170 μm. Slit coater coating on a PET film ("LUMMIOR R80" manufactured by Toray Co., Ltd., thickness 38 μm, softening point 130°C) treated with an alkyd resin-based release agent ("AL-5" manufactured by Linde Corporation) , Hereinafter, also referred to as "release PET"), after drying at 80°C to 120°C (average 100°C) for 10 minutes, a resin sheet was obtained. Cut the resin sheet into a 200mm square sample. The obtained resin sheet (200 mm square) was bonded to a polyimide film ( Single-sided lamination was carried out in the center of the smooth surface of Upilex 25S manufactured by Ube Industries, 25 μm thick, 240 mm square). The method of lamination is to carry out depressurization for 30 seconds to make the air pressure below 13hPa, and then carry out pressing at 100°C and a pressure of 0.74MPa for 30 seconds. In this way, a polyimide film with resin is obtained.

(1-2) Determination of the initial length The prepared polyimide film with resin is placed on the release PET of the resin sheet, at a part of about 20mm from the 4 corners of the resin composition layer, using a punching machine. The hole machine forms 4 (each hole is clockwise, tentatively called A, B, C, D) through holes (about 6 mm in diameter), and after peeling the resin sheet from the support, use a non-contact image measuring device (manufactured by Mitutoyo Co., Ltd.) , Quick Vision, "QVH1X606-PRO III_BHU2G") to measure the length L ( _LAB , _LBC , _LCD , _LDA , _LAC , _LBD ) of the central part of each hole formed (as shown in Figure 2) .

(1-3) Thermal hardening of the resin composition layer. The polyimide film surface of the polyimide film with resin after the length measurement is completed is set on a glass cloth base epoxy resin with a size of 255mm×255mm. Copper-clad laminates on both sides (0.7mm thick, "R5715ES" manufactured by Matsushita Electric Works Co., Ltd.), fixed on four sides with polyimide adhesive tape (10mm wide), heated at 180°C for 90 minutes to harden the resin composition layer , to obtain a hardened layer.

(1-4) Measurement of thermal curing shrinkage rate After thermal curing, the polyimide adhesive tape is peeled off, and the polyimide film with the hardened layer is peeled off from the laminate, and then the hardened layer is removed from the laminate. Peel off the polyimide film, and use a non-contact image measuring device to measure the length L'(L' _AB , L' _BC , L' _CD , L' _DA , L' _AC , L' _BD ).

The length L _AB between the hole A and the hole B and the shrinkage rate s1 _AB after curing can be obtained according to the following formula (1). _The shrinkage ratios s1 _BC , s1 _CD , _s1 DA , s1 AC and s1 _DA of L _BC , _LCD , L _DA , L _AC and L _BD after hardening were also obtained by the same method.

The thermosetting shrinkage rate of the cured product layer can be calculated according to the following formula (2). Thermal hardening shrinkage [shrinkage in the xy direction: S1] (%)

<Warpage Test> The resin coatings prepared in Examples and Comparative Examples were coated on release PET with a slit coater in such a way that the thickness of the dried resin composition layer reached 170 μm. ~120°C (average 100°C), after drying for 10 minutes, a resin sheet was obtained. This resin sheet was laminated by using a batch-type vacuum pressure laminator (MVLP-500 manufactured by Meiki Co., Ltd.) on a SUS304 board with a thickness of 0.2 mm and a thickness of 15 cm×30 cm so that the resin composition layer was connected. For lamination, the pressure was reduced to 13 hPa or less for 30 seconds, followed by pressing at 100° C. and a pressure of 0.74 MPa for 30 seconds. The release PET from which the laminated resin sheet was removed was heat cured at 180° C. for 90 minutes to prepare a sample for warpage evaluation. The surface of the obtained sample for warpage evaluation, on which the convex portion is formed in the central part, is placed on the smooth table in a manner facing downward, and the distance between the smooth table and the sample for warpage evaluation is measured as the maximum distance. Amount of warpage. When the absolute value of warpage is less than 10 mm, it is marked as ○, when it is more than 10 mm, and less than 20 mm, it is marked as △, and when it is more than 20 mm, it is marked as ×.

<Measurement of Average Linear Thermal Expansion Coefficient (Thermal Expansion Coefficient)> The resin coatings prepared in Examples and Comparative Examples were coated on a separator using a slit coater so that the thickness of the dried resin composition layer was 170 μm. Type PET, drying at 80°C to 120°C (average 100°C) for 10 minutes to obtain a resin sheet. The obtained resin sheet was fixed to the four sides of a double-sided copper-clad laminate of glass cloth base material epoxy resin using polyimide adhesive tape, and was thermally cured at 180° C. for 90 minutes. Then the release PET is peeled off from the resin composition layer to obtain a flake-shaped cured product. Thin flake-shaped cured products are called hardened products for evaluation. The obtained cured product for evaluation was cut into test pieces with a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by the tensile weight method using a thermomechanical analysis device ("Thermo Plus TMA8310" manufactured by Rike Corporation). In detail, after installing the test piece in the aforementioned thermomechanical analyzer, measurement was performed with a load of 1 g and a heating rate of 5° C./min. Under the same conditions, two consecutive measurements were performed. Then, in the second measurement, the average linear thermal expansion coefficient (α1; ppm/°C) in the plane direction was calculated in the range from 30°C to 150°C. This operation was repeated 3 times, and the average values obtained are shown in the table.

<Measurement of thermal conductivity of cured product> (1) Manufacture of cured product The resin coatings obtained in Examples and Comparative Examples were coated with a slit coater so that the thickness of the resin composition layer after drying was 150 μm. Spread it on the release PET, and dry it at 80°C-120°C (average 100°C) for 10 minutes to obtain a resin sheet. Two of the obtained resin sheets were laminated so that the layers of the resin composition were connected using a batch type vacuum pressure laminator (manufactured by Meiki Co., Ltd., MVLP-500), to obtain a resin sheet with a thickness of 300 μm. The release PET on one side of the obtained resin sheet was peeled off, fixed to the four sides of the glass cloth substrate epoxy resin double-sided copper-clad laminate with polyimide adhesive tape, and heat-cured at 180°C for 90 minutes. Then the release PET on the other side is peeled off from the resin composition layer to obtain a flake-shaped hardened product.

(2) Measurement of thermal diffusivity α For a thin sheet-shaped cured product, "ai-Phase Mobile 1u" manufactured by ai-Phase Co., Ltd. was used to measure thermal diffusivity α (m ² ) in the thickness direction of the cured product by the temperature wave analysis method /s). The same sample was measured three times, and the average value was calculated.

(3) Measurement of specific heat capacity Cp For thin flake-shaped hardened products, use a differential scanning calorimeter ("DSC7020" manufactured by SII Nanotechnology Co., Ltd.) to raise the temperature from -40°C to 80°C at 10°C/min. From the measurement results up to ℃, calculate the specific heat capacity Cp (J/kg・K) of the flaky cured product at 20℃.

(4) Measurement of density ρ The density (kg/m ³ ) of the flake-shaped cured product was measured using an analytical balance XP105 manufactured by Mettler Toled (used in a specific gravity measurement kit).

(5) Calculation of thermal conductivity λ, the thermal diffusivity α (m ² /s), specific heat capacity Cp (J/kg・K), and density ρ (kg/m ³ ) obtained from the above (2) to (4) , into the following formula (I) to calculate the thermal conductivity λ (W/m·K).

<Measurement of the tensile peel strength (peel strength) of the metal layer and the surface roughness (Ra) of the surface of the insulating layer after the roughening treatment> (1) Underlayer treatment of the inner layer circuit board The glass on which the inner layer circuit is formed Both sides of the double-sided copper-clad laminate of cloth-based epoxy resin (copper foil thickness 18 μm, substrate thickness 0.3 mm, PANASONIC R5715ES) were dipped in CZ8100 made by Merck to roughen the copper surface.

(2) Lamination of resin sheets The resin coatings prepared in Examples and Comparative Examples were coated on release PET with a slit coater so that the thickness of the dried resin composition layer was 200 μm. Dry at 80°C to 120°C (average 100°C) for 10 minutes to obtain a resin sheet. The resin sheet was laminated using a batch type vacuum pressure laminator (MVLP-500, manufactured by Meiki Co., Ltd.) so that both sides of the inner circuit board were connected to the resin composition layer. For lamination, the pressure was reduced to 13 hPa or less for 30 seconds, and then pressed at 100° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Hardening of the resin composition layer The laminated resin sheet is peeled off from the release PET, and the resin composition layer is hardened at 180°C for 30 minutes to form an insulating layer.

(4) Grinding of the insulating layer The insulating layer of the inner circuit substrate forming the insulating layer is ground and cut using a flat grinding disc under the following conditions. Grinding and cutting conditions: Abrasive grain peripheral speed 500m/min, platform speed 13m/min, 1 cut-in amount 3μm, total cutting thickness 50μm, abrasive grain number #1000

(5) Roughening treatment The surface of the insulating layer after grinding is soaked at 60°C for 5 minutes using "Swelling Dip Securiganth P" manufactured by ATOTETCH Corporation of Japan as a swelling solution, and then used As a roughening solution, "Concentrate Compact P" (KMnO ₄ : 60g/L, NaOH: 40g/L aqueous solution) manufactured by Japan ATOTETCH Co., Ltd. was immersed at 80°C for 15 minutes, and finally immersed at 40°C in "Reduction Solution Security Gant P" manufactured by ATOTETCH Co., Ltd., Japan, for 5 minutes. This substrate was used as a substrate A for evaluation.

(6) Plating using the semi-additive process (Semi-Additive Process) In order to form a circuit on the surface of the insulating layer, the inner circuit substrate is immersed in an electroless plating solution containing PdCl ₂ , and then immersed in electroless copper in the bath. Heating at 150°C for 30 minutes, annealing, forming an etch resist, patterning by etching, copper sulfate electroplating, and forming a plated conductor layer with a thickness of 30±5 μm. Next, tempering treatment was carried out at 180° C. for 60 minutes. This circuit board was used as a board B for evaluation.

(7) Measurement of the tensile peel strength (peel strength) of the metal layer Cut the conductor layer of the evaluation substrate B into a part with a width of 10mm and a length of 100mm, peel off one end and clamp it with a jig, and measure it at room temperature , the load (kgf/cm) when stretching and peeling 35mm from the vertical direction at a speed of 50mm/min.

(8) Measurement of the surface roughness (Ra) of the surface of the insulating layer after the roughening treatment. The surface of the insulating layer of the evaluation substrate A was measured using a non-contact surface roughness meter (WYKO NT3300 manufactured by VEECO Corporation) in the VSI contact mode. . Use a 50x lens to measure the measurement range of 121 μm × 92 μm, and obtain the surface roughness of the surface of the insulating layer after roughening treatment. Obtain the average value of 10 different points to determine Ra.

In the manufacture of the resin compositions of Examples and Comparative Examples, the components used and their addition amounts (parts by mass, solid content conversion) are shown in the following table. In addition, the description etc. in the following table|surface are as follows. Content of (D) component (mass %): when the non-volatile content of the resin composition is 100 mass%, the content of (D) component (B) content (mass %): non-volatile content of the resin composition Content of component (B) when the component is set to 100% by mass

It was confirmed that in each example, even when the components (E) to (I) were not contained, the example with a degree of difference was the same as the above-mentioned example, and it was confirmed that the same result was assigned.

100‧‧‧semiconductor chip package 110‧‧‧semiconductor chip 120‧‧‧sealing layer 130‧‧‧rewiring forming layer (insulating layer) 140‧‧‧conducting layer (rewiring layer) 150‧‧‧solder resist layer 160‧‧‧bumps

[ Fig. 1] Fig. 1 is a schematic cross-sectional view showing an example of a semiconductor chip package (Fan-out type WLP) of the present invention. [Fig. 2] Fig. 2 is a schematic diagram illustrating an example of a resin sheet when measuring curing shrinkage.

Claims (20)

A resin composition characterized by comprising: (A) epoxy resin, (B) inorganic filler, (C) hardener, and (D) amphiphilic polyether block copolymer, and (B) component The average particle size is not less than 0.01 μm and not more than 10 μm, and the absolute value of the warpage of the cured product after the resin composition is thermally cured at 180°C for 30 minutes is less than 20 mm. A resin composition characterized by comprising: (A) epoxy resin, (B) inorganic filler, (C) hardener, and (D) amphiphilic polyether block copolymer, and (B) component The average particle size is not less than 0.01 μm and not more than 10 μm, and the curing shrinkage of the cured product after the resin composition is thermally cured at 180°C for 90 minutes is not more than 0.27%. A resin composition characterized by comprising: (A) epoxy resin, (B) inorganic filler, (C) hardener, and (D) Amphiphilic polyether block copolymer, and the average particle diameter of component (B) is not less than 0.01 μm and not more than 10 μm, and the content of component (D) is set to 100 mass of non-volatile components in the resin composition %, it is not less than 0.3% by mass and not more than 15% by mass. The resin composition according to any one of claims 1 to 3, wherein the content of the component (B) is not less than 50% by mass and not more than 95% by mass when the non-volatile content in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 3, wherein component (B) is treated with a silane coupling agent containing nitrogen atoms. The resin composition according to claim 1 or 2, wherein the content of component (D) is not less than 0.3% by mass and not more than 15% by mass when the non-volatile content in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 3, wherein, component (D) contains at least one epoxy resin mixed polyether block segment, and at least one epoxy resin non-mixed polyether block segment Segment-segment block copolymers. As the resin composition of claim item 7, wherein, the epoxy resin mixed polyether block segment is composed of polyethylene oxide block, polypropylene oxide block, poly(ethylene oxide-co-ring Propylene oxide) blocks, poly(ethylene oxide-ran-propylene oxide) blocks, and mixtures of these selected from one or more polyalkylene oxide blocks Segment; Epoxy resin immiscible polyether block segment is selected from polybutylene oxide block, polyhexene oxide block, polydodecane oxide block, and the mixture of these One or more polyalkylene oxide blocks. The resin composition according to any one of claims 1 to 3, which further contains (E) a carbodiimide compound. The resin composition according to any one of claims 1 to 3, which further contains (F) thermoplastic resin. Such as the resin composition of any one of claims 1 to 3, wherein the component (C) is composed of three

One or more selected phenolic hardeners and active ester hardeners. The resin composition according to any one of claims 1 to 3, wherein component (A) is an epoxy resin containing a condensed ring-containing structure. The resin composition according to claim 1 or 3, wherein the hardening shrinkage rate of the cured product after the resin composition is heat-cured at 180°C for 90 minutes is 0.27% or less. The resin composition according to any one of claims 1 to 3, wherein the temperature of the hardened product after the resin composition is cured at 180°C for 90 minutes is between 25°C and 150°C The linear thermal expansion coefficient is above 3ppm/°C and below 30ppm/°C. The resin composition according to any one of claims 1 to 3, which is a resin composition for an insulating layer of a semiconductor chip package. The resin composition according to any one of claims 1 to 3, which is a resin composition for an insulating layer of a circuit substrate formed by using a semi-additive process (Semi-Additive Process). A resin sheet characterized by comprising: a support body, and a resin composition layer of any one of claims 1 to 16 provided on the support body. A circuit board characterized by comprising: an insulating layer formed of a hardened resin composition according to any one of claims 1 to 16. A semiconductor chip package, characterized by comprising: the circuit substrate of claim 18, and a semiconductor chip mounted on the circuit substrate. A semiconductor chip package, characterized by comprising: a semiconductor chip sealed by the resin composition of any one of claims 1 to 16 or the resin sheet of claim 17.

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